(Fortschritte Der Chemie Organischer Naturstoffe - Progress in The Chemistry of Organic Natural Products 81) S. Huneck (Auth.), Prof. W. Herz, Prof. H. Falk, Prof. G. W. Kirby, Prof. R. E. Moore (Eds.

81
Fortschritte der Chemie

organischer Naturstoffe
Progress in the
Chemistry of Organic
Natural Products
Founded by
L. Zechmeister
Edited by
W. Herz, H. Falk,
G. W Kirby, and R. E. Moore
Author:
S. Huneck
Springer-Verlag Wien GmbH

Prof. W. Herz, Department of Chemistry,
The Florida State University, Tallahassee, Florida, U. S. A.
Prof. H. Falk, Institut für Chemie,

Johannes-Kepler-Universität, Linz, Austria
Prof. G. W. Kirby, Chemistry Department,

The University of Glasgow, Glasgow, Scotland
Prof. R. E. Moore, Department of Chemistry,

University of Hawaii at Manoa, Honolulu, Hawaii, U. S. A.
This work is subject to copyright.

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© 2001 by Springer-Verlag Wien

Originally published by Springer-Verlag Wien New York 2001
Softcover reprint ofthe hardcover 1st edition 2001
Library of Congress Catalog Card Number AC 39-1015
Typesetting: Scientific Publishing Services (P) Ltd., Madras
Printed on acid-free and chlorine-free bleached paper
SPIN: 10774546
With 11 Figures
ISSN 0071-7886
ISBN 978-3-7091-7249-0 ISBN 978-3-7091-6196-8 (eBook)
DOI 10.1007/978-3-7091-6196-8
Contents
List of Contributors VIII
New Results on the Chemistry of Lichen Substances

By S. Huneck .
Abbre viations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
I. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. Methods for Identification and Structure Elucidation of Lichen Substances . . . . 5

2.1. Spot Tests 5
2.2. Thin Layer Chromatography (TLC) . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
2.3. High Performance Liquid Chromatography (HPLC) 6
2.4. Droplet Counter-Current Chromatography . . . . . . . . . . . . . . . . . . . . .. 7
2.5. NMR Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 7
2.6. Mass Spectrometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 9
2.7. X-ray Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 10
2.8. Cathodoluminescence and X-ray Microanalysis . . . . . . . . . . . . . . . . . .. 10
2.9. Laser Microprobe Mass Spectrometry (LAMMA) . . . . . . . . . . . . . . . .. 10
2.10. Fluorescence Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 12
2.11. Computer Program for Identification of Lichen Subst ances
(WINTABOLITES) 12
3. General Methods for Derivatization and Regeneration of Lichen Substances . .. 12

3.1. Carboxyl Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 12
3.1.1. Meth ylation 12
3.1.2. Benzylation and Debenzylation 13
3.1.3. Carboxylation and Decarboxylation 14
3.2. Alcoholic and Phenolic Groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 15
3.2.1. Acetylation . . . . . . . . . . . . . . . . . . . ...................... 15
3.2.2. Methylation and Demethylation . . . . . . . . . . . . . . . . . . . . . . . . .. 15
3.2.3. Isopropylation and Deisopropylation 16
3.2.4. Benzylatio n and Debenzylation 16
3.2.5. Oxidation of Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 16
3.3. Substitution at Aromatic Rings. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 17
3.3.1. Halogenation and Dehalogenation 17
3.3.2. Hydroxylation 17
3.4. Synthesis of Aldehydes 18
3.4.1. Reduction of Aldehydes . . . . . . . . . . ...................... 18
VI Contents
3.4.2. Oxidation of Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

3.5. Cleavage and Formation of the Depside Ester Bond 19
4. Structure Elucidation and Synthesis of Lichen Substances . . . . . . . . . . . . . . . . 21

4.1. Nitrogen Containing Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 21
4.2. Phosphorus Cont aining Compounds . . . . . . . . . . . . . . . ............. 26
4.3. Polyols, Mono- and Polysaccharides and Carbohydrates 26
4.4. Aliphatic and Cycloaliphatic Compounds . . . . . . . . . . . ............. 28
4.4.1. Hydrocarbons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 28
4.4.2. Aliphatic Alcohols 28
4.4.3. Aliphatic Acids and Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 28
4.4.4. Aliphatic Tricarboxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . .. 32
4.4.5. y-Lactonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 33
4.4.6. Macrocyclic Lactones and Bis-Lactones . . . . . . . . . . . . . . . . . . . .. 42
4.4.6.1. Aspicilin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 42
4.4.6.2. Lepranthin 51
4.4.7. Anhydride s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 51
4.5. Aromati c Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 51
4.5.1. Aromatic Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
4.5.2. Biphenyls 76
4.5.3. Terphenyls 77
4.5.4. Diphenylmethanes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
4.5.5. Diphenyl Ethers (Pseudodepsidones) . . . . . . . . . . . . . . . . . . . . .. 80
4.5.6. Depsides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.5.7. Depsidone s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
4.5.8. Depsones 147
4.5.9. Chromanes and Chromones . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
4.5.10. Xanthones 151
4.5.11. Benzofurans 169
4.5.12. Dibenzofurans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
4.5.13. Usnic Acid and Related Compounds 178
4.5.14. Naphthopyrans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 186
4.5.15. Quinone s 186
4.5.15.1. Benzofuranoquinones and Benzoquinones 186
4.5.15.2. Naphthaquinones and bis-Naphthaquinones . . . . . . . . .. 187
4.5.15.3. Anthraquinones . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 190
4.5.15.4. Phenanthroquinones . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
4.5.15.5. Phenanthroperylenequinones . . . . . . . . . . . . . . . . . . . . . 194
4.5.15.6. Perylenequinones . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 195
4.5.16. Pulvinic Acid Derivatives. . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 195
4.6. Terpenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 199
4.6.1. Monoterpenoids 199
4.6.2. Sesquiterpenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
4.6.3. Diterpenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 199
4.6.4. Sesterterpenoids 199
4.6.5. Triterpenoids 206
4.6.6. Steroids 211
4.6.7. Carotenoids 214
Contents VII
5. Cultu re and Chemi stry of Lichen Symbionts and Cell Culture of Lichens . . . . . 216
5.1. Culture of Mycobionts 216
5.2. Lichen Tissue Cultures and their Met abo lites 216
5.3. Culture of Lichen Phycobionts 2 17
5.4. Metabolites from Lichen Phycobiont s . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
6. Biosynt hesis of Lichen Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
7. Chemotaxonom y of Lichens " 221
8. Biological Activities of Lichen Substances and Lichens . . . . . . . . . . . . . . . . . . 224

8.1. Activity again st Microorganisms 224
8.1.1. Antiviral Activity 224
8.1.2. Activity Against Bacteria an d Fungi . . . . . . . . . . . . . . . . . . . . . .. 224
8.2. Activity Against Algae 226
8.3. Activity on Bryop hytes . . . . . . . . . ............................ 226
8.4. Activity on Higher Plants 226
8.5. Activi ty on Animals .. ............................ 228
8.6. Activity on Ma n . . . . . . . . . . . . . . ............................ 228
8.7. Tumour and Anti-Tumour Activity 229
8.8. Inhibition of Enzymes . . . . . . . . . . ............................ 229
8.9. Antioxydant Activity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 230
9. Harmful Effects of Lichens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
10. Commercial Uses of Lichens and Lichen Substances . . . . . . . . . . . . . . . . . .. 230

10.1. Uses in Perfume Prod uction and in Cosmetic s 230
10.2. Lichens as Biomonito rs 230
'10.3. Lichens for Dyeing 230
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
Notes Added in Proof . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231
References 239
Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277

Subject Index 291
List of Contributors
S. Huneck , Fliederweg 34a, D-06179 Langenbogen/Saalkreis, Germany

New Results on the Chemistry
of Lichen Substances
S. Huneck
Fliederweg 34a, LangenbogenjSaalkreis, Germany
Contents
Abbreviations 4
I. Introduction 4
2. Methods for Identification and Structure Elucida tion of Lichen Substances . . . 5

2.1. Spot Tests 5
2.2. Thin Layer Chrom atog raphy (TLC) 6
2.3. High Performan ce Liquid Chromatograph y (HPLC) 6
2.4. Droplet Count er-Current Chromatography 7
2.5. NMR Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
2.6. Mass Spectrometry 9
2.7. X-ray Analysis 10
2.8. Cathodoluminescence and X-ray Microanalysis 10
2.9. Laser Microprobe Mass Spectromet ry (LAMMA) .......... 10
2.10. Fluorescence Microscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
2.11. Computer Progr am for Identification of Lichen Substances
(WINTABOLITES) 12
3. General Methods for Derivati zation and Regeneration of Lichen Substances . . 12

3.1. Carbox yl Group s 12
3.1.1. Methylation 12
3.1.3. Carb oxylation and Decarb oxylation 14
3.2. Alcoholic and Phenolic Groups 15
3.2.1. Acetylation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 15
3.2.2. Methylation and Demethylation . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.3. Isoprop ylation and Deisoprop ylation 16
3.2.5. Oxidation of Alcohols 16
S. Huneck, Fortschritte der Chemie organischer Nuturstoffe

© Springer-Verlag Wien 2001
2 S. Hun eck
3.3. Substitution at Aro matic Rings 17

3.3.1. Halogenation and Dehalogenation 17
3.3.2. Hydroxylat ion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 17
3.4. Synthesis of Aldehydes 18
3.4.1. Reduction of Aldehydes . . . . . . . . . . . .................... \8
3.4.2. Oxidation of Aldehydes . . . . . . . . . . . .................... \9
3.5. Cleavage and Fo rmat ion of the Depside Ester Bond 19
4. Structure Elucidati on and Synthesis of Lichen Substances . . . . . . . . . . . . . .. 21

4. 1. Nitrogen Conta ining Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 21
4.2. Phosphoru s Co ntaining Compounds . . . . . . . . . . . . . . . . . . . . . . . . . .. 26
4.3. Polyols, Mono- and Polysaccharides and Ca rbohydra tes 26
4.4. Alipha tic and Cycloaliphatic Compounds . . . . . . . . . . . . . . . . . . . . . .. 28
4.4.1. Hydrocarb ons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 28
4.4.2. Aliphat ic Alcohols . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 28
4.4.3. Aliphatic Acids and Esters . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 28
4.4.4. Aliphat ic Tr icarb oxylic Acids . . . . . . . . . . . . . . . . . . . . . . . . . .. 32
4.4.5. y-Lactonic Acids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 33
4.4.6. Macrocyclic Lactones and Bis-Lactones . . . . . . . . . . . . . . . . . . .. 42
4.4.6.1. Aspicilin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 42
4.4.6.2. Lepranth in 5\
4.4.7. Anh ydrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . ............ 5\
4.5. Aromatic Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5\
4.5.1. Aro matic Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 51
4.5.2. Biphenyls 76
4.5.3. Terph enyls 77
4.5.4. Diphenylmethanes . . .. . . . . . . . . . . . . . .. .. . . . . . . . . . . . . . 80
4.5.5. Diphenyl Ethers (Pseudodepsido nes) 80
4.5.6. Depsides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 84
4.5.7. Depsidones 127
4.5.8. Depsones 147
4.5.9. Chromanes and Chromo nes 150
4.5.10. Xant hones 15\
4.5.11. Benzofurans 169
4.5.12. Dibenzofurans . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
4.5.13. Usnic Acid and Related Compounds . . . . . . . . . . . . . . . . . . . .. 178
4.5.\4. Na phthopyran s 186
4.5.15. Quinones 186
4.5.15.1. Benzofur anoquin ones and Benzoquin ones 186
4.5.15.2. Naph thaquin ones and bis-Naphthaquin ones . . . . . . . .. 187
4.5.15.3. Anthra quinones . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
4.5.15.4. Phenan th roq uinones . . . . . . . . . . . . . . . . . . . . . . . . . . 194
4.5.15.5. Phenant hrop erylenequinones . . . . . . . . . . . . . . . . . . .. 194
4.5.15.6. Perylenequinones 195
4.5.\ 6. Pulvinic Acid Derivat ives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
4.6. Terpenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 199
4.6.1. Monoterpenoids 199
4.6.2. Sesquiterpenoids 199
New Results on the Chemistry of Lichen Substances 3
4.6.3. Diterpenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 199

4.6.4. Sesterterpenoids 199
4.6.5. Triterpenoids 206
4.6.6. Steroids 211
4.6.7. Carotenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
5. Culture and Chemistry of Lichen Syrnbionts and Cell Culture of Lichens . . .. 216
5.1. Culture of Mycobionts 216
5.2. Lichen Tissue Cultures and their Metabolites 216
5.3. Culture of Lichen Phycobionts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
5.4. Metabolites from Lichen Phycobionts . . . . . . . . . . . . . . . . . . . . . . . . .. 218
6. Biosynthesis of Lichen Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 218
7. Chemotaxonomy of Lichens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 221
8. Biological Activities of Lichen Substance s and Lichens . . . . . . . . . . . . . . . .. 224

8.1. Activit y against Microorganisms 224
8.1.1. Antiviral Activity 224
8.1.2. Activity Against Bacteria and F ungi 224
8.2. Activity Against Algae 226
8.3. Activity on Bryop hytes 226
8.4. Activity on Higher Plants 226
8.5. Activity on Anima ls 228
8.6. Activity on Man . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
8.7. Tumour and Anti -Tumo ur Activity 229
8.8. Inhibition of Enzymes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
8.9. Antioxydant Activit y . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
9. Harmful Effects of Lichens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
10. Commercial Uses of Lichens and Lichen Substances . . . . . . . . . . . . . . . . . . . 230

10.1. Uses in Perfume Production and in Cosmetics . . . . . . . . . . . . . . . . . . . 230
10.2. Lichens as Biomonitors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
10.3. Lichens for Dyeing ' . 230
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 231
Note s Added in Proof 231
References 239
4 S. Huneck
Abbreviations
The following abbreviations are used in this article: A = " Alcohol"

part of a depside, ABIBN=AIBN=2,2'-Azabisisobutyronitrile, Ac=
Acetyl, Bf'Oe-Benzoylpero xide, Bu-eButyl, Bn--Benzyl, Bze.Benzoyl,
CD 1= I, I' -Carbonyldiimidazole , CPBA=Chloroperoxybenzoic acid,
DBU = I,5-Diazabicyclo [5.4.0] undec-5-ene, DCBCI=2,5-Dichloro-
benzoylchloride, DCCD=Dicyclohexylcarbodiimide, DCDME=Di-
chlorodimethyl ether, DHP=3,4-Dihydro-2-H-pyran , DIBAH=DI-
BAL=Diisobutylaluminiumhydride , Dlf'Ae.Diisoprop ylamide , DiPy=
Dipyrid yl, DMl'Ae-Dimeth ylaminopyridine, DMF= Dimethylforma-
mide, DMS=Dimethylsulphate, DMSO=Dimethylsulfoxide, EE=
Ethoxyethyl, Et=Ethyl, HMA=HMTA=Hexamethylenetetramine,
HMDS=Hexamethyldisiiazide, HMPA=Hexamethylphosphoric acid
triamide, LAH=Lithiumaluminiumhydride, LDA=Lithiumdiisopropyl-
amine , MCPBA=m-Chloroperbenzoic acid, Mee Meth yl, MEM=
Methoxy-ethoxy-ethyl, MOM =Methoxymethyl, Mpe.Melting point,
MTPA=Methyl-a-trifluoromethoxy-phenylacetyl, NBS=N-Bromosuc-
cinimide , NCS=NCSI =N-Chlorosuccinimide, PCC =Pyridinium chloro-
chromate, PDC=Pyridinium dichromate, PDM=Phenyldiazomethane,
Phe Phenyl, PivePivaloyl, PPTS=Pyridinium-p-toluenesulphonate, Py=
Pyridine, RAMP=(R)-I-Amino-2-(methox ymeth yl)pyrrolizidine , RT=
Room temperature, S= "S iiure" part of a depside, SA=Sulfamic
acid, SAMP=(S)-I-mino-2-(methoxymeth yl)pyrr olizidine, TBA=
tert.-Butanol, TBDM =TBS=tert.-Butyldimeth ylsilyl, TBOK=K-tert.-
but ylate, 2,4,6,·TCB=2,4,6-Trichlorobenzoyl, TFA=Trifluoroacetic
acid, TFAA=Trifluoroacetic anhydride, TFE= Trifluoroethanol,
THF=Tetrahydrofuran, THP=Tetrahydropyran yl, TMDA = Tet rame-
thylenediamine, TMS =Trimethylsilyl, TPM =Triphenylmethyl, Ts=
Tosyl.
1. Introduction
Lichen chemistry continues to be a flourishing branch of natural
product chemistry . Since the last major review by Elix et al. in volume
35 of this series (274) man y new and interesting lichen substances ha ve
been isolated and synthesized. Thi s suggests that an upd ate is desirable .
As in the previous art icles new method s for structure elucidation and
synthesis, biosynth esis, chemo taxonomy and biological activities of
lichen substances will be discussed. Some other relatively recent
treatments of the subject need to be mentioned: A sho rt chapter by
Ref erences, pp . 239-276
Culberson and Elix (100) in Harborne's Methods in Plant Biochemistry

treated lichen constituents. Several minor reviews were published in
1984 (382), 1991 (385) and 1994 (386). Volume III of Galun's
Handbook of Lichenology (311) contains a chapter on chemical
constituents of lichens including secondary metabolic products, storage
products of lichens, carotenoids and phycobiliproteins.
Scholler's booklet on "Flechten" (640) deals with the history,
biology, systematics, ecology, protection and cultural significance of
lichens and contains numerous colourful photos. Two other popular
articles on lichens have been published by Sharnoff and Sharnoff (645)
and by Ahmadjian (5) who also discussed the problems of lichen
symbiosis (6). Huneck (388) gave a review on the significance of lichens
and their metabolites.
Like many other plants lichens are vanishing in many parts of the
world . The distribution of lichen-rich environments across the globe,
their conservation status in regional, national and international terms
and the threats from the environmental factors and human populations
have been discussed by Wolseley (736).
2. Methods for Identification and Structure Elucidation

A comprehensive review on the identification of lichen substances
has been presented by Huneck and Yoshimura (415). This book
contains chapters on extraction, purification, colour reactions, UV, IR,
NMR, MS, ORD, CD, microcrystallization, TLC, HPLC and deriv-
atization of lichen substances. All known compounds are listed with
their structure, melting point , spectroscopic properties and the corre-
sponding reference lichen.
2.1. Spot Tests
Para-phenylenediamine is an excellent reagent for detection of

an aldehyde group in a lichen substance . Its disadvantages are
instability and suspected carcinogenic activity . To overcome the
rapid oxidation of an alcoholic solution of p-phenylenediamine a
method for stabilizing the solution for at least one year by adding
disodium edetate (ethylenediamine tetraacetic disodium salt) has been
described (441) .
6 S. Huneck
2.2. Thin Layer Chromatography (TLC)
Thin layer chromatography is still the method of choice for rapidly

identifying lichen substances and is widely used by lichenologists and
lichen chemists. White and James (721) have published a guide to
microchemical techniques (including TLC) for identifying lichen sub-
stances . A standard method for TLC of lichen substances was reported
by Culberson et al. (89, 102) who published standardized R r values of
numerous lichen substances using a modified solvent system in which
diethyl ether is substituted by methyl tert.-butyl ether (MTBE)
(n-hexane:MTBE:formic acid = 140:72: 18). Wright (739) described a
simplified TLC method and Arup et al. (21) developed a method using
high performance thin layer chromatography (HPTLC) which has the
advantage of being more sensitive, of permitting the analysis of more
samples in a shorter period of time, and greatly reducing the amount of
solvent. A useful new solvent system (ethyl acetate:methanol:ammo-
nia = 75:20:5, VjVjV) for TLC of orcinol p-depsides using 3-methyl-2-
benzothiazolone hydrazone hydrochloride as spray reagent has been
described (16) and according to Ramaut et al. (607) the best solvent
system for the separation of atranorin and chloroatranorin is ben-
zene:dioxane:acetic acid in a rat io of90:25:4 (VjVjV, Pastuska mixture).
R r values of 39 lichen xanthones using ethyl acetate:cyclohexane 1:3 (Vj
V) and ethyl acetate:cyclohexane 1:1 (VjV) mixtures as solvent systems
have been listed (201). A catalogue of standardized TLC data has been
published (206).
2.3. High Performance Liquid Chromatography (HPLC)

High performance liquid chromatography is an ideal supplement of
or replacement for identification of lichen substances because it is more
sensitive and can be interpreted quantitatively. Applications of HPLC
in lichen chemistry are summarized in Table 1.
Culberson et al. (92) found that retention times of a homologous
series of orcinol depsides and phenolic units vary linearly with the
number of carbon atoms. When two or more homologs are known,
retention times of new members of the same series can be predicted
accurately. Combination of this method with other microchemical
techniques allows structural elucidation of depsides in small fragments
of lichens taken from herbarium vouchers.
Referen ces, pp. 239-276

Table 1. HPLC of lichen substances
Analyzed compounds, groups of compounds or lichen Ref.
Atranorin, vulpinic acid (673)

Depsides, depsidones (510)
Rhizocarpon superjiciale (322)
Different lichen substances (321)
Aromatic compounds from the genera Cladina and Cladonia (4/7)
Phenolic compounds from Cladina stellaris and C. rangiferina (4/6)
Aromatic compounds from the genus Cladina (4/9)
Aromatic compounds from the genus Cladonia, section Uncialis (420)
Aromatic compounds (4/8)
Aromatic compounds from the genus Cladonia, section Perviae (421)
Aromatic compounds from the genus Cladonia, section Cocciferae (422)
Aromatic compounds from the genus Cladonia, section Helopodium and (423)
subsection Foliosae
Extracts from Evernia prunastri (64/)
Lasallia brigantium, L. hispanica, L. pustulata (58/ ,583)
Aromatic compounds from the genus Cladonia, section Cladonia, group (424)
Furcatae
Aromatic compounds from the genera Cladina and Cladonia (426)
Sugars and Polyols (710)
Usnic acid (707)
Aromatic compounds from Ramalinasiliquosa (98)
Aromatic compounds from Usena diffracta (755)
Phenol carboxylic acids and depsides (479)
Aromatic lichen substances (29/, 752)
Aliphatic acids (393)
Depsides and depsidones from lichens of the family Umbilicariaceae (556)
(+)- and (-)-Usnic and isousnic acids (456)
Protolichesterinic acid, fumarprotocetraric acid (338)
Pulvinic acid derivatives (68)
2.4. Droplet Counter-Current Chromatography
Vulpinic acid has been separated from an extract of Letharia vulpina

by droplet counter-current chromatography using methanol:acetone:n-
heptane 4:1:5 (V/V/V) (178).
2.5. NMR Spectroscopy
tH_ and 13C-NMR spectroscopy and the corresponding special

techniques are of unique importance in structure elucidation of natural
products and are widely used in lichen chemistry. For example Gagnaire
et al. (309) and Gagnaire and Vincendon (3/0) have discussed the NMR
8 S. Huneck
retention index
2000 Superlatolic
1800 Hyperlatolic
1600 Perlatolic acid

1400 Stenosporic
1200 Divaricatic
I I i i i
6 8 10 12 14 number of sidechain
C atoms
Fig. 1. Linear relationship of retention index and number of sidechain carbons in depsides
spectra of lichenin, B(l --+ 4), ~(I --+ 3) polyglucane from lichens while
Chapman (66) studied the water soluble compounds of some Antarctic
lichen by 13C-NMR spectroscopy. Also 3-acyltetronic acids have been
shown by 13C-NMR spectroscopy (440) to exist in two monoenolic
forms A and B shown in Scheme I.
According to Steglich et al. (668) the NMR spectra of pulvinic acids
show large differences in the chemical shifts of the 2,6 and 2',6'-aromatic
protons. This allows unambiguous differentiation between the two
possible isomers (A, B) of unsymmetrically substituted pulvinic acids
shown in Fig. 2.
°tJt···o
•
ROO
····· H
B
S cheme 1. Monoenolic forms of 3-acetyltetronic acids
A B
Fig. 2. NMR differentiation of protons of pulvinic acids
References, pp. 239-276

Jakupovic and Huneck (442) correlated the lH-NMR spectra of

19 depsides, depsidones , depsones and dibenzofurans by NOE differ-
ence spectroscopy while Malterud and Anthonsen (523) recorded the
13C-NMR spectra of 15 phenol derivatives. Spin-lattice relaxation
times, T J, were measured for the quarternary carbon atoms of these
compounds and signals were assigned to the aromatic carbon atoms
bound to hydroxyl and methoxy groups . T] values for C-OH are
smaller than those for C-OMe within the same molecule. Furthermore,
C-OMe groups with substituents in both ortho-positions have larger
T 1 values than those with at least one unsubstituted ortho-position.
Narui et al. (557) assigned the 1Hand 13C_NMR spectra of the fol-
lowing depsides and tridepsides found in Umbilicariaceae: lecanoric
acid, methyllecanorate, evernic acid, methyl evernate , gyrophoric acid,
hiascic acid, ovoic acid, umbilicaric acid, crustinic acid, lasallic acid,
methyl gyrophorate, 4-0-methylgyrophoric acid, tenuiorin, papulosic
acid, deliseic acid, and methyl 4-0-methyldeliseate, while 13C-NMR
spectra of 14 naphthoquinones and of 31 naphtho- and anthraquinones
have been recorded by McDonald et al. (539) and Hofle (376)
respectively. Numerous papers have appeared on lH and 13C-NMR
spectra of lichen triterpenoids, e.g. lupanes and hopanes (10, 719,651,
731), lupanes and taraxeranes (59), friedelanes and taraxasteranes (572),
migrated hopanes and 2Ia-H-hopanes (571), fernenes (729) and
compounds of the pyxinol group (730) . The 13C-NMR spectra of
pentacyclic triterpenoids have been reviewed (522).
2.6. Mass Spectrometry (MS)

Addison (2) has applied pyrolysis-chemical ionization mass spect-
rometry with protonated molecular ions to the MS of the thermally
labile lichen substances gyrophoric acid and tenuiorin. Tabacchi et al.
(683, 686) used tandem mass spectrometry (TMS) for analysis of
Pseudevernia furfuracea and Lobaria pulmonaria and some lichen
triterpenes [for the technique of TMS see Stach et al. (664)]. Holzmann
and Leuckert (375) identified depsides, depsidones and usnic acid by
their specific fragmentation patterns without prior isolation or purifi-
cation. Mass spectra of ten di- and tri-oxygenated stictane triterpenoids
and their trimethylsilyl derivatives have been studied (374). The major
fragmentations involve ring C, but specific cleavages in ring A, Band E
are also observed which allow the substitution pattern of the skeleton to
be readily determ ined: see Scheme 2. The following classes of lichen
substances have been analyzed by MS: depsides and depsidones (177,
10 S. Huneck
~:: :OH
~
+
Scheme 2. MS fragment ation of 22ct-hydroxystictane
425, 473, 527), xanthones (623), polyporic acid and derivatives (337)
and usnic acid and derivatives (404, 639).
Allemand (9) used MS-MS for identification of triterpenes and
steroids in Evernia prunastri while Shojima et al. (650) reported the MS
of about 100 natural and unsaturated pentacyclic triterpenoids,
including hopanes and lupanes.
2.7. X-ray Analysis
X-ray analyses of lichen substances since the last review are

summarized in Table 2.
2.8. Cathodoluminescence and X-ray Microanalysis
Mathey and Hoder (530) have applied the technique of cathodolu-

minescence and X-ray microanalysis to the identification of vinetorin,
3-0-methyl-2,5,7-trichloronorlichexanthone and of quinones in some
crustose lichens .
2.9. Laser Microprobe Mass Spectrometry (LAMMA)
The principle of laser microprobe mass spectrometry has been

described by Vogt et al. (713). A laser beam focussed on the object
ionizes the organic compound(s) present in the sample; the ions are
separated and recorded in a time-of-flight mass spectrometer. Mathey
(529) discussed the prospects of LAMMA for lichenology, stating that
this method allows not only to analyze minute amounts of compounds
present in lichens (especially in tiny foliculous species) but also to
correlate the data with certain structures. Thus lichexanthone could be
identified in the tropical microlichen Laurera benguelensis. In a further
References. pp. 239-276
New Results on the Chemistry of Lichen Sub stances II
Tabie 2. X-ray analyses of lichen substances
Compound Ref.
7-Acetyl-8, IO-dihyd ro xy-3,9, IOb-trimethylben zofuro[2,3-g)- (81)

I,2-benzisoxazo l-4( IObH)-on e
8-Acetyl-5,7-dihyd roxy-3,4a ,6-trimethylbenzo fur o[3,2-f} I,2- (81)
benzisoxazol-4(4aH)-on e
(+ )-Aspicilin (597)
Atranorin (40)
Cercospor amide (679)
Er iodermin (79)
G raciliformin (7)
Graphenone (549)
Graphisquinone (549)
22C!- Hydroxy-3,4-seco-stictan- 3-oic acid (82)
3-Hydroxy-4,4,6-trimethoxy-2,5-di-(p-methoxyphenyl)cyclohex a- (284)
2,5-dien-I-one (intermediate of butlerin B)
Hypostrep silic acid (548)
Lepranthin (5 79)
Leprolomin (205)
Methyl 2,3-dihydroxy-6-hyd ro xy-5'-methoxy-4-(3-oxopentyl)- (77)
3,3'-dioxo-1' ~-pen tylsp iro [be nzofura n-2, 2'-o xa bicycl o [4.I .O)-hept-
5-ene)-6'~-carboxylate (intermediat e of the synthesis
of epiphorellic acid 2)
Methyl everninat e (35)
Methyl isorhizon ate (34)
Pentaacetylnorstictic acid (Gohrt,
unpublished)
I-n -Pent yl-2-methoxycarbonyl-3,6-dimethoxy-8-m ethoxalyl- (64 7)
dib enzofuran (degradation product of didymic acid)
Phl ebic acid 0 (24)
(- )-Placodiolic acid (78)
Ret igeranic acids A and B (6 78)
Rocc ellaric acid (552)
Scabrosin dibutyrate (ambewelamide A) (283)
Sekik aic acid (452)
Solo rinine (534)
Stict ane 3~,22C!-diol (82)
Tetraacetylsimonyellin (210)
Th iomelin (218)
Tri-O-acetyld emeth ylchodatin (254)
Tri acet ylrh od ocladonic acid (540)
(+ )-Usnic acid sodi um salt 2 Y2 hydrate (620)
Vulpinic acid (41)
W rightiin (5i8)
12 s. Huneck
paper Mathey et al. (533) applied the method to other lichens and
identified 1,3,6,8-tetrahydroxyanthraquinone in Phaeographina chryso-
carpa, russulone, norlichexanthone and parietin in Laurera sanguinaria
and elsinochrome A in a pathogenic lichen from Brazil.
~
OH O OMe
OH 0 OH 0
o
MeO Me
MeO~Me
o
MeO -,['Me
OMe
OH 0
Russulone Eisinochrome A
LAMMA, in combination with IR and NMR data furnishes in most

cases enough information for complete structure elucidation of lichen
pigments (705, 531) .
2.10. Fluorescence Microscopy
Kauppi and Verseghy-Patay (449) studied the distribution of lichen

substances (especially depsides and depsidones) in lichen thalli by
fluorescence microscopy.
2.11. Computer Program for Identification of Lichen Substances
Mietzsch et al. (544) have developed a computer program (Wintab-

olites) for identification oflichen substances based on spot tests, TLC R r
values and HPLC R 1 values. The third edition of this data base contains
data for over 700 lichen substances (545).
3. General Methods for Derivatization and Regeneration

3.1. Carboxyl groups
3.1.1. Methylation
A very useful reagent for methylation of carboxylic acids is
diazomethane. At O°C and within a few seconds only the carboxylic
group of phenolic carboxylic acids is esterified. Alkaline saponification
regenerates the carboxylic acid, but in compounds with a free hydroxyl
group in the para position decarboxylation occur s. Another reagent for

regeneration of the acid from a meth yl ester is lithium propylmercap-
tide. (l- Methylene-y-lactonecarb oxylic acids like protolichesterinic acid
react with diazomethane to form methyl ester s of pyrazolines. In order
to prepare the meth yl ester the carboxylic acid is first converted into the
silver salt which on reaction with meth yl iodide furn ishes the
corresponding methyl ester (see Scheme 3). Carb oxyl group s can also
be protected by formation of an oxazoline (see Scheme 4).
S cheme 3. Reaction of cx-methylene-y-lactonecarboxylic acids with diazomethane and of

their silver salts with methyl iodide
Scheme 4. Transformat ion of a car boxylic acid into an oxazo line
Phenacyl esters are prep ared by heating the potassium salt with
phenacylbromide in the presence of l8-crown-6 in acetonitrile. Such
esters exhibit strong UV absorption near 240 nm and are useful
derivative s for HPLC (393). Para-nitrophenyl esters are prepared from
the acid and p-nitrophenol in the presence of N,N'-dicyclohexylcarbo-
diimide and absorb at about 270 nm (see Scheme 5).
3.1.2. Benzylation and Debenzylat ion

Benzylation of a carboxylic acid is a key step in the synthesis
of depsides and is carried out using a) benzylbromide (BnBr) and
14 S. Huneck
Br~
/
•
S cheme 5. Preparation of phenacyl esters and p-nitropheny1 esters
potassium hydrogen carbonate or b) phenyldiazomethane. Hydroge-

nation of the benzyl ester with PD-C regenerates the free carboxylic
acid .
3.1.3. Carboxylation and Decarboxylation

Reaction of an aryllithium with carbon dioxide leads to the
corresponding carboxylic acid . Aromatic carboxylic acids are decarb-
oxylated by heating a) without NaOH, b) with NaOH or c) with CU20
in dipyridyle (see Scheme 6).
Me
~COOH ) _6._ _
_a..:...
HOAJl.. OH b)NaOH
100·C
Me Me
)yCOOH CUZO ,D iPy ~
RO~OR RO~OR
CHO CHO
S cheme 6. Carboxylation and decarboxylation of aromat ic car boxylic acids
Ref erences, pp. 239- 276

3.2. Alcoholic and Phenolic groups
3.2.1. Acetylation
Primary and secondary aliphatic and phenolic hydroxyls can be
acetylated either by acetanhydride-pyridine (AC20-Py) or by acetan-
hydride-sulfuric acid (AC20-H2S04)' Aromatic aldehydes react with
AC20-H2S04 to form the corresponding diacetates (see Scheme 7).
Scheme 7. Reaction of arom atic aldehydes with AC20-H2S04 to diacetates
3.2.2. Methylation and Demethylation

Methylating agents for phenolic groups are a) diazo methane (the
reaction time varies from minutes to 24 hours) , b) dimethyl sulphate
(DMS) - potassium carbonate in acetone or dimethylformamide (DMF)
and c) methyl iodide - potassium carbonate in acetone . For demethy-
lation of a methyl ether group ortho to a methyl ester group boron
tribromide is used, while demethylation of a methyl ether para to a
methyl ester group is carried out with boron trichloride (see Scheme 8).
Me Me
~COOH
Me OAJlO~OMe
Me Me Me Me
~COOH ~COOH
MeOUO~OH HO~OUOH
Scheme 8. Demethylation of methyl ethers with boron tribromide and boron trichlorid e
16 S. Huneck
3.2.3. Isopropylat ion and Deisopropylation

Phenols are isopropylated with isopropyl bromide - potassium
carbonate. The products are cleaved with either BCl 3 or with TiCl 4 in
methylenechloride at O°C (see Scheme 9).
AMe Me}-Br K C03

Me 1 2 AMe
HO~OH Me>-o),.J(o-<Me
- --
a) BCI3
Me Me
b) TiCI4
Scheme 9. Formation and cleavage of phenol-isopropyl ethers
3.2.4. Benzylation and Debenzylation

Benzylation of a phenol is carried out using benzylbromide -
potassium carbonate. Hydrogenation with Pd-C regenerates the phenol
(see Scheme 10).
BnBt, K,CO,
H2 , Pd-C
Scheme 10. Formation of a phenol-benzyl ether and its cleavage
3.2.5. Oxidation of Alcohols

Primary aliphatic alcohols produce the corresponding carboxylic
acid on oxidation with chromium trioxide. Secondary aliphatic alcohols
are oxidized with either Jones' reagent or with pyridinium chlorochro-
mate (PyCICr04) to the corresponding ketones (see Scheme 11).
Cr03
R-COOH
a) Jones '
reagent
b) PyCICr04
Scheme 11. Oxidation of aliphatic alcohols

3.3. Substitution at Aromatic Rings
3.3.1. Halogenation and Dehalogenation

Halogenation and dehalogenation of aromatic compounds are
summarized in Scheme 12.
Me
~COOR 2CI2
HO OH Raney-Ni
8"'
~ NBS,hV'
~0Ac·
Me
Scheme 12. Halogenation and dehalogenation of aromatic compounds
3.3.2. Hydroxylation
Ethyl everninate is hydroxylated to ethyl 5-hydroxyeverninate by
oxidation with potassium peroxodisulphate (see Scheme 13).
HO)):MeCOOEt
I~
H .h OH
Scheme 13. Hydroxylation of ethyl everninate

18 S. Huneck
3.4. Synthesis of Aldehydes
Common syntheses of aromatic aldeh ydes employ a) the Gatter-

mann reaction , b) the Vilsmeier-Haack reacti on , c) formylati on with
dichlorodimeth yl ether (D CDME), d) the Duff reaction, and e) the
Gassman-Amick reaction (see Scheme 14). Aromatic aldehydes can be
protected either as diacetates or Schiff's base.
Me Me
~COOMe ~COOMe
HO~OH ZnO.o2· HOyOH
a)
AICI) CHO
HCI
Gattermann react.
b) POCI)
DMF
Vilsmeier - Haak react .
Me Me
~COOMe OHC~COOMe
«
MeO~OMe DCDME' MeO.AJl.OMe
HO-«~", Me Me HMTA
OHC
HO
Me
0
O-<Me
Me
TFA
Duff-React .
s:)
6
OH HO
1 0 (I
1. ~N~S')
~s 1.)""O,8F,
2.) Na2C03
~ '-S OH
~CHO
Gassman-Amick react.
Scheme 14. Synth eses of aromat ic aldehydes
3.4.1. Reduction of Aldehydes

An aromatic aldehyde gro up is reduced by sodium borohydrid e to
benzyl alcohol and by hydrogenati on with hydrog en, Pd-C and reaction
with Zn-Hg in HCl to a meth yl group (see Scheme 15).
CH,OH
NaBH._____ I '<::::
(~)
()
roH ~
1'<::::
~ ~
a) H" Pd-e '<:::: Me
b) Zn-Hg, HCI ()
Scheme 15. Reduction of aromatic aldehydes
3.4.2. Oxidation of Aldehydes

Aromatic aldehydes are oxidized a) with sodium chlorite (NaC10 2)
in the presence of sulfamic acid to the corresponding carboxylic
acid (Lindgren-Nilson reaction) and b) with hydrogen peroxide or
m-chloroperbenzoic acid to the corresponding phenols (see Scheme 16).
COOH
NaCI<>,
.i->
1'<::::
()
~
r(YCOH
V ~
bjMCPBA
1'<::::
OH
(~)
Scheme 16. Oxidation of aromatic aldehydes to car boxylic acids and phenols
3.5. Cleavage and Formation of the Depside Ester Bond
Depsides may be cleaved with either cone. sulphuric acid at ODC or

with KOH-H 20 or KOH-MeOH. Prolonged boiling (5-20 hours) of a
depside with tert.-butanol (TBA) yields the tert .-butyl ester of the S-part
of the depside and the phenolic unit (23, 384, 542) (see Scheme 17).
Depsides with a keto group in the ~-position of the side chain in the
S-part of the molecule give with KOH at room temperature a
y,8-unsaturated 8-lactone, e.g. confluentic acid ---+ 4-0-methylolivetonide
(see Scheme 18).
Trifluoroacetic anhydride (TF AA) and N,N' -dicyclohex ylcarbodii-
mide (DCCD) are modern reagents for the synthesis of depsides (see
Scheme 19). A mild con version of carboxylic acids to esters using
20 S. Huneck
M~
~eo-o OH
HO~OH VeOOM~
M~
R
~eo-o OH
HO~OH '9=eooH
R'
JrBA
R M~
J.v-eOO-~-M~ HOyyOH
HOAJl.OH M~. ,eOOH
R'
S cheme 17. Cleavage of depsides
&
n - e ~11
o •
MeO OH
Scheme 18. Cleavage of confluentic acid with KOH
Ref erences, pp. 239-276

(YCOO~ H0'O
a)TFAA ,Toluene ,RT
b) DCCD,Toluene,RT
Scheme 19. Synthesis of depsides
transfer catalysis was described by Puntambekar et al. (592) and may be

useful for the synthesis of lichen depsides.
4. Structure Elucidation and Synthesis of Lichen

Substances
4.1. Nitrogen Containing Compounds

Fujikawa et al. (304-306) analyzed the free amino acids in Japanese
lichens. Solberg (657) isolated from Anaptychia fusca a mixture of an
aminopeptidol (CSH13N04) and an aminocyclitetrol (C6H 1SN0 4) and
from Stereocaulon paschale an aminohexitol (C6H1 SNOs); the structures
of these constituents are unknown. Solorinin (1) is a new amino acid
derivative from Solorina crocea whose structure was determined by x-
ray diffraction (451, 534). Glutathione (2) and glutathione disulfide (3)
have been found in Pseudevernia furfuracea (472). The structure of
picroroccellin (4) proposed initially (301) has been revised to 5 by
Marcuccio and Elix (524). Later on these workers also synthesized
methylanhydropicroroccellin (6) and dimethylpicroroccellin (7) and
established their trans-stereochemistry (525). The properties of dime-
thylpicroroccellin were identical with those recorded for this compound
prepared from the natural product from Roccella fuciformis (670) (see
Scheme 20).
Shin et al. (649) synthesized picroroccellin diastereomers and their
regiomers (see Scheme 21).
Huneck et al. (400) established the structure of arthonin (8), the
dibenzoate of new amino acid amino alcohol from Arthonia endlicheri
as (-)-N-benzoyl-L-valinyl- N '-benzoyl-L-isoleucinate. The synthesis of
arthonin is shown in Scheme 22; the isomeric iso-arthonin (9) was also
synthesized.
22 S, H uneck
MI.'O r N M I . ' 3
COO-
HO
aMI.'
I: Solorinin
mp 149-150, [al D + 9 (MeGII)
2: Glutathione
3: Glutathionedisulfide
4: R ~ II, R' ~ Me or R = Me, R' ~ II 5: Picroroccellin: R ~ /I,R' ~ Me or R ~ Me, R' ~ II
Ano ther dib enzoa te of an aminoacid amino alco ho l is hypothallin,

(- )-N-benzoy l-L-phenyl-alaninyl-N'-benzoyl-L-leucina te (10) from the
lichen Schismatomma hypothallinum (402). It was synthesized by
condensation of (- )~N-benzoxycarbo nyl- L-leuci ne and (- )-N' -benzoyl-
L-phenylalanino l in the presence of N, N'-carbo nyldiimidazole and
subseq uent debenzoxycarbon yla tion and benzoylation (see Scheme 23).
Ref erences, pp, 239- 276
New Results on the Chemistry of Lichen Substa nces 23
Me Me
I IOMe ..Ct
O~N~Ph O~N {A-Ph
PhVN~O Ph~N~~
I - 1 0
Me Cl 2 Me
MeOH
IH2 ,Pd-C
Me
lOMe
OyNY"Ph
Ph~N~O
I
Me
6 : Methylanhydropicrorocccilin
Me CI Me
Ii:'
1 lOMe CI
~
N Ph OyN.:v"'Ph
Ph N Ph~ ~n .
Cl I 0 - . . CI N 0 __
CI Me MeOH MeO ~e H2 ,
Pd -C
Me Me
lOMe rOMe
0yNY--Ph 0yN0Ph
Ph,-+ N ~O Ph'-1'N~o
MeOM1 He!
e
MeO I
Me
7: Dimethylpicroroccellin
Scheme 20. Synthesis of meth ylanh ydropicroroccellin

and dimethylpicroroccellin
o
Mero!"Me
R R'
R R'
11 a: _ NHoCO.ph - NHoCO-Ph
b: .... NH-eo.ph NHoCO-Ph
C: _ NHoCO.ph NHoCO-Ph
d: .... NHoCo-Ph _ NH-eO-Ph
Huneck and Porzel (399) synthesized all stereoisomers esters of

L-and D-N-benzoylalanine and L- and D-benzoylalaninol (lla-lld) and
recorded their CD spectra; in this way the stereochemistry of new esters
can be correla ted easily.
24 S. Huneck
Ac At
OyN OyN
Ph~N~O Ph~Nlo
- H - Me
PhCHO MeJ PhCHO
TBA TOOK
H H Sr H
OyN'f"'Ph OyN..A~ 0yN~Ph
Ph~N~ Ph~N"~O e Ph~N"~'OOMe
Me-Me --Me--
NBS H2,Pd-C 1.) NBS
MeOH H20
2JH2·Pd-C
HOMe HOMe
OyNY'Ph OyN~Ph
Ph~N.l"O + Ph"--'tNl::.o
HO Me HOMe
H Sr
H~ HOH HOH
0.",.. N i, Ph OyNtPh 0jN+--Ph
Ph~~e 0 Ph...,)..N 0 PhyjN.J..o
Me - OMe-
H2,Pd -C NBS Sr Me HZ.Pd-C
MeOH
HOH H OH
0lN ~Ph 0 lN h ph
Ph'-1'N~O + Ph'-1'N.tO
Me
MeO MeO Me
S cheme 21. Synthesis of picroroccellin diastereomers and t~eir regiomers
Huneck and Foll man n (394) isolate d from Arthothelium galapago-

ense a neutral compound which they named arthogalin. Later on
Huneck et al. (395) elucidated the structure of arthogalin as 12 by
hydrolysis to S-phenylalanine, S-valine and two molecules of R-C(-
hydroxyisovalerianic acid. The connectivities of these units were fixed
by proton-detected multiple bond IH, l3C correlation (HM BC).
References, pp. 239- 276
Me
HO-0Me
I
NH2
Ph-COC!
Me Me
Me~COOH HO~Me
1:'
NH
I
CO -Ph
~O-O-CH2-Ph
NH 1.)COI
2.)HBr
3.)Ph-COCI
Me 0 JMe
Me, .tj i ~O : Me
B
'v' Ar\hon in
NH NH mp 165 -167
I I
CO-Ph CO-Ph [«']0 -9(CHCI3)
Me 0 MeyMe
Me~N~o'CO_Ph
NH H 9 Isoar\ honin
I
CO-Ph
Scheme 22. Synt hesis of ar thonin
19
J2: Arthogalin, mp 285-286

26 S. Hun eck
-' 0
Me: /'o..)l »<:«>;
T T '0 i Ph 10: Hypothallin, mp 176-177
Me NH NH
I I
CO-Ph CO-Ph
1.)CDI
2.)HBr
3.)Ph-COCI
Me~COOH HO~Ph
Me NH +
NH
I I
CO-O-CH2-Ph CO-Ph
S cheme 23. Synthe sis of hypoth allin
The structures of the scabrosin esters 13a-13e (isolated from

X anthoparme lia scabrosa) have been revised by X-ray analysis of the
dibutyrate 13c (283). The esters 13b (ambewelamide A) and 13d
(ambewelamide B) were also isolated from an unidentified Usnea species
from Sri Lanka (732).
13.: Scabrosin diacetale: R, = R, = Me

13b: Scablosinacetate butyrate: R, = Me, R, = rK:;,H,
13c: Scabrosindib~te : R, =R, =rK:;,H,
13d. Scabrosinacetate hexenoate: R, = Me, R, = rH:oHll
13e: Scabrosinbutyretehexenoete: R, =noC,H" =
R, n-C,H"
9-cis-Octadecenamide was found in S tereocaulon alpinum (436a) and

indolylacetic acid in Ramalina duriaei (281,282).
4.2. Phosphorus Containing Compounds
Dembitsky and coworkers (164-169) found phosphatidylcholine,

pho sphatidylethanolamine, phosphatid ylglycerol and ph osphatidylser-
ine in Pseudevernia furfura cea and other lichens.
4.3. PolyoIs, Mono- and Polysaccharides and Carbohydrates
The occurrence and function of low and high molecular weight

carbohydra tes have been reviewed (332) as were lichen glycosides (587).
According to Pueyo (586) the following diholosides and heterosides

were found in lichens: saccharose, trehalose, galactosyl-arabitol, galac-
tosyl-pentitol, galactosyl-ribitol, glucosyl-mannitol, galactosyl-manni-
tol, and mannosyl-mannitol, while lactose has been isolated from the
lichen Sticta damaecornis (159). Syntheses of tri- and tetra-saccharides
related to fine structures of lichenan and cereal B-o-glucanes were based
on the silver tirfluoromethanesulfonate-promoted Konigs-Knorr con-
densation (692). The IH-NMR spectrum of lichenin confirmed its struc-
ture (14) as a polysaccharide containing glucose units linked by
B(1 - t 4) and B(1 - t 3) glycosidic linkages in the ratio 2:1 (309). The
crystalline conformation of lichenin was investigated by Tvaroska et al.
(700).
r ~OH 1
# H~OH 0 _c~ I (V~
OH OH OH
l
-0 OIHO 0 HO _
HO 0 HO~O~O-
0 0
OH OH I OH OH
OH ~n
14: Lichenin
The 13C-NMR spectra of lichenin (310) and pustulan (674) have

been reported. Water-soluble polysaccharides from five Stereocaulon
and two Umbilicaria species have been analyzed by Takahashi et al.
(688) and Kjelberg and Kvernheim (462) respectively. Umbilicaria
species contain partly O-acetylated pustulan. o-Galacto-o-mannans
were isolated from six Canadian lichens (333) and from Umbilicaria
pustulata and U. spodochroa (463) . Iacomini and coworkers analyzed
the carbohydrates of Cladonia alpestris, C. confusa , C. amaurocraea
(431), Cora pavonia (432), Stereocaulon ramulosum (26, 27), Letharia
vulpina, Actinogyra muehlenbergii, Usnea spec. (430), Ramalina ecklonii
(543), and Evernia prunastri (695). The polysaccharides from Neuropo-
gon aurantiaco-ater consist of lichenan, isolichenan and a galactoman-
nan (28), while an unusual glucomannan from Tornabenia intricata has
been isolated (694) which has a (1 - t 6)-linked a-o-Man p main chain
substituted at 0-2 mainly with side chains of o-Df-Man p. Three
aldoses , six alditols , eight oligosaccharides and a glycopeptide were
found in Sticta species from Brazil (160). The glycosphingolipid from
Ramalina celastri was characterized as an O-B-o-galactopyranosyl-
(1 - t l')-ceramide; its main lipid components are (4E)-sphingenine,
sphinganine and eicosa-sphinganin, esterified with palmitic, oleic and
2-hydroxypalmitic acids (520).
28 S. Huneck
4.4. Aliphatic and Cycloaliphatic Compounds

4.4.1. Hydrocarbons
The plant growth hormone ethylene was detected in the lichen
Ramalina duriaei by Epstein (281, 282). Ott and Zwoch (569) analyzed
Cetraria islandica, Cladonia rangiferina, C. arbuscula, C. sulfurina,
C. cornuta, C. pyxidata , Peltigera lactucifolia and Usnea aurantiaco-
ater for ethylene and found it in amounts of 0.8-5.5 Ill/g dry weight/
hour. The presence of hydrocarbons with 17-33 carbon atoms has been
reported (317) in Cetraria nivalis, C. crispa and Siphula ceratites; in
other lichens C-27, C-29 and C-3l were the main hydrocarbons (765).
The hydrocarbons of the odoriferous fraction of Evernia prunastri have
been examined (357) .
4.4.2. Aliphatic Alcohols

Aliphatic alcohols have been identified in Cetraria islandica
(C 22H 410H, C z4H4SOH, C z6H490H) (658), Cetraria delisei, Lobaria
pulmonaria, Stereocaulon tomentosum and Usnea hirta (659). l-(O-cr-D-
Glucopyranosyl)-3S,25R-hexacosanediol (15) is a higher alcohol from
Solorina crocea (451, 453). The absolute configurations at C-2 and C-25
were determined by FT NMR (Mosher's IH method) of the MTPA-
derivatives (see Scheme 24).
4.4.3. Aliphatic Acids and Esters

The fatty acid composition of lichens has been discussed extensively
by Solberg (658) and Dembitsky et al. (163, 164, 167-170). Rezanka
and Dembitsky (619) isolated from Acarospora gobiensis (from saline
soils near the lake Ysyk K6l, Kyrgyzstan, Central Asia) the first
bromine- containing lichen substances, (5E, l7E)-18-bromo-octa-5, 17-
dien-15-yonic acid and l8-bromo-octadeca-5,7, l7-triyonic acid . Solberg
(658, 659) has identified oxalic, malonic, fumaric, succinic, glutaric,
adipic, pimelic, octa-l,8-dienedioic, suberic, azelaeic and sebaic acids in
Cetraria islandica, C. delisei, Usnea hirta, Lobaria pulmonaria and
Stereocaulon tomentosum but already earlier Schade (635) had found in
numerous Usnea species calcium oxalate which may be deposited in the
form of two different hydrates: the tetragonale weddellite, (COOhCa·
2H zO, and the monocline whewellite, (COOhCa·HzO, as shown by
X-ray diffraction and scanning microscopy (SEM) (715). The glistening
pruina of 25 investigated Pyxinaceae species consisted of whewellite,
whereas the spotted pruina consisted of weddellite (15). Manganese
OH QH
Me~(CH2)19~O*OH
!
H+ 0-Z::::-~H 15
. OH mp94-99
OH OH ["']D-9 .5
Me~(CH2)19~OH
!TPMCI.Py
OH OH
Me~(CH2)19~OTPM
IMTPAC',py
O-(+)-MTPA O-(+) -MTPA
Me~(CH2)19~OTPM
O-(-)-MTPA O-(-)-MTPA
Me~(CH2)19~OTPM
-CHVMe -CH2VH2-CH20TPM
MeO Ph Ph OMe
2!!R 3S
CF3 CF3
tf l-CH, -H+}-MTPA - d l-CHr H- )-MTPA < 0
0" M.~+)-MTPA - J" M~ -)-MTPA > 0

d -CH~TPM l+)-MTPA - d CH~TPM l-)MTPA < 0
IICH2-H+)-MTPA - dICH:z-H-)-MPTA > 0
S cheme 24. Determination of the absolute configuration at C-3 and C-25 of I (O- Cl-D-
glucopyranosyl)-3S,25R-hexacosa nediol
oxalate has been detected in Pertusaria corallina (733) and fumaric acid
was isolated from a Stereocaulon species from Venezuela (541). Small
amounts of branched aliphatic acids were found in Aspicilia transbaica-
/ica, Evernia mesomorpha and E. prunastri (168) and a mixtu re of tetra-
hydrox y fatt y acids (16) has been isolated from Alectoriafr emontii (655).
Me-{CH2ln-CHOH-CHOH-CHz-CHOH-CHOH-{CH2)rCOOH
16: n = 4, 6, 7, 8, 9
30 S. Huneck
H
MeOOC ":1
. : ..Me
R" "'COOMe
HCI/ H
H
/ threo-Roccell-; acid
Me "':l/cooMe
R " ··· COOMe H

H L~ Me -, :!....CH20H
Roccellic acid R'" "'CHZOH
H
I Cr03
+ -r, H 0
R " '~
H
Scheme 25. Isomerization of roccellic acid, reduction of dimethyl roccellate and oxidation
of the resulting diol
Keto acids (5-keto-15:0, 5-keto-16 :0, 5-keto-18 :0, 5-keto-21 :0, 5-keto-
23:0) have been isolated from Cetraria delisei and C. islandica (659,
658). Fatty acids from Xanthoria parietina collected at different elevations
(400,800 and 1300 m a.s.) have been analyzed (576). The main fatty acid
at the lowest elevation was 18:2, while 14:0 was the major component at
the other two elevations. The isomerization of roccellic acid to threo-
roccellic acid (see Scheme 25) has been studied (407) . Reduction of
dimethyl roccellate with LiAlH 4 gave the corresponding diol which
yielded two isomeric y-lactones with Jones ' reagent (see Scheme 25).
Structure 17 with unknown stereochemistry has been proposed (502)
for angardianic acid from Leproloma angardianum . If its biosynthesis is
similar to that of roccellic acid angardianic acid should have stereo-
!..
structure 17a.
H
M8•••• ,-eOOH
n-C H...>"··· ····'COOH

14 ~ H
17 17.
Angardianic acid
An enantiospecific synthesis (see Scheme 26) of (+)-bourgeanic

acid (18) (37) via (- )-hemibourgeanic defines the latter as 2S,3S,4R ,6R-
3-hydroxy-2,4,6-trimethyloctanoic acid (722, 723). Conformational
/ OH
Li-DIPA
Me'-./"-N" " + Me/ ' y ' " I
L..J Me
/ OH
Me~O Me/"y"'y COOMe

Me Me l.)HCI
2.)CH2N2 Me Me
LAH
Me~OH q}
Me Me Me ~B NH
6-,)
l
COCI
COCl , DMSO ,EI 3N /
Me ~CHO
: : + ,0 X ' COO-IPR
Me Me Me~B
'0 COO -IPR
!
, .lMePh ,4A s ieve
2.)TBS -Ir iflale
QTBS
Me~CH2
Me Me Me
ll 03 ,Me2 S
2.lNaCI0 2
[ 3.)HF
QH P 0
Me ~COOH _ _ Me~
Me Me Me PhS0 2C1 , Py Me Me Me
Hemibourgeanic acid + BuLi
QH
Me~CH2
Me Me Me
HQ ° Me'.fc~OH_
Me~O 'Y1Me
Me Me Me /8 Me Me
Bou rgeani c acid
Scheme 26. Synthesis of (+ )-bourgeanic acid

32 S. Huneck
analysis of bourgeanic lactone (19) shows that the eight-membered ring

adopts a crown conformation with Cz symmetry and all substituents in
equatorial orientation (722).
Me
o Me ~ ~
Q
~Me
,
M~O
~ ~eM! '6
19 : Bourgeanic lactone
4.4.4 . Aliphatic Tricarboxylic Acids

The absolute configuration of norcaperatic acid (20) was determined
as 2S,3S by CD measurements on the natural acid and optically active
synthetic compounds as their molybdate complexes (38).
COOH
n'C14H29$H
HO COOH
H H
COOH
20 : Norcaperatic ad,
The structure of (+ )-isorangiformic acid from Lecanora stenotropa

has been elucidated as (+)-2S-methoxycarbonyl-3S-heptadecanedicarb-
oxylic acid (21); on saponification it produced (+)-norrangiformic acid
and on heating with acetylchloride a six-membered anhydride (381) (see
Scheme 27).
The structure of (+)-rangiformic acid has been revised from 22 (411)
to 23 (31) on the basis of new NMR evidence. Kiimmerling et al. (488)
H H
···.····COOM\OH
HOoC/1· HOoc/l'
" .....COOH
R ; COOH R : COOH
2/
H "'"
AcC""
:
ctoMe
(+)-Isorangiformic acid R~
mp 83 8S.[«']D+ s . 2(MeOHlJ--",l
o 0 0
Scheme 27. Saponification and reaction with acetylchloride of (+)-isorangiformic acid

New Results on the Chemistry of Lichen Subst ance s 33
proposed structure 24 for jackinic acid from Lepraria jackinii; the close
relationship with rangiformic acid makes stereochemistry 24a likely.
/'t"
H
/x'
,.
H
HQ()C"'" If '
" ,COOH Me()()C"" I . ,\ ".COOH
n-C14H:1. ~ COOMe n-c.,H 2 • : COOH

H 'Ii
22 23 : Rangiformic acid
~COOH
n-C12H:15 COOMe
24 24 /I :Jacklnic acid
4.4.5. v-Lactonic Acids

Two v-lactonic acids of unknown stereochemistry were found in
Lecanora rupicola (174) resp. Cladonia impexa (173). 25 from the former
and 26 from the latter species.
=
25 : R CllH23
28 : R = C1SH31
Numerous papers have been published dealing with the synthesis of

stereochemistry of protolichesterinic acid and related compounds.
According to Leffler et al. (512) W-bromodimethylmethylmesaconate
gave in a Reformatsky reaction with myristic aldehyde and zinc a
mixture of racemic methyl protolichesterinate (27) and methyl allopro-
tolichesterinate (28) (see Scheme 28). Another strategy was followed by
Martin et al. (526): the key step was the carboxylation of y-butyrolac-
tones with methyl methoxymagnesium carbonate (see Scheme 29).
Damon and Schlessinger (158) published a stereoselective synthesis of
racemic protolichesterinic acid based on the conjugate addition of (tris-
(methylthio)methyl) lithium to y-tridecylbutenolide and in situ trap-
ping with formaldehyde, followed by hydrolysis and methylene
formation (see Scheme 30). Carlson and Oyler (58) used itaconic
acid as starting material for the synthesis of racemic protolichesterinic,
34 S. Huneck
H,---/COOMe H,---/COOMe
MeOOC~Me - MeOOC~CH2Br - - -
NBS Zn
n-C 13H27-CHO
Meooc"' r - l H2 M+eOOc\-_i H2
R~O)"O R....zO~O
27 28
Scheme 28. Synthesis of (±)-methyl protolichesterinate and (±)-methyl

allo-protoliche-sterinate (512)
Meooc+~ MeOOC'r--I
R-CHO COOMe BPO wAO tOOMe--

'.)KBH 4
2.) H+
MeOOe .. +MeOOC\--.
R~O R,zO)"O
(!) (r)
,·) Na OH
12.)Me-methoxy-MgC03
HOOC\ -f COOH _ HOO)::£C

.... CH2
...z,..~ HCHO
ROO HNEt2 ROO
(t)-Protol ichesterin ic
acid
Scheme 29. Synthesis of racemic protolichesterinic acid by carboxylation

of y-butyrolactones with methyl methoxymagnesium carbonate
allo-protolichesterinic and nephrosterinic acids (see Scheme 31). Finally

Murta et al. (555) described the first synthesis of (- )-protolichesterinic
acid via a facially selective 2 + 2 cycloaddition reaction of dichloroke-
tene with an enantiopure O-alkylenol ether (see Scheme 32).
19-Acetoxylichesterinic acid (neuropogolic acid) (29), 19-acetoxy-
protolichesterinic acid (30), (- )-allopertusaric acid (31) and (-)-
dihydropertusaric acid (32) are y-lactone carboxylic acids with an
oxygen function in the side chain from Neuropogon trachycarpu s (323)
New Result s on th e Ch emistry of Lichen Sub stan ces 35
LiC(SMe)3 (SMe)3 c OH K'"

1\ HCOH ----
R""". 0):::,0 R O O 1.)ft,:j0
2.)BF
3
HOOC~OH HOO~H2
R 0 0 1.)PCI ROO
S
2.)KH (!) -Proto -
lichesterinic acid
Scheme 30. Synthesis of racemic pr otolichesterini c acid (/58)
HOOC "'r--l H2
R" ·(0.1:0
HOOC ....
CH2
- "r -f-'
(-)-Nephroster inic
n C H AO~O acid
- 11 23
Scheme 3 / . Synthesis of race mic pr ot olichesterinic, allo-protolichesterinic

an d nephrosterinic acids (58)
36 S. Huneck
~-Ph l.I-Dib<omo-
tetradecane,
o!?'--J"-~3H27
Phr""".H
Zn .TiCI4.TMDA
g
~{) ~'I'",
U·~tr
.:h ~ H n~c~H
Cl :
O
~ " . o'~~';:·" :N°
CI / C\O
/Cr(CI04)2
Ph C\ Ph"\---.
R~O H2,Pd-C R'zO)"O 1.)RuCI 3 , Na104

2.)CH 2 N2·DBlJ
3.)HCI
HOOC·.. HOOC...; ---/H 2
R~O 1.)Me-MeO-Mg-
carbonate,
Rj 0)",0
DMF (-)-Protoliche-
R =n-C13H27 2.)N-Me-anili~, sterinic acid
HCOH,NaOAc,
AcOH
Scheme 32. Synthesis of (- )-protolichesterinic acid (555)
and Pertusaria a/beseens (414) respectively. (-)-Allopertusaric acid is

isomerized on heating with acetic anhydride to (-)-isomuronic acid and
gives with diazomethane the corresponding pyrazoline methyl ester. The
dithiospiroketal of (-)-dihydropertusaric acid is desulphurized with
Raney-Ni to (- )-pertusaranic acid, a homologue of (-)-dihydropro-
tolichesterinic acid (see Scheme 33).
Lichesterylic acid and methyl protolichesterinate have been found in
Cetraria is/andiea (658); the latter ester was prepared from the
potassium salt of protolichesterinic acid and methyl iodide (413).
Allo-protolichesterinic acid adds diazomethane to form isomeric
pyrazoline methylesters, the stereochemistry of which was established
by their respective CD spectra . Hydrogenation of allo-protolichesterinic
acid with Pd-C in acetic acid produces a mixture of (- )-dihydro-allo-
protolichesterinic acid (33), (- )-nephromopsinic acid (34) and (-)-
lichesterinic acid (35) (see Scheme 34).
References, pp. 239-2 76
6 5
HOOC'l:!f2
Me
29 4
R···· 0 0
30
R = AcO -CH 2-(CH2)12-
19-Acetoxylichesterinic 19-Acetoxyprotoliche-
acid sterinic acid
mp 98-99 '["']0 .18(CHCI 3) mp 94-96
lNaOH
"Me
R.Ao eOOH
HOOC\-_lH 2 HOOC... .: Me
R....zO~O R~O 32
31
(-)-Allopertusaric acid (-)-Oil-tjdropertusar ic acid

mp 76-78 mp 105-107
["']0 -95 .5(MeOH) ["']0 -74 .9(MeOH)
R =Me-CO-(CH 2 )13-
HOOC>=(Me
IAc2 0 . 6.
<,
"<,
CH2N
MeOOC,
2
C~
R~O~O R~O
(-)-Isomuronic
acid
HOOC·.. ..,Me
Me )
X(CH 213
....cio0
U IRaney-N i
HOOC ·.. ..'Me
n-C15H31~O
(-)-Pertusaranic acid
Scheme 33. Structure and chemistry of 19-acetoxylichesterinic, 19-acetoxyprotoliche s-

terinic, (- )-allopertusaric and (- )-dihydrope rtus aric acids
(+ )-Protolichesterinic acid adds diazomethane to give the 2R-

methylesterpyrazoline and adds ethyl diazoacetate to give the corre-
sponding 2R-adduct (see Scheme 35).
38 S. Hun eck
+ MeOOC, (~
RJ:;i~
HOOC\- lH2
R..-ZO),..O
/H 2 ,Pd-C, AcOH
HOOC~e +HOOCH..·Me + HOOC)=(Me
R..(O)"O R..-ZOAO R...zo):,O

33 35
S cheme 34. Reaction of allo-proto lichesterinic acid with diazomethane

and its hydrogenation
S cheme 35. Addition of diazomethane and ethyl diazoacetate to (+ )-protolichesterinic acid
The ORD spectr a shown in Fig. 3 allow an easy differentiation

between (--- )-methyl dihydro-allo-protolichesterinate (36), (---)-meth yl
nephromopsinate (37), (--- )-methylroccellarate (38) and (-)-methyl
dih ydroprotolichesterinate (39) (see Fig. 3).
(+)-Praesorediosic acid (40) and (+) -protopraesorediosic acid (41)
are y-Iacto ne carboxylic acids from Parmotrema praesorediosum (162).
Ref erences, pp . 239- 276

R =HOOC-{CH2lw 41
(+)-Praesorediosic acid, mp 139-140.5 (+)-Prolopraesorediosic acid, mp 123-1 24
Mulzer et al. (553) synt hesized (- )-nephromopsinic acid by the ad dition

of a chira l allylic bro mide to tetradecanal (see Scheme 36). The same
gro up (628, 666) also described total synt heses of (-)- and (+)-
roccellaric acid an d (- )-dihyd rop ro to lichesterinic acid an d secured the
relative configura tion of (+)-roccellaric acid by an X-ray analysis. One
rou te sta rted from (2S,3E)-1,2-isopro pylidene-5-0-benzyl-3-pentene-
1,2,5-triol (42) (see Scheme 37). The second ro ute included the
ozon isation of methyl-(2RS,3 R,4E)-3-benzyloxy-5-hydroxy-oxolan -3-
one and subsequent conde nsation with tridecyltriphenylphosponium
bromide (see Scheme 38). Finally they synt hesized (+ )-roccellaric acid
and (+)-dihyd roprotolichesterinic acid from o-glucose as the chira l
pool (552) (see Scheme 39).
39
[oc 1
100
200 300 400 nm
J::i
R' ROO R' Roo
"~/'
o 0 R~o~O
36 37 38 39
R = n-C13H27, R' = COOMe, R" = Me
Fig. 3. ORD spectr a of (- )-methyl dihydro -allo-protoliche sterinate (36), (-)-methyl

nephromopsinate (37), (-)-methyl roccellarate (38), and (- )-methyl dihydroprotoliche-
sterinate (39)
40 S. Huneck
~COOEt
o ;
:
-'L.O
Me-\
Me
OBn -: Me
o~Br
. :
~6 Me ~R-CHO
., .,R=n-C 13H27- <, ~
9". r":C,"H2 r.
Me~
0\_6 ~e OH
P-TSOH.Me~ Me
OH ~CH2 RCH~.Me
~R .. Pee
HO OH
: :
Me :
OH HJ04 R 0 OH
CH~.Me HOOC\__/ Me
C·.~·I rZ").,,.O
~ Ru04 R 0
ROO (-)-Nephr~mopsinic
acid
. 0 f (- )-nephromop sinic acid

Scheme 36 . Synthesis

___ ..... .....COOMe ......
0' Y""'" 0- T 'OBo
Me-\-6 1.)D1BAH Me-\-O l-
.)-p--:rS-O-H-.-
Me 2.) BnCl .NaH Me 41 MeOH
2.) BoCI
OBo
I
BoO~OBo
- - - BOO~O
OH NNOAOA
1.)NaOH .... N,
2)03 Me Me
BoO-·. Bo O- "
obooH n-c12H25J-\00H -1.1,.

-KI-
THF-H 20
n-C,2 H25- CH=PPh3
2)BU3SnH
;0 Bo /OBo .(OBo .
R~O LOt: R~;l R1:So

e
+
Mel 1.) H2.Pd- C
2.) POC
HOOC ...;---(Me HOOC ... ..'Me
R~O),.O R~
(-)-Roccellaric (-).Oihydroproto-
acid lichesterinic
acid
Scheme 37. Synthesis of (- )-rocce llaric and (- )-dihydro pro to lichester inic acids sta rting
fro m (2S,3E)-1,2-isopro pylidene-5-0 -benzyl-3-pentene- 1,2,5-tr iol
Me~COOM
__e _ _ Me~_O_BO _
OTHP 1.)OIBAH OH Propionic
2.) BnCl.NaH antlfdride
3.)p -TsOH.
MeOH
Me
~ OB_O Me~ OB_o _
OCOE! LOA HoocAMe 1.) 03
Me3SiCI 2.)n-C 12H25-CH=Ph3
(OBO
HOOC\_{Me
n-c 12H25JlOOH R····(O~

R = n-C13H27-
HOOC '--../Ae
R····(O).,O
Scheme 38. Synthesis of (- )-rocce llaric acid and (- )-dihydropro to lichesterinic

acid via (4S,2E)- I-O-benzyl-2-pentene- 1,4-diol
42 S. Huneck
BnO~ HOOC\---i...Me
R· ···(O~O 1.)LDA.Mel R····(O,1"o

2.)H2·Pd -C
3.)PDC +
HOOC'r--(Me
R·..· Z. O ~O
Scheme 39. Synthesis of {+l-roccellaric acid and {+l-dihyd roprotolich esterinic acid
from o-glucose
4.4.6. Macrocyclic Lactones and Bis-La ctones

4.4.6.1. Aspicilin
Already in the first decade of the twentieth century Hesse (364, 365)
isolated from some Aspicilia species a neutral compound which he
named aspicilin, but it was only in 1973 that its structure was recognized
by Huneck et al. (410) as 4,5,6-trihydroxyoctade-2-en-1 :17-0Iide. After
elucidation of the stereochemi stry of (+ )-aspicilin (43) as 4R ,5S,6R ,17S
by X-ray diffraction (597) no less than 9 syntheses of aspicilin have
been described . Quinkert et al. (598, 599) used the photolactonization
of o-quinolacetates (see Schemes 40 and 41). In a further synthesis
Quinkert et al. (595, 599) 1actonized (2S)-12-(2'-hydroxyphenyl)-2-
dodec anol to a cyclic precursor of (+ )-aspicilin (see Scheme 42). Finally
the same group (295, 596) used n-mannose as chiralic pool for the
synthesis of (+ )-aspicilin (see Scheme 43).
s; Me
d~G·G-
Me 0 Me 0 Me 0
d-d-d::
Me 0 Me 0 Me 0
43
(.)-Aspicil in
Scheme 40. Synthesis of (+)-aspicilin by photolactonization of o-quinolacetates
Waanders et al. (714) started the synthesis of (- )-aspicilin from

2R,3R-dihydroxysuccinic acid and 2-propyne-I-ol as shown in
Scheme 44. Solladie et al. (662) synthesized (-)-aspicilin by condensa-
tion of triphenylphosponium iodide 44 with aldehyde 45 prepared
from C-3jC-9 fragment 46 (see Scheme 45) . The C-3jC-9 fragment was
synthesized via two different routes (661, 68a) (see Schemes 46a and
46b) .
44 S. Huneck
OAe
d~2~ Me 0
\ /
/
d Me 0
d O
OH...
OH
···OH
o
Me 0 Me 0
(.)-Aspieilin
Scheme 41. Synthesis of (+)-aspicilin by lactonization of 6R- and 6S-acetoxy-(6-[(ll'S)-

hydroxydodecyll-2-(phenylsulfonyl)-2,4-cyclohexadien-l-ones
The asymmetric synthesis of (+ )-aspicilin has been achieved by

Sinha and Keinan (652, 653) in 14 steps and II % overall yield, starting
from the achiral (3E)-hexadeca-I,3,I5-triene (see Scheme 47). Enders
and Prokopenko (279) realized the synthesis of (+ )-aspicilin in 19 steps
and with high stereoselectivit y. Three of the four stereogenic centres
were generated by employing the SAMP/RAMP hydrazone method (see
Scheme 48a). Finally Kobayashi et al. (467a) described the chiral
synthesis of (+ )-aspicilin by using a furyl group as the masked y-oxo-
ct,~-unsaturated carboxylic acid (see Scheme 48b).

d-
d d'-
Me 0
d" d~FO
Me 0 Me 0
O
MeO MeO
OH..
OH
"'OH
o
Me 0
Scheme 42. Synthesis of (+ )-aspicilin via 6-acetoxyoctadeca-3,5-diene-17-olide

46 S. Hun eck
H
\E1
CHO
Hot
HO H M~ 0 M~XM~
~H OH -
OH
M~ X0 ,0 ,
CH20H
OBo
HOje9>:;e H2C1f1MeXMe
HO~ - , 0,
-
OBo
OBo
O
OH" '
OH
" 'OH
o
Me 0
Scheme 43. Synthesis of <+)-aspicilin from D-man nose

E!OOCHH _ _ M~Q' __
H R R COOE! BnO - ' CHO
M.
9+'
, 0
~O-SiC--
Me COOH tB'
--
M.
o-t-- M•
~_Si/M'
"M.
M. 0 I
TB
OH
; OH
~H
M. 0
(- )-Aspi cilin
Scheme 44. Synthesis of (- )-aspicilin after Waand ers et at.

t-BuOOC~COOM~
~)- (.)-M~.p -tolylsulloKid~
<, 0 ?, 9: H ~5
t-BuOOe~S~ ~
I
t-Buooe~ "C:l~
9+
M~
1.)Raney-Ni
Me
r 9TBOMS 2.)TBDMSO TBDMS9
OHC~
: 0 • Ph3P~M~ _
t-Buooe~M~
MEM
'5 5w~rn - M~
OAe ~OKid. O-+Me
HO : 0
~VMEM
,. rJ'o OAe
c;:c
~ M~
O-+M~ O~e
i 0 ~ 0
~ MEM l.)LiOH
l.) H2' Pd- C
M~ MEM 2.)LiOH
.' OAe 3.) Swern- ..Me 2.)TBAF
COOEt 3.) DeBCI
OTBDMS OK id OTBDMS
Q:
OH
BF3 ,
SH
[ SH
MeO
Scheme 45. Synthesis of the (- )-aspicilin after Solladie et al.
o 9
BnO~COOEt BnO ~S
LDA,T U Me
Me .... Y') Zn02'
VMe DIBAH
OH 0
OMe
Bno~S
1.lLAH
OMEM 2.)Ae20
MEMCI BnO ~ SD
II
-
OMEM o Me
BnO ~OAe ",--0 50 4
<, OH OMEM
Me Bno~OAe
o-\-Me / Me 6H
BnO ~: MeO+Me
OMe
OMEM
OAe -, Me
Raney-N i"'-. O-\-Me
HO : 0
~OMEM
OAe
4.
Scheme 46a. Synthesis of the C-3/C-9-fragment of (-)-aspicilin after Solladie et al.

1. Dihydroxyacetone phosphate -
OH 0
.
~
Na-lriacetoxyborohydrickt
fruc:t08.1 ,tHliphospha!e ak:lolBse
' P_hos_P,,"_'_"'
B~HO _2_"""_ _
0-1-...
~
~~
.
~
) 1. MeOH,H- MEMCl,N ,N-Ci_,.
.' eth)1amine
. 2. Acel, coIlidne.
an ·76- C t' n
...
HO
9
M.
0 ,J-~__
c.:.X
0H
" ",OH
n O:::"" -,
MEMO ''OH
(+)-AspiCilin
Scheme 46b. Synthesis of the C-3jC-9-fragment of (+ j-aspicilin after Chenevert et al.
MEMCI
Me
~~Me
~nt:f'OMEM
OMe COOEt
l.)AcOH
2.)(EtO)3CMe,
Me
Me3SiBr
o--+-Me
3.)Bu3SnH,ABIBN
~'
~eUAC f : ::MEM Me
Me COOEt -'n-Li-OH-- 0 ~Me
2.)2.4,6-TCBCI,Et3N . ~
DMAP 0 -
OMEM
Me O
~
OH " OH
. (.) -Aspicilin
O " 'OH
MeO
Scheme 47. Synth esis of (+ )-aspiciiin from (3E)-hexadeca-1,3, i 5-triene

after Sinha and Keinan
50 S. Huneck
Scheme 48a. Synthesis of (+ )-aspicilin after Enders and Prokopenko
P.
1. 8r2. CHCls
C'CN.THF ~ 2 .NaN~ .NH3

&Mg(CH,)'-CH:CH, - '<:: 3. TBOMCI, DMF
1
",••OH
Me 1. C8r• . PPh3
2. Mg, THF Me
~CH,),-CH-eH,
1.SharpleaSdihyOrOlt)'lation
~
~ 1 ' OisilU'TT)lbol'ane 2. MOMCI. dl-~ylllmlne , C~ C~
2 .2_~", Pd{PPh,lo
3.NaOH
.,•••OTBDP~
M.
n
~"OMOM_
1.NBS 1.Zn(BH.
c:r6
0M0~,,()MOM 2. NeClO,. ,,",C:CHMo 2.MOMCI
3, 2-el-N-methylpyridine, NE~, MeOH 3. NBS
4. LiOH
••••'OTBOM 'P"
l'~~
0= 9:
M. -
1. 2,4.6-Trichlorobenzoylchloride, NEls
2. HS-(C~b-SH, BF:)
(+)-Aspic~in
Scheme 48b. Synthesis of (+ )-aspicilin after Kobayashi et al.

4.4.6.2. Lepranthin
More than 90 years ago Zopf (763) described a new neutral
compound lepranthin from Arthonia impolita (syn. Leprantha impolita).
Much later, in 1995, Polborn et al. (579) elucidated the structure of
lepranthin as the bis-Iactone 47 by NMR spectroscopy and X-ray
analysis.
Me Me
M'~
I OH OAe 0 ?Ae
O~Me
Me Me
47: Lepranthin , mp 185
CD (EtOH) ~£ -4.1 7 (216 om)
4.4.7. Anhydrides
Graphenone (48) is a dicarboxylic anhydride from the mycobiont of
Graphis scripta ; its structure was elucidated by an X-ray analysis (549).
The bis-anhydride homoheveadride (49) was isolated by Archer and
Taylor (17) from Cladonia polycarpoides.
o
~e Me~
Me~O
o 0
48: Grapheno ne, orange plates, mp 163-1 65
n-c~~o
O~O
o 0
49: Homoh eveadride, tal. + 118 (C HCI,)
4.5. Aromatic Compounds

4.5.1. Aromatic Units
Sources, structure elucidation and syntheses of aromatic units are
summarized in Table 3. It is of interest that some orsellinic acid
::tl Table 3. Aromatic un its from lichens V>
tv
~
'"~
=>;
..., Co mpound Fo rm ula M .p. (0C) Lichen Synth . Scheme Ref.
No.
""'"
~ 2'-Acetoxyo liveto l 50 138-13 9 49 (181)
3'-Acetoxyoliveto l 51 Oil 49 (181)
'0
"".....,
~ Atra nol 52 124 Evernia prunastri, (51)
~ S tereocaulon vesuvianum
Fr om orci no l with (85)
DCDMe- T iCl 4
3-Chloroorsellinic acid di-O -benzyl ether 53 146.5-14 7 50 (681)
Dichloroisoeverninic acid 54 128-1 29 51,52 (179, 180)
3,5-Dihydroxy-n-heptylbenzene 55 55-56 53 (19, 297)
3,5-Dihydroxy-4-me thy1acetic acid 56 54 (605) ~
5,7-Dihydroxy-6-me thylphthalide 57 169.4 Alectoria nigricans (655, 391) ::c
1, I-Dimet hylno neicosy1 evern ina te 58 60 Evernia prunastri (561) c
::>
('l)
Divaric acid 59 157-1 59, 179 Protusnea malacea 55, 56 (182, 64, 183) n
i'<"
Divarinol 60 51,84 (452)
Divarinolm onom ethyl ether 61 Oil (452)
Ethy l 3,5-dimethy1orsellinate (2,7-di - 14 C) 62 91-92 57 (29)
Ethy l 3,5-dimet hylorse llina te (l - 13 C,7- 63 58 (642)
13C, _CO I8O Et)
Ethyl divaricatinat e 64 4 1-42 Protusnea malacea (64)
Ethyl haemat ommate 65 59 (521)
Ethyl 4-0 -meth ylolivetolcarboxylat e 66 (329)
Ethyl 5-hydroxyeverni na te 67 10 ~ I0 7 By hyd ro xylation of (3)
ethyl everni nate with
K 2 S2O S-NaOH
4-For myl-5,7-dih yd roxy-6- 68 60 (588)
meth ylphthalide
4-Fo rm yl-5-hyd ro xy-7-iso- 69 60 (588)
prop yloxyphthalide Z
<1l
G lome llin 70 85 61 (546) ~
;>:I
Grammi tic acid 71 ( 735) <1l
6-n-Heptyl-2,4-di hydroxybenzoic acid 72 55 (183) '"

S-
Haem at om mic acid 73 172-1 73 (521,672) '"
0
Hierridin 74 70-72 Ramalina hierrensis 62 (330, 328) ::l
5-Hydroxy-7-ace toxy phtha lide ;.

75 (353) <1l
5-Hydroxyeverninic acid 76 172- 173 By hyd ro xylat ion of (3) oe-

<1l
everni nic acid with 30; 0
K 2 S2 O S- NaO H
3-Hy droxy-5-me thyl-4-6-dimethoxy- 77 (685) ~
0....,
2-(tricos-9'-e nyl)-be nzene
5-Hydroxyorsellinic acid 78 132 63 (669)
r-
"'0
::r
Insignin 79 64 Porpidia glaucophaea 64 (265) <1l
::l
3-Iodoorsellinic acid 80 182- 183 50 (681) en
178- 179 e
5-Io doorsellinic aci d 81 50 (681) sr
Meth yl 3-bromoe verni nate 82 118-11 8 65 (85) '"
~
::l
Meth yl 5-bromoeve rni na te 83 143- 144 (85, 54) n
<1l
Meth yl 3-chloroorsellina te 84 133-1 34 (287) '"

5-M eth yl-2,4-di-O-meth yl- 85 208- 210 66 (55)
o rsellinic acid
Me thyl haematommat e 86 144 Cetraria islandica (658)
M eth yl 5-hydroxyeverni na te 87 153- 154 (3)
v.
....,
::>:l ..."
.j:>.
~ Table 3 (continued)
...,
'"
;:, M.p . (0C)
'"~ Compound Formula Lichen Synth. Scheme Ref.
.'" No .
~
N Methyl 3-hydroxyorsellinate 88 154- 155 67 (3,308)
v.,
'0 Methyl -5-hydroxyorsellinate 89 68 (308)
t!., Methyl 4-0-methylhaematommate 90 65 (85)
~
Methyl olivetolcarboxylate 91 69 (580)
(5,6_di_ 13C,I_ 14C)
Met hyl olivetolcarboxylate (l '_I3C) 92 69 (580)
Methyl 2-0-methyl-l3-orcinol - 93 156-157 X-ray an alysis (34)
carboxylate
70 (339)
Met hyl l3-orcinolcarboxylate 94 143- 144 70 (51) ~
4-0-Methylolivetolcarboxylic acid 95 123 ..
, (429) ::c
::l
Methyl or sellinate 208-210 From met hyl acetoa ce- (70) (1)
'o"
tate and n-BuLi with
NaH in THF and subse-
"""
quent acidification
Oliveto I 96 39--41 Cladina macaronesica 53 (329)
71 (297)
72 (474)
73 (470)
74 (443, 19)
Oliveto I (5,_2H3) 97 75 (326)
Olivetolcarboxylic acid 98 Cladina macaronesica (329)
Olivetolcarboxylic acid (5,6-di- 13C,I- 14C) 99 69 (580)
Oliveto ldimethyl ether 100 76 (637)
Oliveto lmonomethyl ether 101 Cladina macaronesica (329)
Orcinol 102 Evernia prunastri (/9, 320)
J3-0rcinol 103 Evernia prunastri (320)
By reduction of (720)
atranol with
Zn-HgjH CI
J3-0rcinolcarb oxylic acid 104 Pseudevernia f urf uracea (339) Z
Orsellinic acid lOS 55 (183) ::;;
'"
56 (182) ;:0
57 (29) '"
'"
g.
64 (669) '"
0
77 (355) ::>
78 (701) :r
79 (63 1) '"
n
80 (3 18) ::r
3
'"
(448, 336) ~.
81 (71 ) ..,
'<
82 (70) 0
....,
83 (356) e-
0'
(448, 478, ::r
::>
'"
335,336)
en
Or sellinic acid (2_14 C) 106 84 (702) c:
go
Phthalic acid Evernia prunastri (320) ~
M y rothecium spec, ::>
Rhizoni c acid 107 196, 204 (699)
~
v.
v.
56 S, Huneck
*
1 Me COOH
I~
~0Me
50: R = Ok, R'= H I
51: R = H, R'= 0Ac 54
~R
,~
52: R = Roo = H, R'=COO 55: R = Roo = H, R'= n-C,H'5
53: R = COOH, R'= CI, Roo = Bn 5S:R = COOH, R'= rH:,1i" Roo = H
60: R = Roo = H, R'= ".,Ii,
61: R = H, R' = rH:,1i" R" = Me
58
58
62: "Co2, "Co7 54: R = rH:,H 7, R'= R" = Roo,= H

Ooo
65: R = Me, R'= ROO = H, R = COO
63: "Co2, "Co7, .c'800E1 oo
66 R = n.c,H l l , R'= R ,= H, R" = Me
67. R = Me, RO= Ott, ROO = Me, R'oo= H
~
o
I~
OR'
R
68: R = Me, R' = H

69: R = H, R' = CH(Meh
Ref erences, pp , 239-276

R'*~ COOH
R'''O I A OR'"
R"
70
71 : R = n-el1 H'3, R'= R' " = H, R" = Me
*-
72 : R = n-C,H", R'= R" = R' ''= H
73 : R = Me, R'= R' ''= H, R" = CHO
R
o o
1.0 0Ac R~OH

74 75 76:R= Me
~"" 1°",
78:R=H
~ .JCC Me
80: R= R=R"'= R'-=H, R"= I
81: R= R'= R- = R- = H, R'= I
77 79
82: R= R'- = Me, R' = R'" = H, R" = Br
83: R= ~ = Me, R'= Br, R"= R" =H
84: R = Me, R' = R'"= R-= H, R" =CI
85: R = R" = H, R'= Me, R"'= R" " = Me

86: R = Me, R'= R' ''= R.... = H, R" = COH
87: R = R.... = Me, R'= OIl, R" = R"'= H
88: R=Me, R'=R' ''= R.. .. =H,R" =OH
89: R= Me, R'= OIl, R" = R' ''= R.... = H
90: R = R.... = Me, R'= R"'= H, R" = COH
91: 13C6,'3C6,'.C-l
92: . 13e-l'
h:'A
COOMe
OR 95: R =COOH, R' = H, R" = Me

96; R = R' =R" = H
Me
97:'~.5'
93: R= Me
98: R =COOH, R' = R" = H
94: R=H
99: R = COOH,R' = R" = H, 13e-5, 13e-6, "c-i
100: R= H, R'= R" = Me
101:R=R'=H, R"=Me
~
:
102: R= R' =H
103: R= H, R' = Me
'A
COOH
104: R= COOH, R'=Me
105: R = COOH,R = H
106: R = COOH, R = H, "e-2 OH
Me
107
58 S. Huneck
derivatives were found in liverworts: methyl everninate in Blasia pusilla

(751) and methyl orsellinate, methyl everninate, methyI2-methyl-3,4,6,-
tri-O-methylbenzoate,methyl 2-methyl-3 ,4-methylenedioxy-6-methoxy-
benzoate, and methyl 2-methyl-3,4-methylenedioxy-6-hydroxybenzoate
in Plagiochila killarniensis (624) .
lCH2-0Me
MeO-CH2-0~Me
o
1. Raney-Ni I.LAH
2.A c z O- Py 2.Ac ZO- Py
3. Dowex
3.Dowex
50 50
.o.r,
OH OH
HO
50
Me HO~Me 5/ OAc
S cheme 49. Synthesis of 2'- and 3'-acetoxyolivetol
R ef erences, pp . 239-276
an'#
"
HO OH
1 BoBr.K,CO,
BnBr
*
,~ 1.# ~~*~
a ""::::: COOMo COOMo
a C1
1NaOH
...
M
*= a 53
Scheme 50. Synth esis of 3-chloroors ellinic acid-di-O-benzylether

~C~_"C*I:~
HO)lAOO
so,CI 2
.# 00
:
1 BnBr a
tcl
I C~
.#
2
_CI_- . -
axX~~ .6'
a*:C~ a*:C~ ~:~~~d-C a*:C~

BnO· 00 BnO 00
,~
I A
.¥
C_H_2N_ 2_ .-
".#
I "H .# 0Me
BnO 00 BnO 0Me
a a CI
54
Scheme 51. Synthesis of dichloroi soeverninic acid after (179)
J:X
Mo COOMe
I~ PivCl
HO .# 00
a*:
Pi,CI = C(Meh-COCI
PM)
I .#
~
COOMe
0Me
CI CI CI
a*.:C~
NoOH
HO .# 0Me
CI 54
Schem e 52. Synthesis of dichloroisoeverninic acid after (180)

MoO
55 : R = n-CSH 11
0Me
Scheme 53. Synth esis of 3,5-dihydroxy-n-pentylbenzene and homol ogues
o (') ~ NaOH
~
0Me-
OAe Me
HO
- liB,
Me Me Me
56
Scheme 54. Synthesis of 3,5-dihydroxy-4-methyl-acetic acid

62 S. Huneck
)yCOO_R
~o 8r2. AcOH. A"20. HBr
R: H H H H Et El Et a Me
Me Me
59 : Divaric acid
Scheme 55. Synthesis of divaric acid and homologues
Di4mcthylo••ellinic acid, R = Me
Di4mdhyldivaric acid, R = n-C3 H7
Di-o-mcthylolivc:tolcarboxytic acid, R - n.(: SH"
Di4mcthylsphacrophorolcarboxylic acid, R - n.(:,H ts
Scheme 56. Synthesis of di-O-meth yldivaric acid and homologues
" COOEI
"(OOEI
1. EIONa
2. 8 r2
3. H2o Pd-C •
Me*: I "c
"COOEt
HO &' OH
112
Scheme 57. Synthesis of ethyl 3,5-dimethylorsellinate (2,7-di- 14 C)

»
Me
13 18
C 00Et
I 13C
.0 " 00
Me
63
Scheme 58. Synthesis of ethyl 3,5-dimethoxyorsellinate (l _13C,7- 13C,-CO I80 Et)
Me
~
Me
HO~OH
CHO
65
Ph
Scheme 59. Synthesis of ethyl haematommate

64 S. Huneck
b)
Me~
~ I. Br'. I
"
Me
-
2.",0
Me
"
h'
A
OH
0
IIMTA
68
Neitherthe carboxylicacid I nor the benzylated ~-orcinol II did reacttrifluoroacetic anhydride to the wanted
benzophenones.
~~
BOOyOBn
Me
+ ;Y
BoO
" I
~
o
OBo
~
The Smilesrearrangement of the syntheticdepsideIII also failed:
Scheme 60. Synthesis of 4-formyl-5 ,7-dihydroxy-6-methylphthalide and

4-formyl- 5-hydroxy-7-isopropyloxyphthalide
New Results on the Chemistry of Lichen Substan ces 65
EtI,Na
-
KOH
I. HCOOH
2.HBr
MeO
70
Scheme 61. Synthe sis of glomellin
OH OH OH
~~ n-C2oH.lMgBr ~~. - H2• Pd-C
o-Vanillin
I: l/~~
OH
~~.,. I I N"2~04.
o, Salcomine •
OH
l7~'" I #
OH
Mel.K,Co,
.
~~.,.
OM.
74 : Hierridin
Scheme 62. Synth esis of hierridin

66 S. Huneck
a)
Me
n ~ ~NO H
iso-Amyl-
# ---:--
~ Na,S,O,
rutrtte
HO o OH
b)
~OH
JX
OH
OHC
1# ~
OMe OHC
U~ OMe
I. n· Buli
2. Mel
C)~OH
HO~OH--':=----
HOOC: 6
: :OCOOMe
Zn(CN), , A1CI, •
HCI
OHC
HO xx I: OH
OH
CICOOMe ,
I ~
MeOOCO # OCODMe
5-Hydroxyorsellinic acid, mp 132
d) 78
~OMe
MeO~OMe
I
xx'#
Zn(CNl" A1CI, •
IICI
OHC ~ 0Me
MeO
~
OMe
Scheme 63. Synthesis of 5-hydroxyorse llinic acid

Co
;~
- C7H15 Rn-C:15
COOEt
MeO OH 1.)HCI MeO O~

2.)HCOOH 79
Scheme 64. Synth esis of insignin
.:
CI2CH-O-Me ,
TiCl4 COOMe
OH
CHO
te~ Methyl 4-0-methylhaematommate
MeO OH
COOMe
OH
Br
Methyl 3-bromoeverninate
82
Scheme 65. Synth esis of meth yl 3-brom oevernin ate

68 S. Huneck
M'~
<COOEt
COOEt
+ ) ~:.
Me
Br2 ,AcOH
•
Me
Me
Sr
Mete:COOEl
MeO
I
# OMe
NaOH. M'n~
MeO OMe
85
Scheme 66. Synthesis of 5-methy l-2,4-di-O-methylorsellinic acid
Me Me
COOMe I. H202, NaOH

COOMe
2.HCI
•
HO OH HO OH
CHO OH
88
Scheme 67. Synth esis of methyl 3-hydroxyorsellina te
OHCte=#"COOMe ~ I . H202, NaOH

2.HCI . H0te=#"COOMe ~
HO OH HO OH
-----~
89
Scheme 68. Synthesis of methyl 5-hydro xyor sellinate

a) I. CateChol
borane
2. HgCI2 ..
13
Me~HgCl + CI-COMe ..
13 0
+ 14C(COOMeh ..
Me
r;
13
j):
3 n-<:sHll COOM
3 COOMe
13 14
{):
1~Br2
2. Raney-Ni
13
I ~
# Li-propylmercaptide..
# ..
o OH HO OH
91
:&
3 n-<:sHll
I
13 ~ COOH
14
HO # OH
J:
b)
o
~ L~BuU
u~u~
MeD OMe Mea OMe MeO OMe
-
1. Me-MgC03
2. CH2N2 COOMe
HBr
OH OH
OMe
92
Scheme 69. Synt hesis of meth yl o liveto lca rboxy la te (5,6-di- 13C , I ) 4C) a nd
meth yl olivetolcarboxyla te (I ' _13C)
70 S, Huneck
~COOMe BnCI, K,co,. ~--=-_ ~COOMe 1. Mel, K,co,

2. H" P<H:
HO~OH Bn0H ~OMe

Me Me Me
93
:
te 4 4
Me Me
Zn(CN), COOMe
I
COOMe COOMe
I"=:: Ala" HCI
•
~ Zn-Hg, HCI.
1..-:::-
HO ..-:::- OH HO ..-:::- OH H H
HO Me
94
S cheme 70, Synth esis of methyl 3 - 0 - me t hyl- ~-o rci no lcarboxy la te and
methyl ~- orcin o lcarbo x ylate
J
R
rC 0 0Me J-vCOOMe
oJ. Me+ COOMe
) ~ oJ-A OH 8r2'
DMF
Scheme 71. Synthesis of olivetol after (297)

· f ~
~~
Et o
Et
-
H2,Pd -C
~
HS-CHrCHrSH
.
~
b)
f
(l-C,H"
~,, -
MeO~OM'
96
S cheme 72. Synthesis of olivetol after (474)

72 S. Huneck
)Me ,/COOH
U~
+ (COOHh
('""
COOMe
+ Me-e D-CH,COOEI
EION.
::"
j): Ji
H
r:K:. l1 COOEt
Brx>:r:K:.H
11 COOEt
I
COOEI
Br2.A cOH H~ KOH
HO:::::::"" OH-
o 0 o 0
Br
96
S chem e 73. Synthesis of olivetol after (470)
R= n-CsHIl
S cheme 74. Synthesis of olivetol after (443)

RO E OH
LAH
OR RO
~HPBr
OR
3
RO
£Br
OR
H,C\ ~))~:b;~~;H
n 3.)TMSC,.LiBr
B);
' ::::.,&
Li2CuCI"
RO OR RO OR
.,010~~SJ H:10:"·'
Scheme 75. Synthesis of oliveto I (5,_2H 3)
n-C H
1. n-BULi45"
2. n-Bu I Oxyd.
MeoAmw1-;;O~OMeMeo
TMS Cr(CO)3
\ 0;:;-
TMS Cr(CO)3
4
n - C5Hll p_TSOHn~Hll
AcOH All
MeO OMeMeO OMe
TMS
Scheme 76. Synthesis of olivetoldimethylether
105 : OrseUinic acid,R = Me
Scheme 77. Synthesis of orsellinic acid after (355)

74 S. Huneck
1.) R-Li
2.)C0 2
..
::: ~cooo
ix U
R
COOH / ••r
~
HO I .# OH MoO # 00
Scheme 78. Synthesis of orsellinic acid after (70l)
~~
Jv~o t
·w
o~o
Br
Rancy.Ni
105
Scheme 79. Synthesis of orsellinic acid after (63l)

Me
(
Br2..
1.) NaOE;(xCOOEt AcuH
---..
2.) H 2S04
------
COOEt
o 0
Me Me
COOEt Sr
Sr H2.Pd-C
H2SO4
• •
0
0
Sr Sr
I:
iX
Me
COOH
(overall yield: 30%)
HO OH
r1 Me
+ {COOEt_ ,&COOEt
0 0 0
cusr.
MeOH
COOEt
*
Me Me
COOEt Raney _. ~COOEt
- N~
MeO OH MeO OH
Br
o 0 Me
).yCOOMe
Me~OMe 1.)-Na-H-,--
n-Bul. i HOAJl-. OH
2.)HCI

76 S. Huneck
1. NaHor 1lOE!
2.Dik.ten.
3. H,SO.
Scheme 83. Synthesis of orsellinic acid (356)
+
14
):
COOEt
1. NaOE!
2. Br2
3. H2 SO.
4.H,. Pd-C
:
tr;I~
COOH
14
o HO OH
S cheme 84. Synthe sis of orsellinic acid (2_ 14 C)
4.5.2. Biphenyls
The only known biphenyl from lichens is contortin (108) from
Psoroma contortum. It was synthesized together with isocontortin (109)
according to Schemes 85 and 86 (222).
OBn
~ BnBr. K,e<>,
~.~. ~
~I~'I Cu.100"C
~~ ~ ~ ~
1. NBS
M. 2.CuCN
3.Meli
4. Hz. Pd-C •
108 : Contortin
S cheme 85. Synthe sis of con tort in

Me
Me
OH
o 0Me
Me
Me
HO
J09 : lsocontortin
Scheme 86. Synthesis of isocontortin
4.5.3. Terphenyls
Butlerins A (110), B (111), C (112), D (113), E (114) and F (115) are
p-terphenyls from Parmelia butleri (212) and Relicina connivens (207)
78 S. Huneck
0)
O,*"O &~R
·~*IOI -
R
Or
K,co" ",0
II
R
- Io<.,O,Py
~~
111: Butlerin B. R =--0-0'-

1~O,Py
~~
~
cl
112:Bu1IBl1nC. R=--O-~
Scheme 87. Synthesis of the butlerins A, Band C

respectively. The structures of 110 and 111 were established by X-r ay

an alysis; furthermore all butle rins have been synthesized (207, 284) (see
Schemes 87 and 88).
#
OMe
AeO
OAe MeOH,
0 KOH
Me O
H2,Pd-C
MeO
#
Me OMe~H Me
MeO AeO
OAe OAe
MeO OMe MeO OH ~
2 2
us. Butlerin D
#
Me O M e # A eOMe
AeO MeO
OAe + OMe
MeO OMe MeO OAe
lU : Butlerin E u s : Butlerin F
Scheme 88. Synthesis of the butlerins D, E and F

80 S. Huneck
4.5.4 . Diphenylmethanes
2,4,2',4'-Tetrahydroxy-6,6'-di-n-propyldiphenylmethane (116) was
isolated from Solorina crocea (453).
116
4.5.5. Diphenyl Ethers ( Pseudodepsidones)

2'-O-Methylphysodone (117) was isolated from Pseudevernia fur-
furacea (339). p-Alectoronic acid (118) and p-collatolic acid (119) are
diphenyl ethers from Asah inea chrysantha (476) and A . scholanderi (476,
672) and exhibit an equilibrium between the keto-acid and lactol
tautomers. 2'"-O-Ethyl-p-alectoronic acid (120) from Alectoria sarmen-
tosa (327) is probably an artefact formed during extraction by reaction
of p-alectoronic acid with ethanol.
/1 7
Micareic acid (121) and methoxymicareic acid (122) have been

found in chemical races of Mi carea prasina and have been synthesized
from 2-0-methyl-4-hydroxy-6-n-hept ylbenzoate (236) according to
Scheme 89.

118: O·Alectoronic acid,R ~ H
119: Il-Collatolic acid,R = Me
Epiphorellic acid 1 (123) and 2 (124) are diphenyl ethers from

Cornicularia epiphorella (296). Elix and Jenie (225) described the
synthesis of epiphorellic acid 1 (see Scheme 90) and Comber et al.
(77) the synthesis of epiphorellic acid 2 (see Scheme 91).
R
J-vCOOMe Me0'(YoH
HO~O~COOH
n-CsH"
123: Epipborellic acid I, R = n·C,H II
124 : Epipborellic acid 2, R = ·(CH,),.CQ.Et

82 S. Huneck
R R
.J--COOMe .J".,.,COOMe
oJ-A CI +HO~OMeK2C03
R R R R
J.vCOOMe )yCOOMe J.vCOOH J.vCOOH
MeoN--O~Me1.)BCI 3 MeON-O-UOH 119
2.)KOH
=
R n - C 15
7H
121 : Micareic acid
R R R R
J.vco~e MeO-..J..vCOOM..:- NCOOMe MeO J-vCOOM_e_
O~CI HO~OMe O~O----UOMe Br2
R R R R
)..yCOOMe MeO-.J..v.COO~ ).yCOOH MeO~COOH 120
HoN--o~OMe MeO~O--UOH
I.)Mel.K 2C03
2.)BCI 3
122 : Methoxymicareic acid
3.)KOH
Scheme 89. Synthesis of micareic acid and methoxymicareic acid
:te:
R
tt ~ COOEI CI,CHOMe. COOE!

I"':: ~
MoO b OMe ......=:=--_.
SoCl,
M b H
U
R R
HOC cooso
I "':: Bnar. K
,co, •
HOC:xxRCOOBn
1 "'::
HOUCOOBn 1. H, . Pd.c
1. MCPBA
1 HOM
MoO b OH b 2. H,O
Me Bn - - . . MeO b DBn •
jx
R
COOH- TFAA:te
R R
COOBn
R co-:xX: COOBn
H 1: "'::
te +
~ I I~ I~ K,CO, .DMSO.
Me b OH B OH Bn ~ OH b H
JX:
R OM.
COO~OH 1.CH,N,
1 ~ ~ I 2H, .Pd.c
Bz b ~ OOBn H
123 : Ep iphorel ic acid 1
Scheme 90. Synthesis of epiphorellic acid I

BOO
e .
S cheme 9/. Synthesis of epiphorellic acid 2

84 S. Huneck
te H~OMe ;):~CO_O~:
R
COOH
I 1-
DCCO K,Co,
I~ I~-
800 ~OH+ R" ~OH Bn ~OHR" ~OH
OOBn OOBn
te te
R R
I ~
COOH MeO::ytoH
I~ H,. Pd.c
I ~ COOH)yCoH
I ~
BnO ~ ~ COOBn HO ~ ~ COOH
o
125 : Epiphorellic acid 3
Scheme 92. Synthesis of epiphorellic acid 3
Elix and McCaffery (246) reported isolation from Coelopogon

abraxes of another isomer, epiphorellic acid 3 (125) and its synthesis
(see Scheme 92).
4.5.6. Depsides
Depsides isolated and structurally elucidated between 1983 and 1999
are summarized in Table 4.
Most of the newly described depsides were synthesized by Elix and
co-workers by condensation of the appropriately protected S and A
parts with either trifluoroacetic anhydride (TFAA) or N,N'-dic-
yclohexylcarbodiimide (DCCD). Ramesh and Baig (612) synthesized
methyl evernate and methyl gyrophorate by oxidation-reduction
condensation using 2,2'-dibenzoxazolyldisulfide as an oxidizing agent.
The depsides confluentic and 2'-O-methylperlatolic acids were described
as occurring in the higher plant Himatanthus sucuuba, but originate very
probably from lichens contaminating the plant material (280). The
structure of sekikaic acid was confirmed by an X-ray analysis (451). The
synthesis of methyl alectorialate (289) (see Scheme 108) and methyl
barbatolate (290) (see Scheme 109) has been achieved by Elix and
Jayanthi (220).
A depside named vermicularin (349) proved to be identical with
decarboxythamnolic acid (291), the synthesis of which was described by
Pulgarin and Tabacchi (591) (see Scheme 110).
Huneck et al. (408) have investigated the thermal decomposition of
lichen depsides. The main decomposition products were decarboxylated
Table 4. Depsides from lichen s
Co mpo und Formula M .p. (0C) Lichen Synth. Scheme Ref.

No .
5-0-Acetyl-4-0-metylhiascic 126 165-1 67 Koerberiella wimmeriana 93 (277)

acid Z
(1)
Artho niaic acid 127 167 94 (266) :E
Brialm on tin 1 128 102-104 Lecania brialmontii (71/) :;>;I
(1)
From 2,4-dimethoxy- 3,5,6-trimeth yl- (192) '"

benzoic acid and 3-methoxy-2,5,6- ~
0
trimethylphenol with T FAA ::l
Brialm ontin 2 129 106- 109 Lecania brialmontii (711) So
(1)
From 2-hydroxy-4-methoxy-3,5,6- (192) ocr
trimethylbenzoic acid and 3-meth- n>
oxy-2,5,6-trimethylpheno l with T FAA 3
sao
3-Chloro divarica tic acid 130 158-159 Thelomma mammosum ..,
'<
Ramalina seyreana 95 (25/) 0
....,
5-Chlorodivarica tic acid 131 142-143 Dimelaena cf. radiata (245) r-
n·
3-Chloroim bricaric acid 132 128-130 From 3-chloro-2-hydroxy-4-meth- (208) tr-
n>
ox y-6-n-pentylbenzoic acid and benzyl ::l
en
2,4-di hydroxy-6-n-propylbenzoat e with
TFAA and sub sequ ent debenzylat ion
''"c0;-"r
(194) ::l
5-Chl or o-2'-O-methylan ziaic 133 142-143 Lecanora lividocinerea From 4,6-dibenzylox y-3-chloro-2-n- n
acid pent yl-ben zoic acid a nd benzyl 4-hydr- ~
ox y-2-methoxy-6-n-pent ylbenzoat e with
TFAA and subseq uent debenzylati on
I'-Chl o ronephroarctin 134 181 Pseudocyph ellaria 96 (275)
pickeringii
00
v.
::z:., Table 4 (continued) 00
0-
~
-e
'"
::: Compound Formula M .p. (0C) Lichen Synth. Scheme Ref.
'"
~
.'" No .
~ 3-Chloroperlatolic acid 135 128 Dimelaena califarnica From 3-chloro-2-hydroxy-4-methoxy- (208)

w
'" 6-n-pentylbenzoic acid and benzyl
'f 2,4-dihydroxy-6-n-pentylbenzoate with
0\
"'" TFAA and subsequent debenzylation
3-Chlorostenosporic acid 136 138 Dimlaena californica From 3-chloro-2-hydroxy-4-methoxy-6- (208)
propylbenzoic acid and benzyl 2,4-
dihydroxy-6-n-pentylbenzoate with
TFAA and subsequent debenzylation
Conechinocarpic acid 137 > 290 Relicina samoensis (264)
Crustinic acid 138 178-180, Umbilicaria crustulosa (401, yo
dec. 582) :r:
By condensation of 2,4-dibenzyloxy- (223) <=
::s
('l)
6-methylbenzoic acid and benzyl ()
I';"
4-benzyloxy-3-(2' ,4' -dihyd ro xy-6'-rnethyl-
benzoyloxy)-6-hydroxy-2-methylbenzoate
with TFAA and subsequent debenzylation
Decarboxyanziaic acid 139 102-104 Neofusc elia depsidella From 4-benzyloxy-2-hydroxy-6-n- (267)
pentylbenzoic acid and olivetol with
DCCD and subsequent debenzylation
D ecarboxydivaricatic acid 140 Oil Neofuscelia depsidella From 2-hydroxy-4-methoxy-6-n-propyl- (267)
benzoic acid and divarol with DCCD
Decarboxy-2'-O-methyl- 141 Oil Neofuscelia depsidella From 2-hydroxy-4-methoxy-6-n-propyl- (267)
divaricatic acid benzoic acid and 3-methoxy-5-n-
propylphenol with DCCD
Decarboxy-2'-O-methyl- 142 96-97 Neofuscelia depsidella From 4-benzyloxy-2-hydroxy-6-n-pentyl- (267)
norimbricaric acid benzoic acid and 3-methoxy-5-
n-propylphenol with DCCD and
subsequent debenzylation
Decarboxynorimbricaric 143 99-100 N eofus celia depsidella From 4-benzyloxy-2-hydroxy-6-n- (267)
acid pen tyl-benzoic acid and 1,3-dihydroxy-
5-n-propylbenzene with DCCD and
Decarboxynorstenosporic acid 144 84-85 Neofuscelia depsidella From 2,4-dibenzyloxy-6-n-propylbenzoic (267)
acid and 1,3-dihydroxy-5-n-pentylbenzene
with DCCD and subsequent debenzylation Z
(l>
Decarboxyperlatolic acid 145 73-74 Neofuscelia depsidella From 2-hydroxy-4-methoxy-6-n-pentyl- (267) ~

:;:0
benzoic acid and 1,3-dihydroxy-5-n-pentyl- (l>
'J>
benzene with D CCD
Decarboxystenosporic acid 146 Oil Neofus celia depsidella From 2-hydroxy-4-methoxy-6-n-propyl- (267)
~
0
benzoic acid and 1,3-dihydroxy-5-n-pentyl- ::s
benzene with DCCD s:-
(l>
4-0-Demethylbaeomycesic acid 147 171 -172 Dibaeis arcuatus (336) n

;:r
(l>
4-0-Demethyldiffractaic acid 148 Xan thoparmelia duplicata From 4-benzy loxy-2-methoxy-3,6-di- (199) 3
methylbenzoic acid and benzyl 2,4- C;;"
dihydroxy-3,6-dimethylbenzoate with ~
0-,
TFAA and subsequent debenzylation
4-0 -DemethylglomelIic acid 149 152 Neofuscelia loxodes 97 (273)
r-
n"
;:r
4-0-DemethylglomelIiferic acid 150 156 Neofuscelia loxodes 97 (273) (l>
::s
4-0-Demethylimbricaric acid 151 169 Cet relia sanguinea From 2,4-dibenzyloxy-6-n-pentylbenzoic (251) rJl
c
acid and benzyl 2,4-dihydroxy-6-n- go
propylbenzoate with TFAA and 10
::s
(")
subsequent deb enzylation (l>
'J>
4-0-Demethylloxodellic acid 152 146 Neofuscelia loxodes 97 (273)
4-0-DemethylmicrophylIinic 153 162 Parmotrema demethyl- 98 (221)
acid microphy//inum
4-0-Demethylperiatolic acid 154 Ramalina americana (96)
4-0-Demethylplanaic acid 155 122-12 4 Lecidea plana (405)
4'-O-Demethylsekikaic acid 156 Ramalina americana (96)
00
......
::<:l 00
00
~
'"~ Table 4 (continued)
::::
.Cl'"' Compound Formula M .p. (0C) Lichen Synth. Scheme Ref.
~ No.
tv
....,
4-0-Demet hylsp haerophorin 157 136 Sphaerophorus From 2,4-dibenzyloxyorsellinic acid and (262)
'f'
tv benzyl 2-n-heptyl-4,6-di hydroxy-benzoate
melanocarpus
~ with TFAA and subsequent debenzylation
4-0-Demethylsquamatic acid 158 128- 130 Pertusaria squamatica (336)
4-0-Demethylstenosporic acid 159 108 Neofuscelia pulla From 4-benzyloxy-2-hydroxy-6-n-propyl- (251)
benzoic acid and benzyl 2,4-dihydroxy-
6-n-pentylbenzoate with TFAA and
4-0-Demethylsuperconfluentic 160 165 Porpidia glaucophaea 99 (265, :-n
acid 103) ::I:
t::
From 2-hydroxy-4-methoxy-6-n-propyl- (267) ;:l
Depsidellin A 161 Oil Neofuscelia depsidella
(")
benzoic acid and olivetoI with DCCD :-;-
'"
Depsidellin B 162 114-115 Neof uscelia depsidella From 2-hydroxy-4-benzyloxy-6-n-pentyl- (267)
benzoic acid and oliveto l with DCCD
and sub sequent debenzylation
Depsidellin C 163 Oil Neofuscelia depsidella From 2-hydroxy-4-methoxy-6-n-propyl- (267)
benzoic acid and 3'-hydroxy-5'-n-pe ntyl -4-
benzy loxy-2-h ydroxy-6-n-pentylbenzoate
with DCCD and subseq uent debenzyla tion
3,5-Dichloro-4-0-methylpla naic 164 119-129 Lecanora jamesii (46)
acid
Lecanora lividocinerea From 4-ben zyloxy-3 ,5-d ichloro-2-meth- (194)
oxy-6-n-pentylbenzoic acid and benzy l-2-
O-methyl-olivetolcarboxylate with TFAA
and subsequent debenzylation
3,5-Dichloro-2'-O-methylanziaic 165 154-155 Lecanora sulphurella From 3,5-dichloroolivetolcarboxylic acid (251)
acid and benzyl 4-hydroxy-2-methoxy-6-n-
pen tylbenzoate with T FAA and
3,5-Dichloro-2' -O-me thylnor- 166 154-155 Lecanora lividocinerea From 3,5-dichloro-2,4-dihydroxy-6-n- (194)
hyperlatolic acid pentylbenzoic acid and benzyl 2-n- Z
(1l
heptyl-4-hydroxy-6-methoxybenzoate ::E!
;.:l
with DCCD and subsequent debenzylation (1l
3,5-Dichloro-2'-O-methyl- 167 165- 166 Lecanora lividocinerea From 3,5-dichloro-2,4-dihydroxy-6-n- (194) '"
g.
norstenosporic acid propylbenzoic acid and benzyl 4-hydroxy- '"
0
::;
2-methoxy-6-n-pentylbenzoate with DCCD
and subsequent debenzylation s:-
<I>
2,2'- Di-O-methyldivaricatic acid 168 129-13 1 Pertusaria subplanaica From 2,4-dimethoxy-6-n-propylbenzoic (192) (')
::r
<I>
acid and ben zyl 4-hydroxy-2-met hoxy -6- 3
n-propyl-benzoate with TFAA and subse - t;; "
quent debenzylation S
0
..,
2,4- Di-O -met hylhiascic acid 169 By condensation of 3-benzyloxy-4 ,6- (223)
dimethoxy-2-methylbenzoic acid and r:
o
::r
benzyl lecano rate with T FAA and <I>
::;
subsequent debenzylation lZl
c=
2,5-Di-O-methylhiascic acid 170 By condensation of 4-benzyloxy-3,6- (223) go
dimethoxy-2-methylbenzoic acid and ~
::;
(')
benzyl lecanorate with T FAA and ~
2,2' -Di -O -methylimbricaric acid 171 137-138 From 2,4-dimethoxy-6-n-pentylbenzoic (192)
acid and benzyl 4-hydroxy-2-methoxy-
6-n-propylbenzoate with TFAA and
sub sequent dcbenzylation
00
'0
:;., Table 4 (co ntinued) 0
'"
~
'"...
::s
'" Co mpound Fo rmu la M .p. (0C) Liche n Synth. Schem e Ref.
."~ N o.
~ 2,2'-Di-O-meth ylstenosporic 172 135 Pert usaria subplanaica From 2,4-dim eth oxy-6-n-propylbenzoic (192)
~ acid acid and ben zyl 4-hydrox y-2-m eth oxy-
'f' 6-n-pentylbenzoate with TFAA an d
""
~ subseq uent debenzylat io n
Dissectic ac id 173 > 285 He terodermia dissecta From 2,4,5-trihydroxy-3,6-di methyl- (263)
benzo at e and haem atommic acid with
DCCD
Echinoca rpic ac id 174 146-148 Parmelia norcrambidio- (24/)
carpa
Elatinic acid 175 212 Haematomm a (95) ~
ochrophaeum ::r:
Loxospora elatina Fro m 2-hydroxy-4-m eth oxy-6-meth yl-3- (199) c
formylbenzoi c acid and meth yl 2,4-dihy-
...::3n
:>;"
droxy-3,6-dimethylbenzoat e with T FAA
and subseq uent oxidatio n with NaOCh
G laucophae ic acid 176 107 Porpidia glaucophaea 99 (265)
G lomellic acid 177 132 97 (273)
G lomelliferic acid 178 145 97 (273)
8-Hydroxy barba tic acid 179 192- 194 By red uct ion o f baeo mycesic acid (192,
with N aB H 4 96)
8-Hydroxy di ffrac ta ic acid 180 156-158 Usnea longissima (565)
3-Hydroxygyropho ric acid 181 154-1 60 By condensat ion of 2,3,4-tribenzyloxy -6- (223)
meth ylbenzoic acid and ben zyl leca-
nor ate with T FAA and subseq uent
deben zylati on
5-Hydroxy leca nor ic acid 182 (206)
3-Hy droxy-4-0-methylgyropho ric 183 183- 184 By condensa tio n of 2,3-dibenzyloxy- (223)
acid 4-methoxy-6-methylbenzoic acid and
benzy l lecano rat e with TFAA and
3-Hydroxy-4-0-methylum- 184 168-169 By condensation of 3-benzy loxy-2,4- (223)
bilicaric acid dimethoxy-6-methylbenzoic acid and
benzyllecanorate with TFAA and Z
(1)
subsequent debe nzylation ~

:;>;:I
3-Hydroxyovoic acid 185 155- 157 By condensation of 2,3,4-tribenzyloxy -6- (223) (1)
v.
met hy lbenzoic acid and benzyl 2-0-
methyllecano ra te with TFAA and
~
0
::l
:;:.
(1)
3-Hydroxyumbi licaric acid 186 186-187 Parmelinopsis bonariensis IOOa (234)
(J
Hyperconfluentic acid 187 148 Pseudobaeomyces 94 (266) :r
(1)
pachycarpa 3
~.
Hyperhomosekikaic acid 188 125- 126 Cladonia chlorophaea From 2-hydroxy-4-methoxy-6-n-pentyl- (/92) ....
'<;
benzoic acid and benzyl 2,3-dihydroxy-4-
0
....,
me thoxy-6-n-pe nty lbenzoate with T FAA
t"""'
and subsequent debenzylation (So
tr-
Ramalina americana (96) (1)
::l
Hyperlatolic acid 189 113 Ropalospora viridis (/O!) C/l
From 4-0 -methylolivetolcar boxylic acid (262) v.
'cr0;"
and benzyl 2,4-di hydroxy-6-n-heptyl- :::
()
benzoate with TFAA and subsequent (1)
v.
debenzylation
Hyperplanaic acid 190 128 Lecanora planaica From 2,4-dimethylolivetolcarboxylic (/93)
acid and benzyl 2-methoxy-4-hydroxy-6-
n-he ptylca rboxylate wit h TFAA and
'-0
~ '0
tv
~ Table 4 (continued)
...
'"
::
'"
" Compound Formula M.p . (0C) Lichen Synth. Scheme Ref.
~
No .
~
N
w Hypoalectorialic acid 191 190-195 Hypotrachyna (264)
'P
N hypoalectorica
0\
" Hyponep hroarctin (NA -3) 192 165- 170 Nephroma arcticum (453)
Isoh yperlat olic acid 193 103 Ropalospora viridis (101)

From 2-hydroxy-4-methoxy-6-n-hep tyl- (262)
benzoic acid and benzyl 2,4-dihydroxy-
6-n-pentylbenzoate with TFAA an d !Z'
subsequent debenzylation ::r:
c
Isohyperplanaic acid 194 122-1 23 Lecanora planaica From 2,4-dimethoxy-6-n-heptylbenzoic (193) ::>
(1)
n
acid and benzyl 2-0-methy l-4-hydroxy- :>;-
6-n-pentylbenzoate with T FAA and

sub seque nt debenzylation
Isolecano ric acid 195 >300, dec. Parmotrema tinctorum (627)
Isomerochlorophaeic acid 196 146 Ramalina spec. from Fiji From 2,4-dimethoxy-6-n-pentylbenzoic (192)
acid and 4-benzy loxy-2,3-dihydroxy-6-
n-propylbenzoate withTFAA and
subsequen t debenzylation
Isonorobtusatic acid 197 168-1 69 Ramalina americana From 2,4-dibenzyloxy-6-methylbe nzoic (192)
acid and benzyl 2,4-dihydroxy-3,6-di-
met hylbenzoate with TFAA and
Isopatagonic acid 198 146-14 7 Bunodophoron 10 1 (260)
patagonicum
Isop seud ocyphellarin A 199 201 Pseudocyphel/aria F ro m 2,4-dih ydroxy-3- formyl-5,6- (2 75)
p ickeringii dimethylbenzoic acid and meth yl 2,4-dihydr -
oxy-3,5,6-trimeth ylbenzo at e with T FAA
Isosph aeric acid 200 142 Dimelaena oreina Fro m 2-hydroxy -4-methoxy-6-n-heptyl- (262 )
benzoic acid and benzyl orsellina te with
T FAA and subsequent debenzylation
Lasallic acid 201 181-1 83 L asallia asiae-oriental is (556 , Z
(1)
558) :;;
~
By condensa tio n of 2,4-dibenzyloxy-6- (223) (1)
meth ylbenzoic acid and benzyl 4-benzyl- ~

en
oxy-3-(2',4'- dihydroxy-6'-methylbenzoy l- 0
::l
oxy)-2-hydroxy -6-methylbenzoate with
TF AA and subsequent debenzylation s:.
(1)
Lox odellic acid 202 137 97 (2 73) (J

::r
(1)
3-Me tho xygyro pho ric acid 203 175- 177 By condensa tion of 2,4-dibenzyloxy-3- (223) 3
meth oxy-6-meth ylbenzoic acid and 0;'
benzyl lecano rate with T FAA and Q

0
subsequent deb enzylati on -,
t""'
3-Me thoxy-4-0 -methylgyro- 204 192-193 By condensation of 2-benzyloxy-3,4- (223) n'
::r
(1)
ph oric acid dim eth oxy-6-meth ylben zoic acid and ::l
benzyl lecan or at e with TFAA and en
<=
subsequent deben zylat ion g-
3-Methoxyumbilicari c ac id 205 170-1 71 Parm elinopsis bonariensis 100b (234) p;
::l
n
Methyl alectorialate 289 204-20 5, dec, 108 (220) (1)
en
2-0-Methylan ziaic acid 206 116-1 17 Ramalina americana (96)
2'-O-Methylatranorin 207 146-147 Oropogon lox ensis From 3-form yl-2,4-d ihydr oxy-6-methyl - (199)
benzoic acid and meth yl 4-hydroxy-2-meth-
oxy-3,6-dimethylbenzoate with T F AA
Methyl ba rba ta te 208 173 Haemat omma ochrophaeum (95)
\C>
...,
:>::> 'C>
~
~
"''" Table 4 (con tinu ed)
'"
"''""
"" Co mpo und Formula M .p . (DC) Lichen Syn th. Scheme Ref.
~ No .
~
l' Me thyl ba rba to late 290 185-1 86, Alecto ria nigricans 109 (220)
""~ dec.
Meth yl 5-chl o ro -4-0-demethyl- 209 162-164 Erioderm a spec. From 2,4-d ihydr oxy-3,6-dimethyl-5- (244)
barb at at e chl o rob enzoic acid and meth yl
13-orsellinat e with T FAA
Methyl 5-chl or on or obtusat e 210 164 Erioderma spec. F rom 2,4-d iben zyloxy-3,6-dimeth yl-5- (199)
chIorobenzoic acid and meth yl o rsellinate
with T FAA and subseq uent deb enzylat ion ~
4'-O-M eth ylcrypt ochlorophaeic 211 152 Ramalin a asahinae From 4-benzylox y-2-meth ox y-6-n-pentyl- (261) ::t:
acid benzoic acid and 2,3-dihydrox y-4-methoxy- c::
::s
(l)
(')
6-n-p entylbenzo ate with TFAA and ;>';"
subseq uent deb enzylati on
Methyl 2,2'-di-O-methyldivaric a- 212 63- 63 Pertu saria oraraensis (269)
tate
Meth yl 2,2'-di-O -methylerioder- 213 168 Erioderma spec . From 2-meth oxy-3,6-dim eth yl-4-benzylox y- (244)
mat e 5-chl or ob enzoic acid and methyl 2-meth oxy-
3,5,6-trimethyl-4-h ydroxyben zoat e with
TFAA and subseq uent deb enzylation
Meth yl 2,2'-di-O -methylsteno- 214 56-57 Pert usaria subplanaica (269)
spora te
2-0-Methyldivari cat ic acid 215 11 8 Ram alina seyreana From 2,4-dimethoxy -6-n-propylbenzoic (251)
ac id and benzyl 2,4-dihyd rox y-6-n-propyl-
ben zoat e with TFAA and subseq uent
de benzyla tion
2' -0- Methyld iva rica tic acid 216 142-143 Pertusaria velloziae F ro m benzyl 4-h ydro xy-2-m ethoxy-6-n- (191)
propylbenzoate a nd 2-benzy loxy- 4-
methoxy-6-n-p ropylben zoi c ac id with
TFAA and subse que nt deben zyla tion
M ethyl eriod erma te 217 165 Erioderma spec . From 2,4-dibenzyloxy-5-chl oro-3,6- (244)
dimethylben zoi c ac id a nd methyl 2,4-
dih ydroxy-3,5,6-t rimeth ylbenzoat e with Z
f>
T FAA a nd su bseq uen t deb enzylat ion ~
:;>;l
2-0- Me thy lglome lliferic acid 218 104-1 0 5 Ramalina amer icana 94 (96, ~
266) ~
2"-0-Me thylgyro p ho ric acid 219 176-1 78 Diploschistes gy rophoricus, 102 (190) '"
0
::s
R inodina alba
:;:.
2-0- Me thy lhiascic acid 220 137-1 39 Parmelinopsis From 4,5-d iben zyloxy-2-met hoxy-6- (224) f>
(J
neodamaziana methylbenzoic aci d a nd be nzy l leca norat e =0-
f>
wit h TFAA a nd su bseq uent deb enzyla tion
2' -0-Me thy lhiascic aci d 221 207-209 Catillaria corymbosa (712) ~.
..,
4- 0 -M ethylhiascic a cid 222 Parmelinopsis schindleri (277) '<
0
....,
M ethyl 8-hyd roxybarba ta te 223 148-1 52 Erioderma spec . By reduction o f methyl baeo m ycesate (192)
r-
(S.
with N a BH 4
=0-
M ethyl 8-hyd roxy-4-0- 224 156 Oropogo n lox odensis By reduction of a trano rin with N aBH 4 (192) f>
::s
de met hy lbarba ta te en
:::
2-0- Me thy lhyper la to lic ac id 225 82-83 Pertusaria fo llmanniana F ro m 2,4-d ime thoxy-6-n-pen tylbenzoic (19 1) 0"
acid a nd ben zyl 2,4-di hydroxy-6-n- or'"

::s
o
heptylbenzo at e with T FAA a nd ~
su bseq uent deb enzylati on
2'-0-Me thy lhype rla to lic ac id 226 Lecanora ja mesii (46)
4-0-Meth ylhyperol ivet oric acid 227 Pseudobaeomyces (92)
pachy carpa
94 (266)
2'-0- M ethylhyperphyllin ic 228 148 Pseudobaeomy ces 94 (266)
ac id A pachycarpa V>
'"
:>:> Tabl e 4 (co ntinued) 'D
0-
~
n,
.,
'" Compound Formula M .p . (0C) Lichen Synth. Scheme Ref.
.''~"" No.
~ 2'-0 - Methylhyperphyllinic 229 140 Pseudobaeon1yces 94 (266)

tv
...., acid B pachy carpa
'f'
tv Methyl hyperplanaiate 230 53 Pertu saria manam ensis (269)
0-
" 2'-0 -Methylim brica ric acid 231 126 Lecidea cyanosarca From 2-hydroxy-4-methoxy-6-n-pentyl- (/ 92)
benzoic acid and ben zyl 4-hydroxy-2-
methoxy-6-n-propylbenzoate with TFAA
and sub sequent debenzylation
4-0-Methylisoc rypto- 232 152- 153 Pertu saria paradoxica From 2,4 -dimethox y-6-n-pentylben zoic (/92)
ch lorophaeic acid aci d and ben zyl 4,6-dibenzyloxy- 3-
hydroxy-2-n-pentylbenzoate with TFAA V'
and subsequent debenzylation :r:
2-0-Methyli sohyperlatolic acid 233 84 Pertu saria fo llm aniana F rom 2-n-heptyl-4,6-dimethoxyben zo ic (/ 91) <=
::>
acid and benzyl 2,4-dihydroxy-6-n- o
:0;-
'"
pen tylbe nzo ate with TFAA a nd
2'-0-Methylisohyperlatolic acid 234 127-128.5 Biat ora sorediosa From 2-n-heptyl-4-methoxy-6-hydro xy- (204)
benzoic acid and benzyl 2-0-methyl-
olivetolcarboxylate with TFAA a nd
subsequent debenzylati on
Meth yl isohyperpla na iate 235 60-61 Pertu saria manamensis (269)
2'-0 -Methylisopseudo- 236 171 Pseudo cyph ellaria From 5-formyl-2,4-dihydrox y-3 ,6- (275)
cyphella rin A pick eringii dimethylbenzoic acid a nd 4-h ydroxy-2-
methoxy-3,5 ,6-trimethylben zoate with
TFAA
M eth yl 2-0-methyldivaricata te 237 80-82 Pertu saria oraraenis (269)
Meth yl 2-0 -methylerioderma te 238 167 Erioderma spec. From 4-benzyloxy-3-chloro-6-methoxy- (244)
2,5-dim ethylbenzoic acid and meth yl 2,4-
dihydroxy-3,5,6-tr imeth ylbenzoate with
TFAA and subsequent deben zylati on
Methyl 2'-O-methyleriodermate 239 172 Erioderma spec. From 2,4-dibenzyloxy-5-chloro -3,6- (244)
dimethylbenzoate and methyl 4-hydroxy-
2-methoxy-3,5,6-trimethylb enzoate with Z
<'0
~
TFAA and subsequent deb enzylati on
::0
Meth yl 4-0-meth yleriodermate 240 124 Erioderma spec. From 2-ben zyloxy-5-chlor o-4-me thoxy-3,6- (244) <'0
dimeth ylbenzoic acid and meth yl 2,4- ~

dih ydr oxy-3,5,6-trimeth ylbenzoate with '"
0
;:l
TFAA and subsequent debenzylati on
Meth yI 2'-O-meth ylmicro- 241 Porpidia diversa
So
<'0
(334)
(")
ph yllinate ::r'
<'0
Meth yl 2-0 -methylperla tolate 242 Oil Pertusaria x enisoma ta (269) 3
2'-O- Methylmicrophyllinic acid 243 152 Porpidia leptocarpa 94 (266) tn·
2'- O-Me thylnorbarbatic acid 244 162 Pseudocyp hellaria From 2,4-dibenzyloxy-3,6-dimeth yl- (200) S
0
..,
norvergica benzoate and benzyl 4-h ydrox y-2-
r-
methoxy-3,6-dimethylbenzoat e with n'
::r'
TFAA and subsequent de benzylat ion <'0
;:l
4'-O-Meth ylnor crypt o- 245 160 Cladonia merochlorophaea From 2,4-dibenzyloxy-6-n-pent ylbenzoic (261) CIl
e
chlorophaeic acid acid and ben zyl 2,3-dihydro xy-4-meth oxy- 0-
'"
iii
6-n-pentylben zoat e with T FAA and ;:l
()
subsequent deben zylat ion a
2-0 -Methylnordivaricatic acid 246 Ramalina americana (96)
4'-O-Methylnorhomosekikaic 247 176 Ram alina luciae From 2,4-dibenz yloxy-6-n-prop ylbenzoic (261)
acid acid and ben zyl 2,3-dihydroxy-4-metho xy-
6-n-pentylbenzoate with T FAA and
sub sequent debenzylati on
'0
-.I
'J:)
~ Table 4 (continued) 00
~
....
'"
:::
'" Co mpound Formula M.p . (0C) Lichen Synth. Schem e Ref.
...,
.~ No.
~ 2-0- Methylno rimbricaric acid 248 124-1 25 not yet found in lichens F ro m 2-meth ox y-4-b enzyloxy-6-n- (19 7)
"-'
w pen tylbenzoic acid a nd 2,4-d ihydr oxy-
'P 6-n-pro pylbenzoa te with TFAA and
"-'
~ subseq uent deben zylat ion
2'-O- Methylno ro btusa tic aci d 249 191- 193 Pseudo cyphellaria Fro m 4-benzyloxy-2-hyd roxy-3,6- (200)
nor vegica dimethylbenzoic acid and benzyl 4-
hydr oxy-2-methoxy-6-meth ylbenzoat e with
T FAA and subsq uent debenzyla tio n
4' -O- Methylno rsekika ic acid 250 159-1 61, Ram alin a fa rina cea, Fro m 2,4-dibenzyloxy-6 -n-pro pylbenzo ic (261)
182 R. luciae acid and benzyl 2,3-dihydroxy-4-me thoxy- ~
6-n-propy1benzoat e with T FA A and :t
subsequent debenzylati on t:
::l
ro
2-0- Methy1no rstenos poric acid 251 111-1 13 Ram alina ame ricana (96) n
".,.
2-0-Methylno rsuperla to lic acid 252 85-87 not yet found in lichens From 2-methoxy-4-b enzyloxy-6-n- (1 9 7)
hepty1 benzoic acid and 2,4-dihydroxy-
6-n-heptylbenzoate with TFAA and
subseq uent debenzylati on
2'-O -Methylno rsuperphyllinic 253 165 Sti rto nia ram osa (103)
acid
94 (266)
4-0 -Meth yl-2" -oxo- 254 75 Ram alin a subfrax inea (9 7)
cryptochloro phaeic acid
94 (266)
2'-O- Mcthylphena rctin 255 166 Pseudocyphellaria Fro m 3,5-difo rm yl-2,4-dihydroxy-6-meth yl- (275)
pick eringii benzoic acid and meth yl 4-hydroxy-2-
methoxy-3,5,6-trim ethylbenzoat e with
TFAA
Meth yl planaiate 256 58-60 Pertusaria m anam enensis (269)
2'-O-M ethylpseudo- 257 190 Pseudocyphellaria From 3-formyl-2,4-d ihydroxy-5,6-d imethyl- (2 75)
cyphellarin A pick eringii benzoic acid and meth yl 2,4-dihydroxy-
3,5,6-trime thy lbenzo ate with T FAA
Methyl sekika te 258 124 Prot ousnea dusenii (698)
2-0- Methylsqua ma tic acid 259 216-220 Protousnea m agellani ca (3 13)
By oxida tio n of 2-0 -methylbaeomycesic (199) Z
acid with NaOCI2 sulfam ic ac id '"
~
:;0
2-0- Me thylstenos po ric acid 260 108, 112 Ram alina sey reana, Fr om 2,4-d imeth oxy-6-n-prop ylbenzoic acid (251)
Ce trelia sanguiana
'"
'"
and ben zyl 2,4-dihydroxy-6-n-pcnt ylbenzoat e g.
with TFAA and subseq uent debenzylati on '"
0
2'-O -Me thylstenos po ric acid 261 ::l
127 Physcidia cy lindrophora From 2-hyd ro xy-4-meth oxy-6-Il-p rop yl- (192)
ben zoic acid and benzyl 4-hyd roxy-2-
:;.
meth oxy-6-n-pent ylbenzoat e with TFA A '"
n
::r
and subseq uent debenzylat ion '"
3
2-0 -Methylsulphurellin 262 L ecanora ja m esii (46) ~.
2-0- Mc thylsuperlato lic acid 263 71-72 Pertusaria fo llm anniana From 2-n-hep tyl-4,6-dimeth oxybenzoic acid (191) ~
0
....,
a nd ben zyl 2,4-dihyd ro xy-6-n-hep tylbenzoatc
with TFAA and subseq uent dcbenzylati on c:
(")
::r
2'-O-Me thylsuperla to lic acid 264 11 4-11 5 Biat ora sorediosa F ro m 2-n-heptyl-6-hyd roxy-4-mc thoxy bcn- (204) ::l
'"
zoic acid and benzyl 2-n-hept yl-4- en
0::
hydroxy-6-mcth ox ybenzoat e with TFAA ~
and subseq uent debenzylat ion p;
::l
4-0 -M eth ylsupero livetor ic acid 265 11 2 Pseudobaeolny ces 94 (266) o
pach y carpa
'"
'"
2'-O -Me thylsuperphyllinic acid 266 152 Porpi dia glaucophaea 99 (265)
M icr ophyllinic acid 267 116 Cetrelia japonica 98 (221)
M iriq uidic acid 268 140-141 Miriquidica leucophaea 103 (219)
No risoobtusati c acid 269 Ram alina am ericana (96)
No rmir iqu idic acid 270 137 M iriqui dica leucopha ea 103 (219)
'-0
'-0
Tab le 4 (continued) 0
~"" 0
'"~
;:,; Compound Formula M.p . (0C) Lichen Synt h. Scheme Ref.
.'~"' N o.
~ Norob tu sat ic acid 271 Hypotrachyna chicitae (206)
""
""' Oxoste nosporic acid 272 119-1 230 Neofuscelia verruculifera From div arica tinic acid and benzyl 2,4- (273)
:E dihydroxy-6-(2'-oxo-n-pent yl)-benzoate
~
" with DCCD and subsequent debenzy lation
Patagonie acid 273 104-105 Bunodophoron From 2-hydroxy-4-methoxy-6-me thylben - (260)
patagonicum zoic acid and benzy l 2,4-dihydroxy-6-
(2'-oxo-n-nonyl)-benzoate with DCCD
and subsequent debenzylation
Prasinic acid (Superlatolic 274 93-94 M icarea prasina, (92,
acid) Dimealaena oreina 101) !Z'
Pseudocyphellarin A 275 174-175 Pseudocyp hellaria vaccina (383) ::r::
104 (239) :::
::>
(1)
105 (590) n
Pseudocyphellarin B 276 168-169 Pseudocyphe llaria vaccina (383)
...
104 (239)
105 (590)
Ramalinaic acid 277 220-221 Ramalina ameri cana (96)
para-Scro biculin 278 Lobaria scrobiculata 106 (211)
Sphaerophori n 279 141 From 2-benzyloxy-4-met hoxy -6- (262)
methylbenzoic acid and 2-n-heptyl-
4,6-dihydroxybenzoate with TFAA
and subsequent debe nzylation
Subco nfluentic acid 280 163-164 Lecidella cf. cyano sarca (92)
107 (271)
Subdivaricatic acid 281 153-1 54 Ram alina americana (96)
From 2-benzyloxy-4-metho xy-6-
meth ylbenzoic acid and ben zyl 2,4-
dihydroxy-6-n-propylbenzoate
Submerochlorophaeic acid 282 156-1 57 Cladonia merochlorophaea (93)
From 4-benzyloxy-2-meth oxy-6-n-propyl- (192)
benzoic acid and 4-benzyloxy-2,3-dihydroxy-
6-n-propylbenzoat e with T FAA and Z
~
'"
subsequent deben zylati on ;:<:l
Subp al ud osic acid 283 181- 182 Ramalina paludosa (93)
'"
'"
g.
From 4-benzyloxy-2-methoxy-6-n-propyI- (192)
benzo ic acid and 4-benzyloxy-2,3-dihydro xy- '"
0
::l
6-n-pro pylbenzoa te with T FAA and :;.
subsequent deb enzylati on
(J
'"
Subsek ikaic acid 284 159-1 60 Ramalina americana (96) ::T
Fro m 2-ben zyloxy-4-meth oxy-6-methyI- (192) '"
:3
c;; .
benz oic acid and benzyl 2,3-dihydroxy -4-
methoxy-6-n -propylbenzoat e with TFAA 0
a....,
and subsequent deb enzylati on r-
Subsphaeric acid 285 120 Dimelaena thysanota From 2-benzyloxy-4-methoxy-6-meth yl- (208) n·
::T
benzoic acid and benzyl 2,4-dihydrox y-6-n- ::l
'"
pentylbenzoate with T FAA and subsequent I:J)
e
deben zylation g-
Superconfluentic acid 286 139- 140 Porpidia glaucophaea (92)
;-
::l
o
99 (265)
'"
'"
Superp lan aic acid 287 108 Lecanora planaica From 2-n-heptyl-4,6-dimetho xybenzo ic (193)
acid and benzyl 2-n-heptyl-4-hydroxy -2-
met hoxybenzoate with T FA A and
subsequent deb enzylat ion
Wr ightii n 288 216.5 Erioderma wright ii (5 18)
;;
102 S. Hu neck
~~~-y::
~~OH
~ 00
C-)LAOH
o
Me
126
n-C:;H ll
o
'-'::: 0- '-'::: OR
I~ I~ 127: R = Me
153:R = H
n-C:;Hll
Jl
Me c o - : q M eOMe R*n-<:,H,
I
CO-O~OH
I~
I ~ I ~ ~
.0 OR .0 Me .0 OH .0 COOH
Me Me
R i>-C,H,
128 :R=Me =
130 : R CI, R' H=
129 :R=H 131 : R = H, R' = CI
£
n-<:'Hl1co-O~OR
*
~ co-0"{YOH
I ~ I ~
MaO .0
I
OH "LCOOH
il-C,H l1
.0 OH 0
-<:,H,
=
135 : R n-esH11 142 : R= Me
136 : R = n-e3H7 143 : R= H
~oo~oo
~O~ Y'COOH
R Me
147: R = COHoR' =H 154 : R =H
155 : R =Me
148 : R = R' = Me

New Result s on the Chemistry of Lichen Substances 103
o~-yy~
~
~OH
CI
Y"COOH
n.(;3H,
~ Y"- . il-CsH"
132 133
Me Me
:v:»~
CHO
134
Me
137
rl/-'y:: ~~
HQU CH
CH
C-O.#
o
CH
COOH
Me Me
138
rV-yyoo
.i.-, y
1<1O:R = H
141:R=Me
O-CSH11
139
~ccrcyycrco:l
R'-OUOH y. n-CSH11
H O VOR'"
161: R=R"=n-GJH7.R'=R'"=Me
162: R=R"=n-GsH1l.R'=R'''=H
163: R=n-e3H7.R·=Me. R"=n-CsH11.R"'=H
104 s. Huneck
~g-Iij~R
ROVOO "'r n-C SH11
144: R=R"=H,R'=n-C3H7 156
145: R=Me,R'=n-CSH11,R"=H
146: R=Me,R'=n-C3H7,R"=H
159: R=H,R'=n-C3H7,R"=COOH
150: R=n-CsH11
152: R=n-C3H7
J5 g-l(COO
I~
(>C,HH
~
1#00 #COOH
Il-C,H, HO¥OO
~"~yY-
R
~COOH
OR'"
/5/
157: R=R"=R"'=H.R'=Me,R'''=n-C7H1S
158: R=COOH,R'=R"=R'''=Me,R''''=H
160: R=R·'=H,R'=CH2-CO-n-C7H1S,R'''=n-C7H1S,R''''=Me
Ref erences. pp. 239- 276

'4
~ CO-O~OMe ~Co-YY0Me
I~ I~
~OMe
I
OR"
R' COOH Y'COOH
11U: R = R' = rH:SHll, R" = Me 168 : R = R' = n-C3H]

165 : R = R' = n-CSHll' Roo = H 171 : R = rH:SHll , R' = n-C3H7
166: R = n-Cstill, R' = n-C7H1S, Roo = H 172: R = rH:3H7' R' = n-Cstill
167: R = n-C:#i7, R' = n-CSHll, Roo = H
I7l
R':te:
I~
CO-O~OH ~Me
I ~ :::,..1
COOH
R OMe CO- OH
Me
169 : R = Me, R'= H

179 : R= H
170 : R=H, R'= Me
180: R=Me
j(
~ ~~
Me CO-O OR" COOH
I '<::: I '<::: ,:7 I
00
181 : R = R' = R" = H

183 : R = ROO = H , R' = Me 181 :R=H
19Q:R:Me
11U: R = R' = Me, R" = H
165 : R = R' = H, R" = Me
186: R = Me, R' = R" = H
106 s. Huneck
Me Me
~:'¢::-COOH Me
114 175
0
c- OH
COOH OH COOH
0 0
n-CrH u J>.C,H,
176
177
n-C)H,
'Y: :Cc y:
0 1
OH .# COOH
.# OH .# COOH
Me
~ H1 1
178 181
'T'CsHu
.«. ~:xX~
0
.# OH n.c,H,
i1-C,H"
187 188

*Xr Me
192
Me
~Co-~ OR
~»OR ~COOH
n-C5H 11
193 : R" H
194 : R "Me
195
196
r0-~
~~ Y'~
o
C-yY~
Me
~ Y'~
Me
197
198
*~*:~
~~Mo
Me
C~
Me
~-yY~
~ Y'- Me
199 200
108 S. Huneck
Me~ CO-yOH:yeMe
j):
I ~ = I I
Me OH
H h OH h co- COOH
201
'-yY
o
OH iCOOH
n-c,Hr
202
203 : R = R" = H, R' = Me
204 : R = H, R' = R" = Me
frg+
205 : R=R'=Me,R" =H
~OH Y'COOMe
coo Me
206
207

]lJ
208 : R " H, R' " R" " Me
209 : R "CI, R'" Me, R" " H

210 : R" Cl, R' " R" " H
J::O
*
Me 0 *Me
~C-O CI ""':: c-o ""':: OM.
~ ,., ~"'"
""':: OMe
"" I HO I ..9 OMe Me 1..9 COOM.
n·C.H, Me Me
2/] 2/3
n-C,H,
] /4
215 : R" Me, R' " H

216 : R " H, R' " Me
,,~g_,*M. OH
"'~'"" Me
I:
Me
coo..
]17
"Jx'
11 0 S. Huneck
i?-oyOH
I ": I ":
~ 0Me ~ COOH
118
n.c,Hl1
]/9
Mo Me
~
H+CO-nORO ~COOH : g-~: OH
R"~OR ~Co-OA)lOH h
OIl
I~
COOMe
Me OIl Me
220 : R = Me, R' = R" = H ] ]3
221 : R = R' = H, R" = Me

222 : R = ROO = H, R' = Me
~r}-*
~OH ~COOMe
CH,OH Me
..Jj I~
::Hl1g_1C(C0H
0Me
I~
COOH
il-C,H"
]U 225
~Jr;X:' ]]6
il-C,H"
MoO
°te'
I -..::,
h
~~OMe
OIl
I -..::,
h COOH
228 : R = n-C7H15. R' = n-C5Hll

229 : R = n-CsHl1, R' = n-C7H15

~~
MoO OH ~COOH
n-c, H,
231
~~"y)
~0Me ~COOH
233 n-C,Hl l
232
234 : R=R'=H
~ I~
Me
CO-*OMe
OH
I~
236
Me COOMe
235 : R=R'=Me
237 238 : R=Me,R'=R"= H

239 : R = R' = H, ROO = Me
240 : R = R" = H, R' = Me
241 : R =Me
243 : R=H
~ I~
Me CO-"*:OMe
I
~ OH ~ COOH
Me Me
244
:xX
11 2 S. Hun eck
An""""
t>-C,H, co- COOH
I ~ I~
147
150 151
k"'CC;
Y 153
:«-xX:
M:,H,.
CHO Me
154
155
~~"rI)ao
~~ ~~Me
n-c.H"
156
157
Ref erences. pp. 239- 276

15/1 159
~OR
n-C3Hr CO-~OR '
~ I~
I A A
COOH
H"
260 :R=Me,R'=H
261 : R = H, R' = Me
~~~
HOyOMe "('COOH
Cl n-e"H"
161
~+ 164
n-e,H,.
n-e,H"
166 0 167
n-e,H,. ~H"
114 S. Huneck
E o
&~~~
~C»i ~COOH
Me
268 269
h:-y: Me
27/
Me
= =
272 : R R' n-C3H7
273 : R = Me, R'= n-C,H "
JS:
.c,H
n
15g_"'Q:0H
I ~ I ~
h h
OH COOH
il-C,H 15
274
~g-~:C»i
~C»i h 0
Me
277 HO
276

New Results on the Chemistry of Lichen Substances 11 5
&g-1I)"'"
~OH ~COOH
:is:
n-c,~
280 281
£C
R'O
(l-C,~
I~
b
CO-
OMe H
I
~
b
COOH
=
282 : R n-CsH11, R' Me =
=
283 : R n-C3H7,R' H =
~~ ~COOH P-"IIJ" n-c,H15

287
~:uyc. CI
288
Me
116 S. Huneck
Me
Me
~~Bf. K,co,:J:Xl: POC~. OMF HOCx):coosn 1.2. MCPBA

COOSn
• I
Me~H ~~ Off
.0
OSn MoO .0 OSn
):X
0
I
:
..-::;
COOSn
OSn
Ac,~ •
:xX: I
.0
COOSn
H2 • Pd-C.
oen MoO
Ac:xX
I
Me
..-::;
COOH
OH
•
occo
H0ty:0H
I
.0
Me
COOBn
:xX
Me
1'-'::::
.0
CO-0ty:oH
OH
1'-'::::
.0 COOSn
~ :xx Me
1'-'::::
.0
CO-0ty:oo·
H
1'-':::: HO
.0 COOBn
tl 1. occo
OH
...;2::.. :.:.1-1,0.:
. P.;:d.;:oC_ _
ir
Me Me
:xX
Me
0 Me CO-0ty:oH COOH
I '-': : I ~ ::7 I
..-::; OH .0 CO-O:::,... OH
Me
126
S cheme 93. Synthesis of 5-0-acetyl-4-0-m ethylhiascic acid
References, pp . 239- 276

Jx
R"'
C~QR'" I. occo
COOR COOR 2.HCI
I: HOCH,-CH,OH I '-': + 3. H" Pd-C
R" OR' R" h OR'
R R' R" R'" R.... R" '"
117 : Arthoniaicacid H H H n-C,H" Me -CHrCO-n-C,H"
187 : Hyperconfluentic acid H H Me n-C,H"

118 : 2-O-Methylglomelliferic acid H Me Me n-C,H, H n-C,H"
118 : 2'-O-Methylhyperphyllinic acid A H H Me n-C,H" Me -CH,-CO-n-C,H, .
119 : 2'-O-Methylhyperphyllinic acid B H H Me n-C,H" Me -eH,-eO-n-e,H"
143 : 2'-O-Methylmicrophyllinicacid H H Me -CH,-CO-n-e,H"
153: 2'-O-Methylnorsuperphyllinic
acid H H H n-C,H" -CH,-e O-n-e,H"
165 : 4-O-Methylsuperolivetoric
acid H H Me H n-e,H"
267: Micrnphyllinic acid H H Me n-C,H" H -eH,-eO-n-C,H"
Scheme 94. Synthesis of arthoniaic acid and related compounds
.,n ~
R COOEt
0
~
4~
I
H hQH---
I
COOEt OMS
K,CO:.
4~
I
hOMe
I
COOEt
BC1,
4
R
I "':
h
1
COOEt
QH
-!SQ!L
4
R
1 TFM
I '-': COOH HOuycOH
+ I "': 2. H" Pd-C
h QH h CGOBn
R
Scheme 95, Synthesis of 3-chlorodivaricat ic acid

118 S. Huneck
C1*:COOEt ~:c~OH C1xXOSiMe,Me
~ lAH.
~I
I '-':: Me Me
I -&
~ I -&
Me,SiCI
---
1.0 ~ -& +
MaO aBn aBn MaO aBn aBn
*-#-*
Me Me Me Me
HO~\ Me HOy
/34
Scheme 96. Synthesis of I'-chloronephroarctin
:2x
R
~
o
1. DMS.K,co,
2. BnONa
3. OIlS , K,co, R cooss
..
CODEI
~I I~
::,.,. OH h OH
I:
1. H" Pd-C
uY
~ R
COOH HO OH ~
MoO OH
+
T <,COOH
DCCD
I ~
8-0YCOH
I ~
, g-y:,:
/m,",=",o"" ..:.
h h
OH COOH
R'
-CH,-CO-n-C,H,
~ n-C,H"
1x,
OH 178: Glomellifericacid
/: /: 101 : Loxodellic acid n-C,H,
OH COOH
R'
R R'
149 : 4-0-Demethylglomellic acid n-C,H, -CH,-CO-n-C,H,
/50 : 4-O-Dernethylglomelliferic acid n-C,H"
/51 . 4-O-Demethylloxodellic acid n-C,H,
Scheme 97, Synthesis of glomellic acid and related compounds
References, pp, 239-276

Me-(CH,I, QCH=Ct+-~t A?R COOEt

~R
I "
0 COOEt
A NaOBn
t)
~
A
o -- OH ---
R
£
B" 'NaOAc/
I~·DCCO
)
R 0
I '::
H,.
COOEt......!SQ!i V'COOH
+ ':: COOH 2.1<
BnO A OBn BoO A OBn
IA 3. f'd.C
R ~ OH
o OH COOH
153 o
R R= n-CsH" 267
Scheme 98. Synthesis of 4-0-demethylmicrophyllinic acid (/ 53)
R R' R"
160 : 4-0-0emethylsupereonfluentie aeid H H n ~C7H15
176 : Glaueophaeie aeid Me H -CH,-CO-n-C,H"
266 : 2'-O-Methylsuperphyllinie aeid H Me
286 : Supereonfluentie acid H Me n-C,H"
Scheme 99. Synthesis of 4-0-demethylsuperconfluentic acid and related compounds

120 S. Hun eck
4
Me
COOH HOy:OH lxCOOBn 1.TFAA

I '-':: +I '-':: c-: I 2. H,. Pd-<:
BnO h 0Me h c- ~ OH
OBn o
Me
Me
I: :1
OH ~Me
*
0
C-O COOH
HO 0Me
y:: OH
C-
o
Me
186
Scheme lOOa. Synthe sis of 3-hydroxyumbilicaric acid
H"'qOHjxMeCOOBn 1.TFAA
*
Me COOH
I '-':: I '-':: I Hz. 2. Pd-<:
OH
+
~ c ~
Me o
BnO : OMe
205
Scheme lOOb. Synth esis of 3-methoxyumbilica ric acid
Ref erences, pp. 239-2 76

RV n-8uU + ]xBr~'
CI
, -
~
h OBn
I~
h
.'-
OBn
-
2. Co,
2c
R
J. DeCD o
HOyyOH C- OH
': li) ~
2. CUO. CuC!,
~CooBn OBn " ( ' coosn
2cI: ""
Me Me
~""'" ,
o
c- OH
e .."".
Me
198 : lsopatagonic acid
..JX I Me
~
h
g_~OH
OH
I~
173 : Patagonie acid

h COOH
0
R~~H15
Scheme 101. Synthesis of isopatagonic acid and patagonie acid

122 S. Huneck
tr
Me Me
I. H2, Pd-C
COOH 2. BnBr, KHCO,
H'u:(COMe lFAA BnOy e O B n ((COOBn
I "'= • 1,& -- 1,& ::,.,1 -----
oc-~
BnO ,& OBn CooBn 0Me
.o h
Me Me
Me
COOH 1.lFAA
HOyeOll 1"'=
,&
s-:
I
coos-+ I ,& ~
C-::'" BnO, OBn
o 0Me
Me
J6c Me
,"'=
,&
g-oyeOll
OIl
1"'=
Me
,& C-O/::'"
o
((MeCOOH
?'J
0Me
2/9
Scheme 102. Synthesis of 2"-O-methylgyrophoric acid
lx
· :OClC-CHNH:OOEl
C'
I~
RO h OR
1 h
H
I:
Ex
:: t
1. n-BuLi
"
1.SOC12 Br
Br ~ Br z.co,
1"'= 2. El2CuLi CH(OEl),. EtCH
H+ I h
3.BC!,
---
'
R ,& OR RO OR R OR
1 1 ~
0 OX><
1 "'= •
E I g--Ote: OIl
,& OIl
R OIl COOH
SH 11
268: Miriquidic acid, R = Me
270 : Normiriquidic acid , R = H
Scheme 103. Synthesis of miriquidic acid and normiriquidic acid

Me Me
OH:te
Me
~COO::CHOMe
*: I»:
OHC)):COOMe COOMe
I:
MeOM I BCI, Zn-Hg. HCI
OMe SnC!,
MaO ~ OMe -- H OH
~-C
Me)):MeCOOMe
'.:::
I M e * :COOMe /COOH" OH
I ~
HO --HO ~ ~
CI,CHOMe H,SO. I + 1
HO h OH ~ OH OH COOMe
CHO HO TFM
Me
*
Me o»Me
Me
HO
I: I:
c-
H
OH
COOMe
~
CH,OH Me
276
Scheme 104. Synthesis of pseudocyphellarin A and B after Elix and Lajide
:
J:X I
LcOOMe ;:aM.COOMe
)(;.l
h
exx-
OMS, K,co,
OH MeO
Cl;,CHOMo, TiCI,
OMs
I:
OMe
~
:6:
c~» ·Me
Me
exx-
BCI, y t M e exx-
Me*Me
I "':: ~ I "':: C1,CHOMe 1 "':: BB', ,"':: COOH
h 00 h OH T0C4 h 0 0 - - HO h 00
TFM
HO CHO
I:Me 0xX
I:
~
Me c-o 00
~
H 00 COOMe
H,OO Me
276 275
Scheme 105. Synthesis of pseudocyphellarin A and B after Pulgar in et al.

124 S. Huneck
*
BnO
I ~~
ho OH
~
BnO
*~
Iho H,.p~
COOMe
0Ac
~
~ ~COOH
I ho
COOEt
BnBr, K,Co,
J X RCOOEt
I:
OBn
....Q!!.- M
MeO OBn
..lEM.-
&g-o~OAc H,~
0Ac
R)Cc
~
o
C-
I ":
COOMe
H,.p~
~OBn yCOOMe
R
~ OBn
, ho
R
--
R= n-C,H,
178 : p-Scrobiculin m-Scrobiculin
Scheme 106. Synth esis of p-scrobiculin
OJxR ~R
~
R .
COOEt COOEt COOH
I ": 1. HOCH,-<:H,OH I ": KOH I ": H'
ho 2. CH,N, ho - - ho --
HO OH- OH OH
HOycOMe
I
1.occo
ho
r\-CsH"
COOH
R
2.H"P~
=n-C,H,
~" g-o~OMe I ":
ho OH
180
I ":
ho
H"
COOH
Scheme 107. Synt hesis of subconfluentic acid

HOH,CVOMo
I
MeOH,yOMe
I MeOH,cy:OMe~:
I .NaH I I 1. PhU NBS
0Me I.
2
PhLi
co,
./
././ ~ ./
"./ __
. _
20MS _ 0
./ Me- - h- Me ~
0Me OMe 0Me
*=
Me COOK
I"':
I
HO h-
CliO
HO
qI
Me
CHO
co - ~OMe
OH
I
"":: OH
h
OH
Me
289: Methylalectorialate
Scheme 108. Synthesis of methyl alectorialate
MeOH,llOMe
1
"':
h-
MoClH,C
.
1. PhU
2. HCONMe,
Y "':
h-
OMs
~
NBS
MeOH,~Br
1
"':
h
OMs MeOH,~Br0Ms~'~~
MeOCH,PPh,C1
c-o MeOH
1
"':--
Me
CH(OMe),
290: Methyl barbatolate
Scheme 109. Synthesis of methyl barbatolate

126 S. Huneck
0:te:
MoO
I ~
COOMe
0Me
1.PClIlA
2.1lCl,
- - - MoO
:xx: I ~
COOMe
0Me
~.=::A )-o~:
3. NaOH ~
COOH 1.Cu,O,Dipy
MoO
2. BBr,
~ ~ ~
(;~'O'D~y4~ NaClO,=1~ BnBr, NallCO,

HOl{:
HO OH MoO~OH ~ OH ~ OH
HO CHO HO
~
~~
~.,
CI,cHOMj;tMe 1. TFAA
CHO 2. H" PdoC
I ~ TiCJ. ': ~
MoO
COOBn
OBn - - -
COOBn
OBn
~OBn
COOBn
29/: Decarboxythamnolic acid
Scheme 110, Synthe sis of decarboxythamnolic acid
~-~~'~~
",~I """"
H'g-
NaOMe, MeOH
~OH O~
Me Me
295
:¢(
Me OMe MeJ9CMe
COOMo
1"-': ~I
h c-if~
o
Me Me
296
S cheme Ill. Methanolysis of methyl thielavinate B

compounds, phenolic units, rearranged depsides and xanthones.

Trimethylammonium salts of depside carboxylic acids decomposed at
considerably lower temperature than the corresponding acids. Thielavin
A (292), B (293) and C (294) are tridepsides from the fungus Thielavia
terricola and are inhibitors of prostaglandin synthetase (459, 460).
Methyl thielavinate B (295) gave the depside 296 on methanolysis (see
Scheme Ill).
292: Thielavin A, mp235-236°C
293: Thielavin B. mp250°C
294: Thielavin C. mp 107-I09°C
4.5.7. Depsidones
The newly described depsidones, their occurrence and synthesis are
listed in Table 5. The synthesis of depsidones with a lactole ring like
those in norstictic, stictic or salazinic acids have caused considerable
difficulties. Hareed (353) tried to prepare a depsidone by a) oxidative
coupling, b) by a Smiles rearrangement and c) by an Ullmann reaction
of a diphenyl ether, but all three attempts failed (see Scheme 123). Some
time later Rama (604) successfully synthesized the lactone depsidone
359 and the lactole depsidone 360 via oxidative coupling of a
dibenzophenone (see Scheme 124). The structure of the precursor 358
::.:, Tab /e 5. D epsidon es fro m lichens tv
~ 00
Co mpou nd Form ula M .p. (0C) Lichen Synt h. Schem e Ref.

......
~a" No .
~ ex-Acetylconstic tic acid 297 >230, dec. Men egazzia p/at ytrem a, (214)
.....
v.. Pseudocyph ellaria fa veo/ata
1"
..... ex-Acety lhypoconstictic 298 220-240, dec. Menegazzia dispora, Xa n- By ace tylation of hypocon stictic (213)
~ acid thoparm elia meta st rigosa acid with AcOH in DM F
Allor hizin 299 230-232 Psorom a allorhizum 112 (240)
Chloro lecideoi din 300 234 Lecanora su/phurescens By chlorina tion of lecideoidin with (515)
SOzClz in di oxane
Chlorophyllopso rin 301 228-229 Phyllopsora corallina va r. By chlori na tion of ph yllop sorin (258)
ochroxantha with Clz
Co nfuma rpro tocetra ric 302 240-245, dec. Cladonia phy llophora By redu ction of fuma rpro toce tra rtic (2 76) C/J.
acid acid with NaBH 4 in 1,2-dim eth oxy-
ethane
::r:
Co nhypoprotocet ra ric 303 >330 Lecanora my riocarpoides 113 (243) ':<>:>"
n
:0<"
acid
Co nphysoda lic acid 304 >230, dec. F/avoparmelia spring tonensis (214)
Co npro toce tra ric acid 305 230-235, dec. Usnea trichodeoides By red uction of prot ocet raric acid (276)
with N a BH 4 in 1,2-dim eth yoxyeth an e
Co nsuccino pro tocetra ric 306 237-240, dec. F/avoparme lia succinoproto- By red uction of succino pro to- (2 76)
acid cetrarica cetraric acid with NaBH 4 in
1,2-dimethoxyethane
Co nvirensic acid 307 235-240, dec. S ulcaria virens By reduct ion of virensic acid with (2 76)
Na BH 4 in 1,2-dimeth oxyethane
Cyclographin 308 245- 246 Catarrap hia dicty oplaca 114 (250)
Decarb oxyalectoronic acid 309 144-14 8 Hypotrachyn a gra cilescens (189)
3-0echlorogangaleoidin 310 226-228 Ty /otha llia pa hiensis (259)
Oechloropannarin 311 182-1 84 Lecanora dispersa (497)
115 (240)
3-0 - Demethylscensidin 312 226-227.5 Diploicia canescens By regioselective deme thylati on (230)
of scensidin with NaI in DM F
Didechlorolecideoid in 313 245 By hydrogenati on of lecideoidin (259)
with H 2-Pd C
4,2' -D i-O-methylcon- 314 Lobaria pulmonaria (9)
norst ictic acid Z
(I)
lE
2'-0-Methylphysodic acid 315 160 Pseudeverina furfuracea (339)
::0
(I)
Dinorscensidin 316 not yet found in lichens (206)
'"
Divaronic acid 317 110, 160-1 62 Cladonia chlorophaea (93) ~
116 (228) 0
:>
Eriodermin 318 234-2 36 Erioderma physcioides (79)
117 (589)
e-
(I)
(J
8'-0 -Ethylstictic acid 319 245 S tereocaulon vesuvianum ;:r
(I)
(Vesuvian ic acid) 3t;; '
(probabl y an ar tefact) (438,
412)
~
0
...,
Fulgidin 320 204-20 7 Fulgensia fulgida 118 (32) r-
Furfuric acid 321 250-254 Pseudevernia fu rfura cea (340) n'
;:r
(I)
Synthesis of meth yl tri-O-methyl (341) e
desoxyfurfurate 119 en
Synthesis of furfuric acid 120 (209)
=
r:r
'"
S
Gang aleoidin 214-215 Lecanora gangaleoides (633) :>
()
(I)
Glomelliferon ic acid 322 184-18 5 Neofuscelia subincerta Th e 13C NMR signals of glomelli- (227)
'"
feroni c acid could be assigned
by the relaxat ion time T I of the
co rresponding C atoms
N
'-0
::.:, w
~ 0
...'" Tab /e 5 (continued)
..,;:,'"
~ Compound Formula M .p . (0C) Lichen Synth. Scheme Ref.
~ No.
N
~
'0 G lomellonic acid 323 149-151 Neofuscelia subincerta (227)
I
N Hypophysciosporin 324 238-240 Erioderma phaeorhizum By chlorination of methyl (348)
~ hypoprotocetrarate with S02CIz
Isidiophorin 325 268-270 Lobaria isidiophora (36)
Isofulgidin 326 260-261 Fu/gensia canariensis, (32)
Hafellia fu/gida
Isonorpannarin 327 195-198 By ch lorination of nordechloro- (226)
pannarin with S02C12
Ison otatic acid 328 166-167 Ramalina americana (96) f/l
Xanthoparmelia notata 121 (238) ::r::
Isovicanicin 329 247-249 Psoroma athrophy//um (240) ::l
'"
Leoidin 330 232-233 Lecanora ganga/eoides (206) :>;"
"'"
Loxodellonic acid 331 159-1 61 Neofusce/ia subincerta (227)
2'-0-Methylconorstictic acid 332 Lobariapu/monaria (9)
4-0-Methyl-5-dechloro- 333 not yet found in lichens (206)
vicanicin
Methyl 2'-0-demethyl- 334 Lecanora intumescens (270)
psoromate
Methyl 5, I'-dichloro- 335 230-232 Phy//opsora cora//ina (258)
norpsoromate var. ochroxantha
Methyl 5, I'-dichloropso- 336 204.5-207 Phy//opsora corallina By ch lorination of methyl psoromate (258)
romate var. ochroxantha with chlorine in AcOH
4-0 -Methyldiploicin 337 220 Diploicia canescens By methylation of dip loicin (230)
4-0-Methylhypo- 338 200-203 Erioderma phaeorhizum By ch lorination of methyl 4-0- (348)
physciosporin methylprotocetrarate with S02CI2
3-0-Methyllividic acid 339 156.5- 159 Hyp otrachyna livida By methylation of ben zyl lividate (256)
and subseq uent debenzylation
4-0-Methylpannarin 340 not yet found in lichen s (206)
Methyl pseudoalectoronate 341 Parmotrema poolii (268)
Methyl pseudonorstictate 342 Pertusaria fa lklandi ca (270)
Methyl pseudosalazinate 343 265, dec. (270)
Methyl psoromate 344 Lecanora intumescens (270) Z
<1>
~
O-M ethyl vicanicin 345 Erioderma spec. (230) ;>;l
Norar gopsin 346 152- 154 Erioderma chilense By ch lorination of norpann arin (226) <1>
with SOzClz g.
Nordechloropannarin 347 Lecanora dispersa (497) '"
0
::>
Nor ison otatic acid 348 Ramalina americana (96)
So
<1>
Norpannarin 349 198- 202 Erioderma chilense By decarboxylati on of 5-chloro- (226)
vire nsic acid with C uO-2,2'- n
::r
<1>
bipyridyl in bis-(2-methoxyeth yl)cth er 3
Oxolob aric acid 350 178 Anzia hyp oleucoides (2 72) ..,~:
'<
Ph yllop sor in 351 233.5 Phy l/opsora corallina var. (258) 0
....,
ochroxa ntha r-
Siphulellic acid 352 >240, dec . S iphulel/a coraI/oidea Structure confirmed by co nversion (216) n'
::r
<1>
into methyl O-methylpsor om ate ::>
Steno sporonic acid 353 139-140 Cladonia grayi 116 (228) V>
Subl ob ar ic acid 354 183-1 84 Anzia hyp oleucoides (272) ''"cr-"

~
Subnor stictic acid 355 > 315 Diploschistes ocel/atus (189) ::>
Subnot atic acid 356 223-22 5 Parmelia notata 122 (238) <1>
"'"
Sub sticti c acid 357 >270, dec . Aspicilia mashiginensis (2 14)
Vesuvianic acid : see
8'- O-Ethylstictic acid
:::;
132 s. Huneck
~g_~~OH
~
Me g_~~H
1 ": I ":
~O ~ 0 ~ 0 ~ 0
CHO Me 0
:v
297 298
*c:xt
Me
1 ": g-* 1 ": OMe I": g-*OH

I":
~
o
~
CI
~
o ~
COOMe
Me CHO Me
299 CI 300
Me
1 ":
g_»Me 1 ":
0Me
~ ~
H 0 CI
o CHO
301
if~~
~O~COOH
H,OH 304 Me
&g-~~
HO~O~COOH
CH,OH Me
:v
305
~~*
g-*COOMe
OH
I Me
1 ": 1 ":
CH,OH
~ 0 ~
Me CHO Me
307 J08
was determined by an X-ray analysis. Pannarin (361) undergoes rear-

rangement on treatment with sulphuric acid to isopannarin (362) (176)
(see Scheme 125). The reactions of stictic, norstictic and salazinic acids
with MeOH , EtOH and tert-BuOH have been investigated by Huneck
C~8-:y:0Me
~~
CHO 311
Me
,)lA
HO 0
312
I h
Me
Cl
&a-li)
~O~COOMe ~~~
Me
.~
:
313 CH,OH
314 HO
o
~:~~
~O~COOH
315
n-c5H11
:xX 8-:y:OH
I h
o
316
I h
Me
CI
1~>-1IY
MeO~O~COOH
317
n-C,H, :«1 Me
I h"'"
CHO
8-:yc0Me
o
I "'"
3/8
h-
Me
CI
*~*~ CI
320
Me
and Tabacchi (412). Methylstictic acid from Lobaria oregana is identical

with 8'-O-methylstictic acid (363) while Handong's cetrariastrumin is
identical with 8',9'-di-O-ethylsalazinic acid (364).
134 s. Huneck
':&-~oo
MaO O ~COOH
~H"
322
~O
°i'~:xg-,y,:(:
~
0
h-
OH
323 H,-CO<l-C,H,
Me Me
MaO ~~o
I":::
h- 0 *~~
~ O~CI
s-: 0 CI Me
325 326
0
#* CHO
327
Me
g_*MeOH
~
I
~~*
:
Me
I ~ I ":
h-
o
h-
CI ~O 00
COOMe
Me Me CI Me
329 330

331
~~
Me Me
333
#*
CliO
335
COOMe
~8-~~
~O~CI
CliO
336
COOMe
g-*OH
#*~ #
I~
Me I ~
h 0 h COOMe
CI Me Me Me
337 338
O~-g-lIY
J;lo~c~
0Me
339
il-CsH ll
-*~*~ CHO
340
Me
136 S. Huneck
n-eSH11
#y
0 Me
0
c- OH
~ 0 ~ 0
342 0
#*
Me Me
COO
o .
0
0 ~~~ CHO COOMe
343 MaO 344
I: I:
*~ **
g- OH
o CI 00 0 CI
Me Me Me
345 346
Me Me Me Me
~*~ CHO
347
Me
ff~ 348
Me
#~ I~
COO
0
I~
Me
~:y~ o
n-c.Hl1
COOH
349 350
#~~ I~
CHO
0
I~
COO
~~~ I "':
~
CHO
0
I "':
~
COOH
351 352

g-YfCOH
~
:H,
I h I h
o COOH
n--C5 H11
353
JX
H
I h
CHO
g-~
I
O
355
OH
HO
h
.
0
0
&~))'"
~O~COOH
356
Me
~~O
&g-~:OH 0
CHO
HO
357
8-oXzOH
Me M.
CuO'BiPy'Pt#j~Me~
I I Lif, (Me,N),PO
fi 0
Me
°
HypostlcllcllCid
~.OH
~. Me
I .SO,CI,
2. OMS. K,co,
299 : Allorhizin
Scheme 112. Synthesis of allorhizin

138 S. Huneck
~~=
~ ~
PrcIoaltrarie acid
1. Aclltone
2. BnBr, K,CO
I ,4-:; Me
~
0:q~
C-O
o
'-'::
1,-:;
~
0 ~
cooa-
2.H,.~
1. NaSH.
303 : Conhypoprotocetraric acid
:»:
Scheme 113. Synthesis of conhypoprotocetraric acid
w¢c I Me'-'::
h
Me
COOMe
OH
Hexamine. TFA ~:
I
h
Me
COOMe
BnBr, K,Co,
OH BnO
I,-:;~.:~
COOMe
Me
I
o~nO
=*: h
Me
COOMe
OMS. K,co,
OBn
BnO
I:
MoO*MOCOOMe
OBn
~ I:
~Me COOMe
OH
+
Cln
I":
BnO
Me
h
COOH
OH
~
"Xx' Clk
Me Me
Me
CI
I ": o=*Me
C-O
I:
OH
K,co,. DMSO 1 '-':: COOH MoO*Me
c-: I COOMe
I .CH,N,
BnO h COOMe BnO h 0------·:;,.,. OH ~
OH
Me
Me
Mo
Cl>x:
I:
:¢eMe
: I
COOMe COOMe
Hexamine. TFA
Cl;¢CMe
I:
:¢eMe
: I
COOMe
~
Me
HO 0------ OH HO OH
CHO Me
1MeOH,H'
:¥
Me g_*MOCOOMe
1 ": 1 ":
h h
o OH
Me
308 : Cyclographin
Scheme 114. Synthesis of the methanolysis product of cyclographin

Fumarprotoce\nlr1e acid
(i I: *Me
~
Me
o
C-O OH c-o OH
I "': a I ';:::
Me*
1, DMS, K2COa
0 "'Ok. K,co,
h- 2, H" Pd-C
~
BnO a -&
Me HO Me
4
Me
g_*Me, OMe
I "': I ';:::
h- h-
a
HO Me
311 : Dechloropannarin
Scheme l l S, Synthesis of dechloropannarin
te
HO~COOMe
R
~COOli ~AA
': JCl
' COOH
BnO 011
~ BnO 011
+
~OH
o)):R'
A
R
I "':
c-
I "':
COOMe
~COOH BnOrrOli ~ ~~
MeO~O-------"('COOMe
K,Co" DMSO
h h 011
OHBnO
;:Xg-~011
Me
R'
I"':
R
h
0
,"':
h
COOH
317 : Divaronic acid, R = R'= n-C,H,
373 : Stenosporonic acid,R = n-C,H,. R'= n-C,H"
Scheme Jl6 , Synthesis of divaronic and stenosporonic acids

:er »: .:n
140 S. Huneck
:te
Me Me
l
I Me-. .: : COOMe
OMS, K,co, I -. .: : COOMe
NaOH I coos
.co, I -. .: :
:
h h - h h
OH OH OH OH
n
BnBr,K2C~
Cl COOMe CIte:OOOH
I ~ I +
BnO h OBn BnO h OBn
)6(
1 Me
I:
»0
OH
Me CI
I:
0Me
K,Fe(CNlo
245·C
g-:qOMe
yt Me
I -. .: :
h
I -. .: :
° Me
h
CI
318 : Eriodermin
S cheme 117. Synthesis of erioderrnin

4Me44* I: I: ~ I: ~
'-':: COOMe COOMe COOMe e, COOMe
IlMS.K,co, . BnBr. K,co,

h
OH OH OBn OBn
I I I
e,*Me
I '-':: CCXlH
+
h
MoO OBn
1
1.NCSI
Me
2. H,. P<H:
3.KOAc
g_*C1
=*
0Me
I '-':: I '-'::
.& h
o
Me
320 : Fulgidin
Scheme 118. Synthesis of fulgidin

142 S. Hun eck
~
Me I. BnBr
I ~ ~
h-
Br
~ +
I
8oOy oBn
:
MgBr
OH 2.
Me
1.POCI,.DMF =*
:it
BnO
BnC ~ K,Co, MoO

7·
~I
h- OBn
M- ~.=
*
COOMe COOMe
~01{:
Me
coos Me COOMe
?;X
I
OBn I ~ __
Bno J l ) OBn BnO h- 0 80
;nO
Me
h- OBn
;{ 7, ~
Me
,!?*f
Me I. H,. Pd·C COOMe
COOMe COOMe 2. K, Fc(CN).
*~
~g-~~
~O~COOMe
Me Me
:xt:..
'M
.
~~
Scheme 119. Synthesis of methyl tri-O-methyldesoxyfurfurate

":
Jt:
OH
:Ix
Me co_»:OACOH COOMe
~ I I +
I~
H ~ ~ COOH Me
OH Me
M e * O HCOOMe
I":::
H ~ Me
~
: CO-~OH
HO ~ ~COOH
OH Me
321 : Furfuricacid
Scheme 120. Synthesis of furfuric acid
4 * '-:
M. o ~H M. CH,OAc
~'-'::
0
,-,:: c- OH c- OH1 ~
h I h'-':: AcOHin 1,2-dimethoxy-

etIIBne
.H,.
2. BnBr, NaHCO,
H 0 COOH HO 0 0 ° COOH
Me CHO Me
g-*:
_acid
Me'-': C-O* I Me: OMe

~
:
~
OH l. Me:r.K, co,
I I 2. NaCIO,
I 0
0
Cu,O .BJPy
HO 0 . 0 ° COOBn
o
Me
COOBn
HO Me
~Me O * C- OH
I '-'::1'-':: H,. ~
h 0 ---
o COOBn
Me
328 : lsonotatic acid
Scheme 121. Synthesis of isonotatic acid

-* *
144 S. Huneck
4 Me:q OH BnBr,NaHC~ %OH

o c g-o 0M0
- '-':: 1. '-':: PCC
I h I h 2.~K2co, I h I h --
o COOH 0 COOBn
Me HO Me
_rtcocld
H,. PcI-C
JY)yC Me
356 : Subnotatie acid
Scheme 122. Synthesis of subnotatic acid
~OH ~ Me
ooVOBn
Me
Scheme 123. Attempts to synthesize a depsidone with a 1actole ring

g»:
HO
:
te I -&
OH
I -&
COOMe K3 Fe<CN)"
0Me
K,C0 3
---
j;(
H O e
Me
I:
C-O
0 ~Me
I:
0Me
Mel, K,co,
Me Me
g_*Me
~
Me OMe 1. Br,.light
I"=: I"=: 2.H,O
h h
o COOMe
Me
358
Me
59
Me
~ I ~
o_~
o I "=: e / :1. Br"CCI.,light
2. H,O
-& 0 -& 0
360 HO
Scheme 124. Synthesis of the depsidones 359 and 360
Me g_*Me
~
I
*~f
0Me
I"=: ,"=:
'Yo
H,SO,
h h
o
CHO Me Me
361 362
Scheme 125. Rearrangement of pannarin to isopannarin
365 : Physodic acid 366 : 5'-Hydroxyolivetoric acid
Scheme 126. Enzymatic conversion of physodic acid to 5'-hydroxyolivetoric acid

146 S .Hun~k
3~ 3~
The depsidone physodic acid (365) can be converted by a hydrolase

from Pseudevernia furfuracea to 5'-hydroxyolivetoric acid (366) (315)
(see Scheme 126). It would be of great interest to look for further
hydrolases able to cleave the ether linkage of other depsidones .
Certain lichens (Acarospora smaragdula, Lecidea lactea, Lecidella
bullata, Tephromela testaceoatra) from cupriferous substrata form
complexes of copper with norstictic acid (367) (593) and psoromic acid
(368) (594).
367 (dmf > dimethylformamide)
368

Aurantiacin A (369) and B (370) are depsidone s from the fungu s

Preussia aurantiaca growing on a mangrove species (577). Three depsi-
done s, emeguisin A (371), emeguisin B (372) and emeguisin C (373) were
isolated from the mycelium of the fungu s Emericella unguis (450).
COOH
~
Me
~ I: ~
Me
~
OR
HO 0
CI
R
Me
Me
Me
369 : AurantiacinA • R = CHPH
370 : Aurantiacin B • R = COH R R' R"
371 : EmeguisinA : H H H
372 : Emeguisin B : H Me H
373 : Emeguisin C : Me H Cl
4.5.8. Depsones
New depsones are summa rized in Table 6. They differ only in the
length of the n-alkyl side chains. Their syntheses are shown in Schemes
127 and 128.
::0 Table 6. Depsones from lichens .j:>.
~ 00
'" Compo und Fo rmula No . M.p. (0C) Lichen Synth. Scheme Ref.
~
~ Hyperpicrolichenic acid 374 95-97 Pertusaria truncata 127 (257)
~ Isohyperpicro lichenic acid 375 107-107.5 Pertusaria truncata 127 (257)
Isomegapicrolichenic acid 376 145 Pertusaria truncata 127 (257)
~ Isosubpicrolichen ic acid 377 Pertusaria truncata 127 (257)
~ Megapicrolichenic acid 378 11 6-117 Pertusaria truncata 127 (257)
Subpicrolichenic acid 379 164-165 Pertusaria amara 128 (197)
Superpicrolichenic acid 380 108-110 Pertusaria truncata 128 (197)
R
I
OH
~
COOH ::r:
c
:::
(l)
n
:>';""
R R·
374 : n-esH 11 n-e7Hl s

375 : n-C7Hls n-CsHl l
376 : n-e gH19 n-e7 H1S
377 : n-eSHl l n-C;\H7
378 :n-e7Hls n-CgH19
379 :n-e3H7 n-esH ll
380 : n-e7Hls n-e7H1S
R-eHO _ R-CHoCI+COOEI + IolIo-CO-COOEt--
~ - .te
~
R
tc COOEt
o
Br, I:
R
COOEI
anar, K,Co,
OH BnO
R
I:
COOEt
OMS, K,co,
OH BnO
)lA
~COOEt~
0Me
J): J):
R COOH R 0
c- OH
BnO
I""
.& 0Me + &0
"" _y=~
I"" .& I .&
H,. f'd.C
---
R R'
374 : Hyperpicrolichenic acid n-C,HII n-C,H"
375: lsohyperpicrolichenic acid n-C,HII
376: lsomegapicrolichenic acid n-e.H••

377: lsosubpicrolichenic acid n-C,HII n-C,H,
378 : Megapicrolichenic acid
Scheme 127. Synthesis of hyperpicrolichenic, isohyperpicrolichenic, isomegapicrolichenic,

isosubpicrolichenic, and megapicrolichenic acids
BnO· te""
I~
COOH HOyrOH
0M0
+ I""
~ COOBz
~
/1;y
R -0
,;7 OH
I""
o .& OM. ~ COOH
R R'
379: Subpicrolichenic acid n-C,H, n-C,HII
J80 : Superpiaolichenic acid n..c7H"
Scheme 128. Synthesis of subpicrolichenic and superpicrolichenic acids

150 S. Huneck
4.5.9. Chromanes and Chromones

The only chromane known from lichens (Erioderma phaeorhizum) is
acetyl-n-tocopherol (381) (348). The chromone siphulin (382) was
synthesized by reaction of 2-hydroxy-4-benzyloxy-6-n-heptylacetophe-
none with 2-carboxy-3,5-dibenzyloxyhomophthalate in the presence of
NaH to give tri-O-benzylprotosiphulin; this yielded siphulin after acid-
induced dehydration and hydrogenolysis (461) (see Scheme 129).
Me
Me
Jill : Acetyl-a-tocopherol
te MeOOC~:
n-e, H15
1. NaH. THF
CO
"'=: 'Me 2.H'
I + 3. H2• Pd-C •
BnO b OBn
OOH
HO OH
J1I2: Siphulin
Scheme J29. Synthesis of siphulin
The final structures of the chromones galapagin (383) , lobodirin

(384) , mollin (385) and roccellin (386) from lichens were established by
NOE difference spectroscopy (398).

385 : Mollin
386 : Roccellin
4.5.10. Xanthones
Numerous xanthones have been isolated from lichens structurally
elucidated and synthesized by Elix and co-workers and other authors
since 1984; these are summarized in Table 7. Formulae 387-464 are
listed separately.
2,2',4,4',6'-Pentahydroxy-6-methylbenzophenone (465) has been
postulated as a precursor of xanthones. It was synthesized by Sundholm
(682) and found to undergo facile dehydration to norlichexanthone (see
Scheme 139). Base-catalyzed aldol-type cyclization of 1-(2,4,6-trihy-
droxyphenyl)octane-l ,3,5,7-tetraone gave a benzophenone which un -
derwent cyclodehydration to form norlichexanthone (630) (see Scheme
140).
~ Table 7. Xanthones from lichen s V>
~ N
...
'" Compound Formula M.p. (0C) Lichen Synth. Scheme Ref.
~
~ No .
~ Aotearone: see 5,7-Dichloro-

~ 3-0-methylnorlichexantho ne
'f' Arthothelin (2,4,5-Trichloro- 387 268-269 Leeanora broeeha
'"
~ norliche xanthone)
283- 285 Lecidella asema, L. (198)
subalpicida
Dimelaena cf. australiensis, (201)
Leeanora sulphurata,
Lecidella meioeoeea,
L. vorax, Mie area V1
isabe/lina, Pertusaria
::t::
py enothelia :::I
Byssoloma poly ehromum, (242) ""o
i'<"
Sp oropodium antonianum,
S . leprieurii
Asemone : see 4,5,7-Trichloro -
3-0-methy lnorlichexanthone
Capistrat one : see 2,5,7-Tric h1oro-
3-0-methylnorlichexantho ne
2-Chlorolichexanthone 388 222-223 Leeanora spec., Pertusa ria (201)
cieatrieosa
4-Chlorolichexanthone 389 199-200 Sp oropodium eitrinum (242)
5-Ch loro lichexan thone 390 156 Lecanora eontraetula (201)
By methylation of 5-ch1oro-6- (202)
O-met hylnorlichexanthone with
D M S-K 2C0 3 and subsequent
demethylation with BCl 3
7-C hlorolichexa ntho ne 391 320, dec. not yet found in lichen s By methylati on of 7-chl o ro -6- (202)
O-methylnorl ich exanthon e with
dia zomethan e
2-C hlo ro -3-0 -methylnorliche- 392 325 By meth ylation of 2-chloro-6-0- (202)
xa n tho ne benzylnorl ich exanthon e with
DMS-K 2C0 3 and su bseq ue nt
deb enz ylation wit h BCI 3 ~
~
2-C hloro-6-0-m ethylno rliche- 393 280-283 Leeanora salina, (20 1) :;>::l
Pertusaria cieatrieosa l1l
xa n tho ne
4-Chl oro -3-0-m eth ylnorliche- 394 249-250 Spo ropodium citrinum (242) ~
xa nt ho ne (G riseoxan tho ne B) Synthesis (680) 0
::s
4-Chlo ro- 6-0-methyln orliche- 395 232-235 Spo ropodi um citrinum (242)
So
l1l
xa ntho ne
5-C h lo ro -3-0-me thy lno rliche- 396 yellowish Leeanora vinetorum (201) o
rr-
l1l
xa ntho ne (Vinetori n) needles, Byssoloma polych romum ,
~.
256-2 56 .5 B. subdiseordans,
B. trieholomum ,
~
0
....,
Sporopodium eitrinum (242 ) r-
130 (68 1) n'
::r'
l1l
5-C hlo ro -6-0-methylno rliche- 397 Leeanora contractula (20 1) ::s
~
xant hone e
7-C hloro-3-0- me thy lno rliche- 398 283-284 (681) go
0;-
xantho ne Syn thesis (680) ::s
("l
7-C hloro-6-0-met hylno rliche- 399 pale yellow Leeanora populieola, (201) Dl
xan tho ne crys tals L. alina
3 10-3 12
By co nde nsatio n o f methyl (202)
3-chloro- 6-h ydroxy-4-metho xy-
2-methylben zon ate a nd
phl oroglucin ol
;:;:
w
:>:l Table 7 (continued)
V>
~ .j>.
....
'" Co mpo und M .p. (0C)
Fo rm ula Lichen Synth. Scheme Ref.
N o.
''"""'>
'"
.'"
~ 2-C hloro nor lichexa ntho ne 400 310-335, dec. 313- Lecanora populicola (201,
t:: 314.5 Synthesis 202)
'0
I (680)
'"
~ 4-Chlor on orl ichexan th one yellow Synt hesis (680)
needles, 296--298
5-Chloro no rlichexa nt ho ne 401 yellow Lecidella elaeochroma (467)
needles, 304--305 Synthesis (680)
7-Chloro nor lichexantho ne 402 285-286 Lecanora populicola (201)
Synthesis (680)
Chlorovi neto rin 403 Lecanora dispersa (497)
2-Dechloro-8-0-me thylthio melin 404 ~
224--225 Rinodina thiomela 131 (2 15)
4-D echloro -8-0 -met hylth iomelin 405 35-38 ::I:
Rinodina thiomela 132 (215) c:
::s
2-Dechlorothiomelin 406 193-1 94, dec. Rinodina thiomela 131 (215) (')
4-D echlo ro th iom elin 407 224--227, Rinodina thiomela 132 (2 15)
":-:-
24 1-243
Demeth ylchod at in 408 yellow Lecanora pachysoma X-r ay ana lysis of triacetylde- (254)
crys ta ls, 284--286 meth ylchod at in
2,4-Dichloro- I- hyd roxy -7- 409 pale yellow Rinodina thiomela 133 (215)
meth oxy-6,8-dim ethy lxanthon e crystals,
157-1 58
2,4-Dich lorolichexa ntho ne 410 184--1 86 Dim elaena cf. australiensis, (20 1)
Pert usaria cicatricosa
2,7-Dichlorolichexanthone 411 pale yellow Lecanora behringii, (201)
crysta ls, L. populicola, L. salina
290-293
4,5-D ichlo rolichexan th one 412 yellow Dimelaena cf. australiensis, (20 1)
crysta ls 283-283.5, Pertusaria cicatricosa
285-286.5 Sporopodium citrinum (242)
4,7-Di chlo ro lichexanthone 413 274 no t yet foun d in lichens By bri ef meth ylat io n of 4,7- (202)
dichl o ro -3-0 -meth ylnorli che-
xantho ne with CH 2N2
5,7- Dichlorolichexan th one 414 pa le yellow Sporop odium vezdeanum (203)
crysta ls
202-205
Z
n>
2,4- Dichloro-3 -0-methyl- 415 no t yet found in lichens By meth ylat ion of 6-benzy loxy-2 ,4- (202) ::;::
norlichexantho ne dichlor on o rlichexanth on e with ;:e
DMS-K 2 C0 3 and subseq uent ~
e
debenzylat ion wit h BCl 3 on
0
2,5-D ichlo ro-3-0-me thyl- 416 276-268, (445)
-
::>
no rlichexanthon e 296-29 7 So
n>
2,5-Dichloro-6-0-met hyl- 417 yellow crysta ls, Dimelaena cf. austra liensis (20 1)
()
no rlichexan th on e 255-257 Leeanora eontraetula ::r
n>
Pertusaria cieatrieosa ~o
By co nde nsa tio n of 2-ben zyloxy-3- (196) ...,
'<
chloro -4-meth oxy-6-methylbenzoic 0
....,
acid a nd 1,3,5-trib enzyloxy-2-chlo ro - r-
(i 0
ben zene with TFAA and subseq uent ::r
n>
deb enzylat ion with BCI 3 ::>
2,7-Dichloro-3-0-me thyl- 418 pale yellow Leeanora behringii, By methylati on of 6-ben zyloxy-2,7 - (202) en
c
cr
on
no rlichexa ntho ne crysta ls, 262- L. salina dichlor olichexanth on e with DM S-
OJ
264, 297-298 K 2 C0 3 and sub seq uent eo
n>
debenzylation with BCI3 on
2,7- Dichloro-6-0-methyl- 419 pale yellow Leeanora behringii (201)

norlichexa ntho ne needles,
309-3 11
By co nde nsation of ethyl 3-chlor o-6- (202)
hydrox y-4-meth oxy-2-meth yl-
ben zoat e and 2-chlorophloroglucino l
v.
v.
~ Table 7 (continued) V>
~ 0'-
~
:::
'" Compound Formula M .p. (0C) Lichen Synth. Scheme Ref.
~a No .
~ 4,5-Dichloro-3-0-methy l- 420 yellow-needles, Sporopodium citrinum (242)
.....
w norlichexanthone 255-257
'P
..... 4,5-Dichloro-6-0-methyl- 421 280-282 Dim elaena citrinum (201)
~ norlichex an thone
Sporopodium citrinum (242)
4,7-Dichloro -6-0-methyl- 422 yellow prisms, not yet found in lichens By condensation of 3-chloro-6- (202)
norlichexanthone 286-288 hydroxy-4-methoxy-2-methyl-
benzoate and 2-chlorophloroglucinol
5,7-Dichloro-3-0-methyl- 423 pale yellow 134 (231)
norlichexanthone crystals, 248-250 til
Lecanora broccha, L. vinetor- (201)
:I:
um , Lecidella meio cocca, c
::>
<l>
L. vorax , Byssoloma subdis- ()
:>;"
cordans, B. tricholomum, Spor -
opodium , phyllocharis
5,7-Dichloro-6-0-met hylnor- 424 yellow rods , Byssoloma subdiscordans (242)
lichexant hone 275-278
2,4-Dichloronorlichexanthone 425 yellow prisms, Lecidella vorax (201)
285-287
2,5-Dichloronorlichexanthone 426 yellow needles, Buellia spec., (/98)
245-247
Lecanora broccha, Le cidella (201)
meiococca,
L. vorax
2,7-Dichloronorlichexanthone 427 yellow crystals Lecanora broccha (/98)
298-299
Lecanora behringii, (20/)
L. populicola, L. salina,
Lecidella meiococca
Syn thesis (680)
4,5-Dic hloronorlichexanthone 428 yellow Lecanora broccha, Lecidella (/98)
prisms 291-293 asema, L. subalpicida, Z
L. vorax, Micarea isabellina, (20l) :;:;
'"
Pertusaria pycnothelia
4,7-Dichloronorl ichexanthone 429 yellow crystals Lecidella asema (/98) ''"g."
L. meiococca
'"
0
290-293, (20 /) ::>
297-298 Synthesis (680) SO
5,7-Dichloronorlichexanthone 430 yellow crystals, Lecanora broccha, Lecidella (20/) ()
'"
285-290 vorax ::r
1,7-Dihydroxy-2,4-dic hloro- 431 pa le yellow Rinodina thiome la 133 (2/5) 3
'"
<n'
6,8-dimethylxanthone crysta ls ...,
'<
188-1 90 0
-....,
1,8-Dihydroxy-3,6-dimethoxy- 432 pale yellow Diploschistes spec. 135 (2 /7)
<S
r-.
xant ho ne crystals 193-1 94 ::r
1,5-D imeth oxy-4-chloro-6- 433 yellow crystals Rinodina thiomela 131 (2 /5) '"::>
C/l
met hyl-8-hydroxyxanthone 222-224
3,6-Di-O-me thylthiopha nic 434 yellow crystals, By permethylat ion of 6-0-methlythio- (202) ''"0;sr"
acid > 315, dec. phanic acid wit h DMS-K 2C0 3 and ::>
()
subsequent demethylation with BCI3 '"'"

Ergochro me BB (Secalonic 435 254-2 56, dec. Diploicia canescens (229)
Acid B) [Ci)D+ 156 ssp . austra lasica
(CHCL 3)
G ra nu losin: see 6-0-Methyl-
arthothelin
Isoartho thelin : (2,5,7-Tri - 436 yellow needles Lecanora broccha, 136 (232) V>
chloronorlichexanthone) 253-255 Buellia spec . --.l
::>::: Table 7 (continued)
v.
~ 00
.,'" M .p. (0C)
;:,
'" Compou nd Formula Lichen Synth. Scheme Ref.
".'"'" No.
~ Lichexanthone 437 yellowish needle s Lecidella patavina , (464)

N
...., 189- 190 L. stigmatea
'0
~ I-Metho xy-4-ch lor o-5,8-dih y- 438 yellow cry sta ls Rinodina thiomela 131 (215)
~ dr ox y-6-methylxa n thone 194-196
6-0-Methylarthothelin 439 yellow need les Dimelaena cf. aust raliensis , (201)
282- 284 Micar ea isabellina,
Pertusaria py cnothelia
Buellia granulosa, Lecidella (464)
elaeochromo ides
By methylation of a rtho the lin (/95)
with DMS-K 2C03 :-n
3-0 -Methy lnor lichexa nthone 440 253-255 Lecanora vinetorum (201)
::c
(Griseoxanthone C) r>
"
("l
'=
:>;"
8-0 -Methylthiomelin 441 yellow thread s, Rin odina thiomela (2 15,
219 218)
3-0 -Methylthiopha nic acid 442 yellow need les Lecidella meiococca By chlorination of 3-0-methylnor- (202)
290-222 lichexa n tho ne with S02CI2
6-0-Methylthiopha nic acid 443 yellow need les Mi carea isabellina (201)
250-252
N orthiom elin (1,5, 8-Tri hyd roxy- 444 yellow cr ysta ls Rinodina thiomela By demethylati on of thi om elin (215)
2,4-dich loro-6-me thy lxantho ne) 212-213 with BBr3
Thi ome lin 445 yellow thread s Rin odina lepida , R . thiom ela 137 (252)
185
Thiophanic acid 446 yellow need les Dimelaena spec., L ecanora (201)
242-243 sulphurata, Lecidella
meiocarpa, L. vorax ,
M icarea isabellina, Pertusaria,
pycn othe lia,
Byssoloma polychromum, (242)
Spo ropodium antonianum ,
S. leprieurii (467)
Lecidella asema , L. elaeochro-
ma, L. flavisoredia ta , L. Leuck-
ertiana, L. meiococca
T hio pha ninic acid 447 yellow pr ism s Dimelaena spec . (196) Z
:l;
'"
278-279 :;:<:l
<1l
D. australiensis (201) 'J>
T huri ngione 448 yellow needl es Byssoloma polychromum (242) ~

278-279 0
2,4,5-T richloro lichexanthone 449 yellowish Dimelaena cf. australiensis (201) ='
So
<1l
needles 225-227 Pertusaria cicatricose
(")
2,4,7-T richlorolichexa nthone 450 pale yellow By perm eth ylati on of 2,4,7-trichloro- (202) ::r
<1l
crysta ls 254- 3-0-methylnorl ichexanthon e with 3
~.
256, dec. DMS-KzCO ) and subsequent
~
dem eth ylat ion with BCI 3 0
2,5,7-T richl or olichexanthone pale yellow (20 1)
....,
451 Dimelaena cf. australiensis,
crystals 245 Lecanora broccha c:
(')
cr-
<1l
4,5,7-Tr ichlor olichexanthone 452 pale yellow not yet found in lichens By meth ylati on of 4,5,7-trichloro- (202) ='
crystals 6-0-meth ylnorlichexanth on e with en
0-
205-2 10 CH zN z 'J>
';:;;"
2,4, 7-T richloro-3 -0-methyl- 453 yellow crys ta ls no t yet found in lichen s (445)
o='
norlichexanthon e 257-259, dec. ~
2,4,7-Tri ch lo ro- 6-0-methyl- 454 yellow crys ta ls not yet found in lichens By chlori nation of 7-chloro-6-0- (202)
norliche xanthon e > 310, dec. methyln orli chexanthone with SOzCl2
2,5,7-Trichlo ro- 3-0-methyl- 455 pale yello w Lecanora broccha, Lecidea (198)
no rlichexa ntho ne crystals asema, L. subalpicida,
259- 261
L. behringii, Spo ropo dium (20 1)
V>
vezdeanum , '0
Table 7 (continued)
;.;, ~
S, Compound Formula M .p. (0C) Lich en Syn th. Scheme Ref. 0
'=:~" N o.
'"
'"
.'" S. xantholeucum, (203)
~ By ssoloma po lychromum, (242)
~ B. subdiscordans, B. tricholo-
'C
I mum, Sporopodium phyllo-
'"
0-
'" charis
2,5,7-Trichloro-6-0-methyl- 456 yellow need les By condensation of ethyl 3-chloro- (202)
norlichexanthone 249-253 6-hydroxy-4-methoxy-2-methylben -
zoate and 2-chlorophlorogluci nol
4,5,7-Trichloro-3-0-methyl- 457 yellow needles Lecanora broccha, Lecidella (201)
norlichexanthone (3-0- Methyl- 285-287, meiocarpa, Synt hesis (680)
asemone) 294-295
Bys soloma subdis cordans , ~
(231,
B. tricholomum 242) :r:
e
::l
4,5,7-Trichloro-6-0- 458 yellow needles Pertusaria pycnothelia (201) <'1l
(')
~
methylnorlichexanthone (6-0- 298-300, dec .
Me th ylasemone)
138 (233)
2,4,7-Trichloronorlichexanthone 459 yellow crystals Lecanora sulphurata (201)
228-229
4,5,7-Tric hloronorlichexanthone 460 yellow needles Micarea austroternaria (233)
308-309, dec . var. isabellina
1,5,8-Trihyd ro xy-4-ch loro-6- 461 yellow crystals Rinodina thiomela 131 (215)
methylxanthone 212-2 14
1,5,8-Trimethoxy-2-chloro-6- 462 pale yellow Rinodina thiomela (215)
methy lxant hone gum
1,5,8-Trimethoxy-4-chloro-6- 463 yellow crystals Rinodina thiomela 131 (215)
methylxanthone 197- 199
1,3,6-Tri-O -met hylarthothelin 464 yellow need les By meth yla tion of arthothelin (/95)
200-202 with DMS-K 2C03
**
"'"
R'" R
"'"
I ~ I~ 00
R R' R" R' "

337 : CI CI CI H
41)() : CI H H H
401 : H H CI II
402: II II H CI
403 : CI OM. CI CI
425: CI CI H H
426: CI H CI H
427: CI II II CI
423: II CI CI II
429: II CI II CI
430 : II II CI CI
436: CI II CI CI
446: CI CI CI CI
459: CI CI II CI
460 : II CI CI CI
OMe
R" R'
R R' R" RH '
388: CI H H H
389 : H CI H H
390 : H H CI H
391 : H H H CI
410: CI CI H H
411 : Cl H H CI
411 : H CI Cl H
413 : H CI H Cl
414 : H H CI CI
434 : Cl Cl CI CI
437 : H H H H
449 : CI CI CI H
450 : Cl CI H CI
451 : CI H CI CI
451 : H CI CI Cl
162 S. Hun eck
OMu
R R' R" R'"

391: CI II H II
394: II Cl II II
396: II II CI II
39B : II II II Cl
403 : R" ~ CI,R = R' = R'" ~ II, II, Cl
4/5 : Cl Cl II II
416 : Cl II CI II
4/B : Cl II II Cl
410 : II CI CI II
413 : II II CI Cl
440 : II II II II
441: CI Cl Cl CI
448: CI CI CI II
453 : CI CI II Cl
455: CI H CI CI
457: H CI Cl Cl
~~
MeO
1 0 0
0
011
R" R'
R R' R" R'"

393 : CI H H H
395 : H CI H H
397 : H H CI H
399 : H H H CI
417 : CI H CI H
419 : CI H H Cl
421 : H CI CI H
421 : H CI H CI
414 : H H CI CI
439 : CI CI CI H
443 : CI CI CI CI
447 : CI CI H H
454 : CI CI H CI
456 : CI H CI CI
458 : H CI CI CI

R R' R"
404 : H CI Me
405 : Cl H Me
406 : H CI H
407 : CI H H
441 : CI CI Me
445 : CI Cl H
R R
R R' R" R R' R"

433 : H CI H 438 : H C1 Me
462 : CI H Me 444 : CI CI H
463 : H CI Me 46/ : H CI H
~OMe
:
4: co~:
*
Me COOH 1.TFM
I: + I '>:::: 2. H2o Pd-C.
I I
KOH.ctOH
•
BoO OBo MeO ~ OMe H ~ OH MoO ~ Me
I I
-
Me OMe
OMe
BBr,
OHyoMOH
~~
396 : Vinetorin
Scheme 130. Synthesis of vinetorin
-
DCCD
OMoo E~~ ~"'" TFM
~~
K,co,.
:
4! coX?: ~
Me
0 ~
BC~
~ 404
Scheme 131. Synthesis of 2-dechloro- 8-0-methylthiomelin and related compounds

JfC
HO OH
I ~ +
Et .b Me
Me
OMs
~ I~~~
EIOOC CI
/V
1.KOH
2. Cu,O, BiPy.
Me .b
1. OMS, K,CO, a
2.BCI;,
•
407 405
S cheme 132. Synthesis of 4-dechloro-8-0-methylthi omelin and 4-dechloroth iomelin
1.BBr,
2. H,O. 120' C
•
DMS,K,co,. MeO+CO*:a ~
~O .b
I
431
409
Scheme 133. Synthesis of 2,4-dichloro-I -hydroxy-7-methoxy-6,8-dimethylxanth one

166 S. Huneck
CO)XOMe
~
Me
CI*MeCOOH
I '<::: +
CI
I:
coer,
I:
1. BCl,
2. KOH, ElOH,
BnO ~ OBn BnO OBn
423
Scheme 134. Synthesis of 5,7-dichloro-3-0-methylnoriichexanthone
~~
~~Me
432
Scheme 135. Synthesis of 1,8-dihydr oxy-3,6-di-O-methylxanth one
I: ):X
080
~
co
~
CI CI
800 080 BnO ' OBn

I
*
KOH,BOH 1 Me )):OHCI
• I '-':: I '-'::
# # H
1
Scheme 136. Synthesis of isoarthot helin

C»O
OMe
CCI
I~
.0
--
4
0H
-
c*OHCI 1. CH,N,
BB<3 I ~ I ~ 2.BC!,
.0 ° .0
:
H I
4 1.0
Me
CO*H
°
us
1.0
S cheme 137. Synthesis of thiomclin

I
CI
1f
#
4I 1
CI
1
I
: COOH
+
H01(COOB~
I~ ~ :
Me co-o
I:
OH
K2CO,-CMSO..
.0 H .0 CI H COOBn
I H I H
Clxf::
#
1 Me c*OHCOOBn
I coohCOOBn
::r I ~ I ~ I ~ 1. Bel,
MaO.o ~ OH .0 .0 2.KOH
OH -
I I 1 I
~S8
S cheme 138. Synthesis of 4,5,7-trich1oro-6-0-methylnorlichexanth one

168 S. Hune ck
~
Me COCI
I ~ +
hOMe
HOMH
~oo'1S
HM~
_
465 Noclichexanthone
1
1. TFAA
2.H, . PdC
rt
OBn
HOOC~
BnoUoBn +
Bno M oBn
Scheme 139. Dehydrat ion of 2,2',4,4' ,6'-p entah ydroxybenzophenone
to norlichexanth one
Norfichexanthone
Scheme 140. Cyclizatio n of 1-(2,4,7-trihydroxyphenyl)-octane-1,3,5,7-tetrao ne

to norlichexanthone

4.5.11. BenzoJurans
1,3-Dihydrox y-6-(l'-hexano yl)-benzofuran (466) is the only known
benzofuran from a lichen (Letharia vulpina) (685).
466
4.5.12. Dibenzofurans
Structure, occurrence and synthesis of new dibenzofurans are
summarized in Table 8.
Shibata and Iitaka (647) confirmed the structure of didymic acid by
an X-ray analy sis of its oxidation product 491 (see Scheme 151).
467
J50CC
~
I -.. : : Me
I -.. : :
c~
-...:::-...:::
0
~.& 0Me
I~ I~ 0Me
470 • 471
47/
M
Me
COOMe
1-"'::: I-"':::
Me.& ~OH
OOH
473
::0 -.I
~ 0
...'" Table 8. Dib enzofuran s from lichen s
:::
'"
.a Co mpound Formula M .p. (0C) Lichen Synth . Scheme Ref.
~ N o.
N
W
Alectosarmentin 467 29 1 A lectoria sarmenlosa (327)
~ Ascomatic acid 468 242 Bunodophoron palagonicum 14 1 (260)
~
3-0- Demethylschizopeltic 469 292-294 Roccella hyp omecha Syn thesis by demeth ylati on (392)
acid of schizopeltic acid with
BC l3
Didymic acid 470 165- 167, 172- 173 142 (6 1)
Dim ethyl di-O- 471 162-1 64 Roccellina luteola (300)
methylpan nar at e
143 (325) ~
Di-O-methylstrep silin 472 256-257
Ha emop haein (F urfuraceic 473 208-2 10 Phyll opsora haemophaea (369) ::r:
to
::l
acid) <1>
(")
,.,..
Phyllopsora furfu race a (259)
4-H ydro xypannari c acid 474 180- 18 1 Leproloma dijJusum 144 (249)
9-methyl ester
Hypostrepsilalic acid 475 yellow crystals M ycobi ont of S tereocaulon M ethyl di-O-meth ylhy- (550)
256-257, dec. japonicum po strepsilalat e gave o n
C lemmensen reduction
methyl di-O-meth ylhy-
postr epsilat e
Hypostrepsilic acid 476 228-230 Mycobi o nt of Evernia X-ray analysis of meth yl (468,548)
esorediosa di-O-m et hylhypostr epsilat e
Isod idymic acid 477 148-1 50 Cladonia didyma 145 (69)
Isoschizopeltic acid 478 199- 201 Comb ea californica (24 7)
Isostrep silic acid 479 210-220 M ycob iont of Usnea (468)
orientalis
Melacarpic acid 480 148-149 Neop hy llis melacarpa 146 (60)
Meth yl asco ma ta te 481 154 Bunodophoron pa tagonicum 141 (260)
M eth yl di-O-met hylpo r- 482 280- 282 147 (632)
phyri late Z
<1l
~
Me thyl 6-0-methylnoras- 483 147-149 Bunodophoron patagonicum 141 (260)
;:tI
coma tate <1l
'"
6-0-Met hylno rasco matic 484 204 Bunodophoron patagonicum 141 (260) ~
ac id 0
::
3-0-Meth ylpannaric acid 485 164--1 66 Combea californica 148 (247) :;.
N orascomatic acid 486 227-229 Bunodophoron patagonicum 141 (260) <1l
(J
Norschizopelti c acid 487 Structure not yet Roccellina luteola (300) ::-
<1l
esta blished 3c;; .
Pannaric acid 9-methy lester 488 218-220 R occella capensis This compo und was (397)
er ro neo usly assigned th e S
0
-,
str ucture 3-0-meth ylpannaric l'
acid; its struc ture was revised "'cr-.
<1l
by Elix et al. (248) ::
Pa nnaric acid 10-meth ylester 489 pale yellow crysta ls 149 (253) C/l
226-2 28 'cr'"0;-"
Subdidymic acid 490 158.5-1 60 150 (237) ::
()
<1l
'"
::::
172 S. Huneck
475
477
478 479 480
~~
COOR.
1.0 :::,.. I
OR
R'
R R' R"
468 : Me Me H R R' R"
476 : H H 485 : Me H H
H
48/ : Me Me Me 48 7 : Me H Me
483 : H Me Me 488 : H H Me
484 : H Me 489 : H Me H
H
486 : H H H
490
482

New Result s on the Chemistry of Lichen Sub stan ces 173
- NaCIO,
481 : Methyl ascomatate 486 : Norascomatic acid
j"'
~
e HO
I ":: I ":: 0
HO h- 0 h- OH
483: Methyl 6-o-methylnorascomatate 46 7 ; Alectosarmentin
Scheme 141. Synthesis of ascoma tic acid and derivativ es
470 ; Didymic acid
Scheme 142. Synthesis of didymic acid

174 S. Huneck
rt~
1.Br,
2. NaOH.DMF
3. CuCN
4.KOH
.. MeOMMoMe
472 : Di-O-methylstrepsilin
Scheme /43 . Synthesis of di-O-methylstrepsilin
H n-GSH11
~
n-GSH1 1
o 0
I"':: I"':: 0
HO h- 0 h- OH
473: Haemophaein
Me Me OH Me
~ Jt~
BnBr, NaHC0 3
H"P~
Bn h- ::::,.. OH ~ 0::::'" OH
Me
M'
OH Me
-
COOMe 1.B03
I ~ 7' I Pd(OAcl:z 2. BB<3
Me ~ ::::,.. OH OH
OOBn Me
OH Me
-
COOMe COOMe
180"C
OH OH
474 : 4-Hydroxypannaric acid 9-methylester
Scheme 144. Synthesis of 4-hydroxypann aric acid 9-methylester

~H7
I"HgO } j C I
-1-":::'
MaO A' OMe
1
CU, 205 ' C
£c-:6
n-C,H" n-G,H,
1. OMS, K2CO,
-:r HBr 2. C~CHOMe, TiC~
I 1-
MeO A' :::,... OMe
Me
1. NaGICl,
2. BC~
477 : lsodidymic acid
Scheme 145. Synth esis of isodidymic acid
»N
I
-..:::,
A' Br
+
I.KOH
2. Bel3 •
480 : Melacarpic acid
Scheme 146. Synthesis of me1acarpic acid

176 S. Huneck
OMs
1. B',.light
-
12 • .aq.Triftuoroaeelafll
2. NaOAc
3.NaOH
1. NaCN.DMF
2.KOH
3. Mel, K2CO,
•
482: Methyl di-Q-methylporph}Tilate
Scheme 147. Synthesis of methyl di-O-methylporph yrilate
HO
.c.c:I
R
.0 0
I
Me
.0
COOH
OH
475: R=CHO
479: R=Me
tc
Me
. ~'(YOH 1. K,co, . DMSO

2. BnDr, KHCo, ~::Lc
I -" I ~
COOBn •
Bno~ ~
3.DMS.K,co,
• Dna'''' ....
Me
OH Me
-....50.
COOH
485 : 3-Q-Methylpannaric acid
Scheme 148. Synthesis of 3-0-methylpannaric acid

469: R=R"'=H,R'=R"=Me
~
OR' Me COOR"
471 : R=R'=R''=R"'=Me
I "':: I "':: 478: R=R'=R"'=Me,R"=H
Me .Q a .Q OR
485: R=Me,R'=R'=R"=H
COOR'"
488: R=R"=Me, R'=R"'=H
489 : Pannaricacid IO-methylester
Scheme 149. Synthesis of pannaric acid lO-methylester
-HBr, ill
490 : Subdidymic acid
Scheme 150. Synthesis of subdid ymic acid

178 S. Huneck
Didymlcacid 491: l -<H'en1y1-2-mo1holl)'Qlrt>onyl-3.Ek1inelhoxalyl-

dbenzofuran
Scheme 151. Oxidation of didymic acid to 1-n-pent yl-2-methoxycarb onyl-3,6-

dimethoxalyldibenzofuran
4.5.13. Usnic Acid and Related Compounds

Usnic acid is one of the biologically most active compounds which
ju stifies a discussion of its three-dimensional structure. According to
an X-ray ana lysis of (- )-usnic acid by Norrestam et al. (566) the three
hydroxyl hydrogens of the molecule are all involved in strong
intramolecular hydrog en bonds and no intermolecular hydrogen
bonds were found (see Fig. 4). In an X-ray ana lysis of (+) -2-
deacylusnic acid (a biodegradation product of usnic acid) Mac Donald
et al. (519) observed the O-O-distances shown in Fig. 5. Kutne y and
Sanchez (481) carr ied out an X-ra y anal ysis of (-)-~2, l l -enaminousnic
Fig . 4. Hydrogen bond s in (- )-usnic acid
Fig. 5. a - a -Distances in (+) -2-deacylusnic acid
Ref erences, pp . 239-2 76

N~
Fig. 6. Computer generated structure of (- )-tJ. 2·"-enaminousnic acid
I
Fig. 7. Tautomeric forms of (+ )-usnic acid
Me Me
Fig. 8. Computer drawing of the structure of the sodium 2 y, hydrate of (+ )-usnic acid
180 S. Huneck
acid which was prepared from (+ )-usnic acid with ammonia. The
computer generated structure of this compound is shown in Fig. 6.
Behrens et al. (30) found by X-ray analysis of (+ )-usnic acid that the
molecule exists in the two energetically equal tautomeric forms shown
in Fig. 7. However a theoretical study by Buemi and Zuccarello (49) led
them to conclude that tautomer I predominated in solution. Ribar et al.
(620) carried out an X-ray analysis of the sodium salt of (+ )-usnic acid
which showed that both usnic acid ligands are different as shown in
Fig. 8: one is bound to the sodium 1 ion as a monodentate, the other is
bidendate.
The absolute configuration of (+ )-usnic acid has been determined by
an X-ray analysis of the (- j-o-phenylethylamine derivative 492 (389).
492
(+ )-Usnic acid afforded on photolysis in tetrahydrofuran-methanol

the ring C-open compound 493 shown in Scheme 152 (690) .
The fungus Mucor globosus degrades (+ )-usnic acid to (+ )-desacet-
ylusnic acid (494) (480) (see Scheme 153).
---
Me
MeOH
,Me
Scheme 152. Photolysis of (+)-usnic acid

OH
Mucor gIobosus
EIOH,15O"C
a
(+)-U&nic acid 494 : (+}2-Desacetylusnic acid
Ethylac:eI1Jsnetale
OH
o
0Ac
(+)-Usnicacid
Scheme 153. Degradation of (+)-u snic acid by Mucor globosus
496 : l-Dihydrousnic acid
Scheme 154. Enzymatic hydrogenation of (+)- and (-)-usnic acid

182 S. Huneck
Estevez et al. (285) isolated from cell-free extracts of Evernia

prunastri the enzyme DL-usnic acid dehydrogenase which catalyzed
the reduction of (+)- and (-)-usnic acid; formula 495 was presumed
to be that of the reduction product. Some time later Vicente and
co-workers (708, 709) purified a second dehydrogenase which converted
only the dextrorotatory enantiomer of usnic acid to l-dihydrousnic acid
(496) (see Scheme 154). The structure proposals for both dihydro
derivatives were primarily based on the IR spectra and need to be
confirmed by NMR, MS and /or X-ray analysis. Phenyl and isonicot-
inoyl hydrazones of (-)-usnic acid (497, 498) have been reported, while
reduction with sodium borohydride gave a mixture of 13cx- and 13~
dihydrousnic acid (499) (585).
497 : R=-e"H.
499: 13-Dihydrousnic acid, R = H, OH
498 : R = -co-C N
The trans-stereochemistry at the ring junction of (-)-placodiolic

acid (500) from the lichen Rhizoplaca chrysoleuca was established by
an X-ray analysis (78). (- )-Cercosporamide (501) is a phytotoxin from
the fungus Cercidosporidium henningsii; its structure was established by
X-ray crystallography (679) and its absolute configuration was deter-
mined as C-9b-S by correlation with synthetic (+ )-8-methylcercospor-
amide (502) (81) (see Scheme 155).
Me
Me 0
500 : (-)-Placodiolic acid 501: (-}-Cercosporamide, mp 188-189°C
The absolute configuration at the C-9b-position of (+ )-usnic acid

was fixed as R (389). Since the optical rotation of (+ )-8-methylcer-
cosporamide, synthesized from (+ )-usnic acid, is opposite in sign to
that of naturally occurring (-)-cercosporamide, the latter should have
the S-configuration at C-9b. The CD spectra of (-)-cercosporamide,
References , pp. 239-276
1. NHzQH.Py
2. EtCH
..
(+HJsnIcacid (+}-UInlcacidoxinllanhydr1dll (milor)
B A
!
(major)
N-{leIt-llliytdinelhyl&i1yt}N-mol/1ylrl
acetamide in OMFfTliF
Structure A (482,483) was revised to B (81)
Pb(OAcl.
..
COOH 1. l ,l'-cartxlnykl~
--
triaZllle
2.NH, Hrl't
3, HCI
..
HOyC;~OH
~
502 : (+)-8-Methylcercosporamide
Scheme 155. Synthesis of (+)- 8-methylcercosporamide

184 S. Huneck
+6
e
- 6 +-------,,-------.---,----.-
250 350 450 nm
Fig. 9. CD spectra of (-)-cercosporamide (a), (-)-usnic acid (b), (+)-usnic acid (c),
and (+ )-8-methylcercosporamide (d)
(- )-usnic acid, (+)-usnic acid and (+)-8-methylcercosporamide are

shown in Fig. 9.
(-)-Usnic acid amide (503) is another phytotoxin from Cercospo-
ridium henningsii (80).
503 : (-)-Usnic acid amide, yellowpowder
Structures of the phytotoxins (- )-mycousnine (504), (+)-isomy-

cousnine (505) and (+)-oxymycousnine (506) from the phytopathogenic
fungus Mycosphaerella nawae which causes the circular leaf spot disease
of Diospyros kaki were elucidated using spectroscopic and chemical
evidence. (-)-Mycou snine and (+)-isomycousnine were synthesized by
reaction of (+)-usnic acid with HCI-MeOH. (+)-Oxymycousnine gave
with methanol (+ )-desacetyloxymycousnine (507) which was oxidized to
triketone 508, identical with the H 20 2 oxidation product of (-)-
mycousnine (634). Isoplacodiolic and isopseudoplacodiolic acid from
the lichens Haematomma flexuosum and H. matogrossense (255) are
identical with mycousnine and isomycousnine respectively.
New Result s on the Chemistry of Lichen Substances 185
504 : (-)-Mycousnine, mp86-89°C
#ti
Me 0Me
(+)-Usnic ecid He> OH
I~ I
b f
Me Me
505 : (+)-Isomycousnine, mp 78-79°C
OH
- MeOH
H
506 : (+)-Oxymycousnine, mp 119-122°C 507 : (+)-Desacetyloxymycousnine
508
Scheme 156. Structure and synthesis of (-)-mycousnin e, (+ )-isomycousnine and

(+ )-oxymycousnine
186 S. Huneck
~~OH
~ _~----:H,-=Iig:-.hl_.
509 : Simonyellin, yellow crystals, 510
mp 274-275°C
Scheme /5 7. Reaction of simonyellin with meth anol
4.5.14. Naphthopyran s
The structure of simonyellin (509), a naphthopyran from the lichen
Simonyella variegata, has been establi shed by X-ray analysis of the
tetraacetate derivative (210). In solution of alcohols or acids simonyellin
is light sensitive; thu s with MeOH it forms the colourless naphthalene
derivative 510 (see Scheme 157).
4.5.15. Quinones
4.5.15.1. Benzofuranoquinones and Benzoquinones
Miyagawa et al. (549) isolated from the cultured mycobiont of
Graphis desquamescens the benzofuranoquinone graphisquinone (511).
Dallacker and Ditgens (156) synthesized polyporic acid (512) starting
from 1,2-dimethoxy-4,5-methylenedioxybenzene as shown in Scheme
158.
:¢=>-~
o
511 : Graphisquinone, red needles
mp J27_128°C
References, pp. 239- 276

-
~0Me HM1PT
~ NaOH
1 .~ o
-
2. CycIohexanone
3. poTsOH HNO,
o o
- It
512 : Polyporicacid, violetcrystals,
Scheme 158. Synthesis of polyporic acid
4.5.15.2. Napthoquinones and bis-Naphthoquinones

The structure of the red pigment from the apotheciae of Cladonia
deformis and C. flo erk eana, rhodocladonic acid , was shown to be 2-
acetyl -3,4,6-trihydroxy-7-methoxynaphtho[2,3-b]furan-5,8-dione (513)
(540). Lichenicolous mites trigger the production of rhodocladonic
acid in Cladonia bacilliformis and C. norvegica (697).
513 : Rhodocladonicacid, red crystals, mp > 360°C

-. :
188 S. Huneck
:0::
Me
I 0Me
~
l.rHluU=*=:
I _Cu_--.-_
-
.Q .Q
Bar3
2,3,5,6-Tetramethoxy- 1
lokJene
:ce :xx: I -..: :

.Q
l.rHlI,.
2.
uU I -..: :
.Q
1,2,4,5-Telnmllhoxy-
benzene
-- Otf
514 : 3,3',6,6'-Tetrahydroxy-4-methyl-
biphenyl-di-p,p -quinone
S cheme /59. Synthesis of 3,3',6,6'-tetrahydroxy-4-methylbiphenyl-di-p,p'-quinone
In 1965 Chandrasenan et al. (65) proposed structure 514 for pyxiferin,

the main pigment from Pyxine coccifera. This substance was subse-
quently synthesized (see Scheme 159) and found to differ from natural
pyxiferin. Later on Huneck (380) identified pyxiferin with chiodectonic
acid and proposed structure 515 for this pigment.
515 : Chiodectonic acid (Pyxiferin)
darkred plates, mp 294-296°C
The naphthoquinones 1,4,5,8-tetrahydroxy-3-ethyl-naphthalene-2,6-

dione (516) and 7,7'-bis-(l ,4,5,8-tetrahydroxy-3-ethyl-naphthalene-2,6-
dione (517) have been found in Cetraria cucullata (475). Islandoqui-

none, 2-0-(3' -ethyl-l ',2',3',4'-tetrahydro-5',7',8'-trihydroxy-l ',2',4'-tri-
keto-3' -naphthyl-3-ethyl-7-hydroxynaphthazarin (518), is a new
naphthaquinone from Cetraria islandica (671).
E1W1'"
o ~ ~
0
5/6 : red crystals, mp 183-1 85°C
OH OH
5/7 : red crystals, mp265°C, dec. 5/8 : orangecrystals, mp 243-244°C
Formula 519 was originally proposed (47) for the red pigment
haemoventosin of the apotheciae from Ophioparma ventosa and
subsequently revised to 520 (536). Its structure was finally established
5/9 520
--
KOH
52/ : Haemovenlosin, redbrown crystals, Norhaemoventosin
mp202-204°C
Scheme 160. Structure and saponification of haemoventosin

190 S. Huneck
as 521 on the basis ofNMR studies and ORD data (625). The encircled
part of the structure explains the facile saponification of haemoventosin
to norhaemoventosin (see Scheme 160).
The lichen Squamarina cartilaginea is sometimes infected by a
Wardomyces fungus and then forms deep red spots on the thallus . The
structure of this pigment, squamarone, has been elucidated by NMR
spectroscopy as 2,6,8-trihydroxy-3-methyl-7-ethyl-1,4-naphthaquinone
(522). This is the first example of the formation of a phytoalexin by a
lichen (370) . The naphthaquinones cristazarin (523) and 6-methylcri-
stazarin (524) have been isolated from cultures of the spore-derived
mycobiont of Cladonia cristatella (744).
W
Et
=
H
IOH
Me
522: Squamarone, orange needles,
mp275-27rc
:O
:w
Me A
H °
I
523 : Crislazarin, R H
Et
OH
=
524 : 6-Methylcrislazarin, R = Me
4.5.15.3. Anthraquinones
New anthraquinones from lichens are summarized in Table 9.
Syntheses of the following anthraquinones have been described :
islandicin (531) (see Scheme 161) (734), erythroglaucin (532) (see
Scheme 162) (42), citreorosein (533), fallacinol (534), fallacina1 (535)
(see Scheme 163) (373), and chrysophano1 (536) (see Scheme 164) (560) .
In 1907 Zopf (764) isolated from the lichen Cladonia bellidiflora a
red-brown crystalline compound which he named bellidiflorin. More
than 80 years later Alagna et al. (7) showed by X-ray crystallography
that bellidiflorin is an iron complex of the bis-anthraquinone graci1i-
formin (186); the coordination of the ligands to the iron atom is shown
in Fig. 10.
New Result s on the Chemistry of Lichen Substa nces 191
Table 9. Anthraqu inones from lichens
Co mpo und For mula M .p. (0C) Lichen Ref.

No.
Asa hinin 525 red crystals, Asahinea (54 7,

> 320 chrysantha 672)
Averythrin 526 red pri sms, Solorina crocea (48)
229-231
Haem at ommon e 527 red needles, Haematomma (390)
> 300, dec. puniceum
Nemetzo ne 528 orange red needles Haematomma (396)
289- 290 nemetzii
Ru ssulon e 529 red substance Lecidea (528,
russula 532)
1,5,6,8-Tetrah ydroxy- 530 dark red crysta ls, Asahinea (547)
3-me thyla nth ra q uino ne > 320 chrysantha
~
H O :R
Me HO
I~ I~ OH
o
525 : R =OH 526 : R = -CH=CH-{CH2b-Me
530 : R=H 527 : R = -eO-Me
ME
528 529
192 S. Hun eck
-
~
Br
zn.AcOH
I~
~ Br
531 : Islandicin
S cheme 161. Synthesis of islandicin
~
0M0 u. I .H,SO,
- I ~
~
~ A
Me
2. HBr-AcOH
Mea
I:
~
~
I ~Me
~ 531 : Erythroglaucin
I.H2S0,
Islandicin
f 2. AIC~
S cheme 162. Synthesis of island icin and erythroglaucin

Me
- NBS
-
OAe
NaOH
533 : Citreorosein
1. NBS
2.Ac,~0Ac
3. NaOH
Me
53" : Fallacinol
535 : Fallacinal
Scheme 163. Synthesis of citreorosein , fallacinol and fallacinal
OMe
~- Me
MaO
-
I. Mel 1.TI'M
2.MeNO, 2. CrO:.
3. NaOH 3. H!l<
536: Chrysophanol
Scheme 164. Synthesis of chrysophanol

194 S. Huneck
Me
Me
Gracilifonnin
Fig. 10. Coordination of the gracillifo rmin ligands to the Fe atom in bellidiflorin
4.5.15.4. Phenanthroquinones
7,7'-Dichlorohypericin (537) and 2,2',7,7'-tetrachlorohypericin (538)
are new phenanthroperylenequinones from Nephroma laevigatum and
Heterodermia obscurata respectively. Both compounds were synthesized
by chlorination of hypericin with N-chlorosuccinimide in dimethylform-
amide (73, 74).
Me
Me
537 : 7,7'-Dichlocohypericin. R = H
538 : 2.2'.7,7'-Tetrachlorohypericin , R = CI
4.5.15.5. Phenanthroperylenequinones
Mathey (528) isolated from the lichen Laurera sanguinaria the
quinone isohypocrellin and proposed structure 539.

539: lsohypocrellin
4.5.15.6. Perylenequinones
Biruloquinone is the only phenanthrenequinone known from a
lichen (Parmelia birulae). Structure 540 was originally proposed by
Krivoshchekova et al. (477) but was later revised to 541 by Arnone
et al. (20) who isolated it from the fungus Mycosphaerella rubella.
0Me
o
OMe
HO
Me
541 : Biruloquinone, dark violet crystals.
mp 307-308°C
4.5.16. Pulvinic Acid Derivatives

Demethylleprapinic acid (542), 4-hydroxyvulpinic acid (543),
2-hydroxypulvinic acid dilactone (544) and methylcalycin (545) have
been isolated from Himalayan Lepraria species and from Letharia
vulpina respectively (14, 685). The structure of vulpinic acid (546) has
been confirmed by an X-ray analysis (41). More than twenty years ago
Pattenden (573) reviewed naturally occurring 4-ylidenebutenolides in
vol. 38 of this series. Since then numerous new synthetic ways to
pulvinones have been developed (see Schemes 165-168).
196 S. Huneck
542 : Demethylleprapinic acid
543 : 4-Hydroxyvulpinic acid 544 : 2-Hydroxypulvinic acid dilactone
545 : Methyicalycin 546 : Vulpinic acid
Fully methylated pulvinic acid derivatives are cleaved by alkali to

2-aryl-3-methoxymaleic anhydrides and arylacetic acids (see Scheme
169). The products formed indicate the structure of the particular
pulvinic acid (184). By reaction of vulpinic acid with 2-hydroxy-
ethoxyacetamide a mixture of pulvinic acid monolactam (547) and
pulvinic acid dilactam (548) (see Scheme 170) has been obtained (656).
Further new pulvinic acid derivatives are vulpinic acid isopropyl ether
(549) (660) and the pyridazine 550 (600) (see Schemes 171 and 172).
Chawla et at. (67) investigated the photochemical conversion of pulvinic
acid to leprapinic acid.
1.1·-Car!lonyldiimidazole
•
Scheme 165. Synthesis of pulvinones after Jcrris et at. (444)

ots·
1· ..000<'"-0
P~:):XJ
Scheme 166. Biomimetic synthesis of pulvinic acids after Ramage et al. (606)
-
OMS,
K,co,
Br-CH,-COOEt ----
~Ot~~
NBS
AzoisobtJlyronitrile
• 0" 'La ~h-cHO, NaOE~
{Z)-f'ulvinone {~ulYinone
Scheme 167. Synthesis of pulvinones after Campbell et al. (53)
Scheme 168. Regiospecific synthesis of vulpinic acid after Weinstock (7/7)

198 S. Huneck
~o
R
-..
':
R'
Me
~
Scheme l69. Alkaline cleavage of fully meth ylated pulvinic acid derivatives
548
Scheme l 70. Conversion of vulpinic acid into pulvinic acid monolactam and
pulvinic acid dilactam
- no-a (Me),CHI
•
Scheme l 7l . Synthesis of vulpinic acid isopro pyl ether
550
Scheme l 72. Conversion of pulvinic acid dilactone to the pyridazine 550

4.6. Terpenoids
4.6.1. M onot erpenoids

The following well-known monoterpenoids have been described
from lichens , but without identification of their optical rotation:
borneol, camphene, camphor, I,8-cineol, p-c ymene , fenchol , limonene,
linalool, a-pinene, ~-pinene , terpinen-i-ol, a -terpineol, o-thujone,
~-thujone [all from Evernia prunastri (319)], and car vone [from Cetraria
islandica (658)].
4.6.2. Sesquit erpenoids

Only a few sesquiterpenoids have been encountered in studies of
lichens : ~-caryophyllene , o-copaene, ~-elemene, farne sane, ~-gurjunene,
longifolene, ce-muurolene, ~-selinene , and thujopsene from Evernia
prunastri (319) and fukin anolide A (bakkanolide A) from Cetraria
islandica (658). Absci sic acid (ABA) was detected in all 26 lichen species
investigated (175).
4.6.3. Diterpenoids
Phytol and manool ha ve been isolated from Letharia vulpina (685),
rimuene was isolated from Evernia pruna stri (561) and (- )-sandara-
copimaric acid from Ram alina hierrensis (330).
4.6.4. Sesterterpenoids
Retigeranic acid , a sesterterpenoid from the lichen Lobaria retigera,
was separa ted by HPLC int o two stereoisomers, retigeranic acid A (551)
and retigeranic acid B (552); the structures of both components were
determined by X-ray analysis (6 78).
Me
551 : (-)-Retigeranic acid A 551 : (-)-Retigeranic acid B
mp 20Q-202°C mp 188·190°C
The structures of these rather complex sesterterpenoids were a

challenge to organic chemi sts and between 1982 and 1990 no less than 5
syntheses of the retigeranic acid s have been publi shed. Corey et al.
200 S. Huneck
(83) synthesized (± )-retigeranic acid via the ring annelation AB --+ ABC
--+ ABCDE shown in Scheme 173. Paquette et al. (570) used
(- )-S-limonene as a precursor of ring A for the synthesis of (-)-methyl
retigeranate A (see Scheme 174). Hudlicky et al. (377, 378) followed
strategy A --+ AB + DE --+ ABCDE for their synthesis of (-)-retigeranic
cU cb
Me
MitstJnobtHn-.ion Me 1. H,. Rh
KOH , 2. Jonea' magent ,
: ::::,.. " " 'OH
~Me
~
cDS
Me
H Me" " '~Me r-.-\Ak~
, ~ ::::,..
t'COOMe~lAH
2.-H,O
(.LVCH, COOHI (COCI),
s A 3. H,SO,
, = 2. NEt,
""'"""'Me 4. NaOH ~MeH -
1. MoH;H<SMel,
2. n--BtLl
3. Cu-1Ji1Iate, NEt, 1. H" Pd-C
4.NaJO, 2.NaOMe
5. Aklmalgame •
..•"H i.oso,
~
1. Toe-loIH-NH, ff
2. catecholboome ,.", Me 2. NaHSo,
3. Tetrabutylnmonium- 3. Pb(OAo)',
acela1e .: ::::,..
i A
->,
(+)-Religeranic acid A
Scheme 173. Synthesis of (±)-retigeranic acid after Corey et al.

1. 0.
2. i-Pr-,SICI
3.llibel-H
4. poo,-Py •
Me
d' '''\r-f+~
-( Me Me
O=(}"'\r-f+
Me 1. H,N-NH,. K.co,
2. Ph,P.lJ1Br•• ~
-(\ Me Me
t\
~"'~'H ~
,,~..,,~
95p
H
Me
1. Me,SiCN. KCN. 18-CroM16
H,.Pl
.•.•\H --.. 2. POC!,. DBU. Py
f b " " !Me
Scheme 174. Synthesis of (-)-methyl retigeranate A after Paqu ette et al.
acid A (see Scheme 175) and Wright et al. (740) used (+ )-R-pulegone
and (- )-S-limonene as sta rting materials for the synthesis of (-)-
retigerani c acid (see Scheme 176), while a convergent synthesis of
(-)-retigera nic acid A, based on a Diels-Alder and arene-alkene
cycloaddition (CD E ---.-, ABCDE) strategy was described by Wender
and Singh (718) (see Scheme 177).
Synthe ses of potential retigeranic acid intermediates (379, 509, 621)
are described in Schemes 178, 179 and 180.
202 S. Huneck
6 6-::-:
Me
I. Ethyl 4~dimetholtyphosphonyl)- ~
.a, J.<nolha><yaotcnata.
"""A. _
UlA. CH,
"'" ~ COOEI
~CHO
...
2. _11,8< .
~ ~
UlA.THF
1.NaBH.,
~
Mo
2. _
..•,Vi KOH
3.~SnHI
i "'- .... .. -
......-'\.. I
...
~
..••,H
j e-, ""!Me
~
(-)-R8tlgefwInic acid A
Scheme 175. Synthesis of (-)-retigeranic acid A after Hudlicky et al.
~ ..
lj.. ,We
1. 1.3-Oioxan-2·yt-CH,-eH,-MgBr, CuBr, We,s , THF
2.HCI
3. p-T06Cl. Py
28
(+}-(R~Pulegone
~
1. H,N-NH,. K,C0 3
o
.
~ " " iii 2. Na,crO., AcOH • IC ,." H
.
I E " " oMe
···"Me
o
A (-)-(S)-Umonene
X
We Mo
~CH,OH
1. KH. (n-BuhSnCH,J
.
2. n-BuLi
,·-OH 1.0,. We,s ~" '-O-Si(M.lrC(Me),
o
.
CH, 2. CI-Sl(We),-e(We), 1. (l-8u),AlH
• 2. POC~ . Py
~M. We We We
Scheme 176. Synthesis of (-)-retigeranic acid A after Wright et al.

.
;:>:. Me
o-Si(Me),-C(Meh
H,N-NH" K,co,
o , - CH, •
~Me
DEAD, Ph,P,
~"'-oH --=-_. ~"'-Br ....::...-~-=-...•

Mg
ZnBr" lHF Br-CH,-eH,-8r
+A
lA=CH, lA=CH,
~Me
~
Me Me .,.Ii
NaH, toluene
.' ." lIMe
•
, COH
Me~Me ~Me
~
H
~
H
Me .•~' .•,\,Me Me ....' ._.., Me
H,
H"" -,
Me -: 1. Me,SiCN, KCN, llH:rown-6 Me ~ (iso-Bu),A1H
a 2. POCI" DBU
N
. ." +1 . ." '+1
Me~Me
~
H
~
H
Me ....' ._"Me Me }' ..,..,Me
H.....~-, H" -»,

Me -"" Me ...-::;;
NaCIO, COOH
COH
. .."'+1 . .."'+1
~Me ~Me
(-)-Retigeranic acid A
Scheme 176 (continued)

204 S. Huneck
1. (Ph,Pj,RhCl
2. Br"AoOH
3. KOIi
4. Ph,PCH,Br, rHluU
b- ~--:-6f-:
~
1. p-XylylBr. U, CuJ
~--
2.lAH
3. H" Pd-C
1. HCONH"MeCOMe.Ught
2. KOIi, OMSO, MoJ
LIlA, THF
3.SeO, + A
DioJs.Aldor 1 .~PIlA
2. tort-lluOK, DMSO
25CrC
... ,~ •
i AM..
Me~
- ~
H Me
H" Pd-C ABC o ....Vi _lAH

. .: ~ E .," IMe
i Ii Me,
~.
~ -
H Me
~
H Me
••,\Ii .•,\H
NaCIO,
. .: ~ ''' lrMa . .: ~ ..'I!Me
i A
-r-, ~A DOli
(·~icacIdA
oc:
S cheme 177. Synthesis of (-)-retigeranic acid A after Wender and Singh
H,N-NH" NaJO, « : T S O I i
KOAc, I-Ao<Jll CUSO" MeOH. I -
f Me
~H, Me-~
(Mej,CuU
-
Scheme / 78. Synthesis of a ring A intermediate of
retigeranic acid A after Roberts
1. Br2'AcOH Me&:'COOMe 1. Hydrolysis

2.NaOMe
3.0,
C'" Br-CH,-<:OOEt
• ..
2. Decarl>oxylalion
(+)-Pu1Bgone
Me
~''cooet . Me~
In..eu, M e t t e 1. (COCl),
DBU,lHF H 2. MeCHN,
Br-CH2-CH=CH-COOEt 0- •
o
OOEt
:=:0.. Me~""~ ~ 1. NaBH.

2. NaH
E~)-0> 3. (rHlu),SnH
.
t ""'Me
H,
E~:" ~'" ··' II

Me
Triquinane portion of
retigeranicacid
Scheme 179. Synthesis of the triquinane portion of retigeranic acid
Me Me
~O
6:"~
1.LDA, THF H" Rh, AJ,O,
2. HMPA,NC-C00Me
• U ; COOMe
· . COOMe
~CH2
Scheme 180. Synthesis of ring A intermediate of retigeranic acid A after Llera and
Fra ser-Reid
206 S. Huneck
4.6.5. Triterpenoids
Newly described triterpenoids from lichens are summarized in
Table 10.
The stucture of phlebic acid D was determ ined by X-ray crystallog-
raphy as 7~-acetoxy-22-hydroxyhopan-27-oic acid (581) . Its conversion
to phlebic acid C (see Scheme 181) established the structure of the latter
as 22-hydroxyhopan-27-oic acid (580) (24).
Zeorin and hopan-3~,6ct,15~,22-tetrol were found in the higher
plants Iris missouriensis (737), Tripterygium regelii (435) and Mollugo
pentaphylla (663) respectively. The C-70 polyterpene ficaprenol (588)
was found in serverallichens (618).
Table 10. Triterp enoid s from lichens
Compo und Fo rm ula M .p. eq Lichen Ref.

No .
3~-Acetoxyfern-9(l1)- 553 230-232 Pseudocyphellaria (727)

en- 12 ~-ol aurata
3~-A cetoxy fern-9( 11)- 554 200-202 Pseudocyphellaria (727)
en- 19 ~-ol aurata
3~-Acetox yfern-9(11)-en - 555 266--268 Pseudocyphellaria (727)
12-one aurata
3 ~-Acetoxyhopan-I~ , 556 273-275 Canoparmelia (403)
22-diol texana
6cx-Aceto xyhopa n-22-01 557 221- 226 Physcia aipolia ( 728)
(Acetylzeori n, Lesdainin)
Lepraria lesdainii (484, 503)
15cx-Acetoxyhopan-22-01 558 200-205 Nephroma parile (617)
(Do lichorrh izin)
Acetylisoarborinol 559 285 Cladonia macaronesica (329)
Aip olic acid 560 Phys cia aipolia (728)
o-Amyrone 124-126 Cladonia macaronesica (329)
~-Amy rone 178- 180 Evernia prunastri (9)
Fern-9 ( 1 1 )-en-3 ~, 561 210-2 12 Pseudocyphellaria (727)
12~-d iol aurata
H opan-6cx,7~, 22-triol 562 Nephroma spec. (726)
(N eph rin)
3~-Hydroxyhopan-29- 563 Evernia prunastri (9)
oic-acid
3~-H ydroxy- 30-n or- 564 Evernia prunastri (9)
hopan-22-one
3~-H ydroxyolean- 565 2 12-231 Evernia prunastri (727)
12-en-11-one
22cx-Hydroxy-3,4- 566 (82)
secostictan-3-oic acid

Table 10 (conti nued)
Compound Formula M.p. (eC) Lichen Ref.

No .
3~-Hydroxyserrat-14-en- 567 Evernia prunastri (684a)

21-one
21 ct-Hydroxyserrat-14-en- 568 Evernia prunastri (684a)
3-one
Isomul tiflorenone 569 188-1 95 Evernia prunastri (9)
Lanosterol 138-1 44 Evernia prunastri, (353)
Usnea articulata
Lupeone 160 Evernia prunastri (9)
Cladina macaro- (329)
nesica
2Ict-Methoxyserrat-14-cn- 570 Evernia prunastri (684a)
3~,16~ -dio l
3~-Me t hoxyscrrat - 14- 571 Evernia prunastri (684a)
en-Zla-ol
21o-Methoxyscrrat- 572 Evernia prunastri (684a)
1 4-en- 3 ~-ol
3 ~- Met hoxyserrat-14-en- 573 Evernia prunastri (684a)
21-one
Methyl aipolate 574 Physcia aipolia (728)
Moretenone 575 Evernia prunastri (562)
30-Nor- hopa n-3, 22-dione 576 Rhizoplaca chrysoleuca (687)
Usnea hesperina (353)
30-Nor-21ctH-hopan-3 , 577 Evernia prunastri (562)
22-dione
Rhizoplaca chrysoleuca (687)
30-Nor-21ctH-hopan -22- 578 234-235 Platismatia glauca (428)
one (lso adiantone)
30-Nor-2IctH-7~-hydroxy- 579 Pseudocyphe//aria (629)
hopan -22-one sulphurea
Phlebic acid C 580 Peltigera aphthosa (24)
Phlebic acid 0 581 Peltigera aphthosa
Conversion of ph lebic (24)
acid 0 into phlebic acid
C see Scheme 181
Serrat-14-en-3 ~,21 n-dio l 582 Evernia prunastri (684a)
Serrat- 14-en-3,21-dio ne 583 Evernia prunastri (684a)
Stictan-3~ ,22Q( -dio l 584 283 Pseudocyphe//aria
(Re tigeradiol) j/avicans
X-ray analysis (82)
Taraxerone 240-2 42 Cladina macaro-
nesica (329)
22,29,30-Trinorhopan-3, 585 Rhizoplaca chrysoleuca (687)
2I-dione
Tylolupenylacetate 586 Usnea articulata (353,684)
Zeor inone 587 251-255 Rinodina thiomela (728)
208 S. Huneck
OIl
SSJ ss~
· . ,foo
556
· "too
558
"'''foo
561 561
563 su
565 566

57/ 571
573
575
577
210 S. Hun eck
580
579
581 581
584
SB6
" '''~

...,,~
581 : Phlebic acid D

580: Phlebic acid C
t WoIfI-l<lshner reduction
..../~ ..../~
Scheme 181. Conversion of phlebic acid 0 to phlebic acid C
OH
588 : Ficaprenol
4.6.6. Steroids
Newly described steroids are summarized in Table II.
A synthesis of lichesterol (599) has been described (see Scheme 182)
(11).
Table ll . Steroids from lichens
Compound Formula Lichen Ref.

No .
Cerevisterol 589 Ramalina hierrensis (330)

Cholesta-3,5-dien-7-one Umbilicaria cylindrica (406)
Cholest-8-en-3 ~-ol Pseudeverniafurfuracea (339)
Cholest-4-en-3-one Pseudevernia furfuracea (339)
Ergosta-5,22-dien-3~-01 Pseudevernia furfuracea (339)
Lobaria pulmonaria, (626)
L. scrobiculata,
Usnea longissima
Ergosta-7,22-dien-3~-01 Pseudevernia furfuracea (339)
Lecanorastenotropa, Parmelia (687)
omphalodes, Usnea antartica
212 S. Huneck
Table 11 (continued)
Compound Form ula Lichen Ref.

No.
Ergosta-7 , 24(28 )-dien -3 ~-o l Pseudevernia furfuracea (339)

Ergosta-8 ,22-dien-3~-ol Pseudevernia furfura cea (339)
Ergosta-3,5-dien-7-one Umbilicaria cylindrica (406)
Ergostan-Jp-ol Pseudeverniafu rfuracea (339)
Ergosta-5 ,7,9(11),22-tetraen-3~-ol Pseudevernia fu rfuracea (339)
Evernia mesomorpha, (687)
Lecanora stenotropa,
Leptogium saturninum,
Parme/ia omphalodes,
Rama/ina terebrata,
Umbilicaria decussata,
Usnea antarctica
Ergosta-5,7,22-trien-3~-o l Pseudeverniafurfuracea (339)
Ergost-J-en-Jb-ol Pseudevernia furfuracea (339)
Ergosta-4-en-3-one Pseudevernia furfuracea (339)
Ergosterol-Sa.So-peroxide 590 Ergosterol peroxide from
lichens
Ergosterol-Sb.Sp-peroxide 591 is a mixture of 590 and 591 (18)
24-Ethylcholesta-5,22-dien- Lobaria pulmonaria, (626)
3~-o l L. scrobiculata, Usnea
longissima
Evernia mesomorpha, Lecanora (687)
stenotropa, Leptogium
saturninum, Nephroma
helveticum, Parmelia
omphalodes, Rama/ina
terebrata, Umbilicaria
decussata, Usnea antartica
Fremontol 592 Bryor ia fremontii (655)
24-Methyl-23-dehydrolo- 593 Umbil icaria cylindrica (406)
phenol
4Cl-Methylergosta-7,24(28)- 594 Pseudeverniafurfuracea (339)
dien-Jp-ol
4Cl-Methylergost-7-en-3~-ol 595 Pseudeverniafurfura cea (339)
Stigmasta-r.Zz-dien-Sp-ol 596 Pseudeverniafu rfuracea (339)
Stigmastan-Jb-ol 597 Pseudevernia furfuracea (339)
Stigmasta-3,5,22-trien-7-one 598 Umbilicaria cylindrica (406)
Stigmast-Sen-Jp-o l Pseudevernia furfu racea (339)
Stigmast-J-en-Jb-ol Pseudevernia furfuracea (339)
Co//ema polycarpon (405)
Stigmast-4-en-3-one Pseudevernia fu rfuracea (339)
Cladoniafur cata (9)
Umbilicaria cylindrica (406)
Stigmasterol Usnea articulata (353)
Loba ria pulmonaria (659)

a "
590 591
HO 591
594
596
214 S. Huneck
U.EtNH,
..
599 : Lichesterol
Scheme 182. Synthesis of lichesterol
4.6.7. Carotenoids
The carotenoid contents of many lichens from all over the world
have been reported by Czeczuga et al. (106-155) and by Leisner et al.
(495). Carotenoids from lichens up to ·1988 have been reviewed by
Czeczuga (109) who also discussed ecological differences in the
carotenoid content (111).

Table 12. Metabolites from lichen mycobion ts
Lichen mycobiont Metab olites Ref.
Aspergillus terreus ~-O rci no lca rboxylic acid (691)

Baeomyces rufus Ergostero l, triglyceride (616)
Caloplaca fe rruginea 7-Chloroemodin (615)
Cetraria islandica Usnic acid (757)
Cetraria nivalis Squamatic acid, barb atic acid (757)
Cladonia grayi 4-0-Demethylsphaeroph orin, graya nic (90)
acid, 4-0-demeth ylgrayanic acid
Cladonia polycarpia Homoheveadr ide (l05)
Cladonia polycarpoides Homoheveadrid e (l 05)
Cladonia vulcani Cytoc hro mes (307)
Evernia prunastri Usnic acid (757)
Graphis desquamescens G raphenone, graphisquinone (549)
Graphis scripta Graph enone, graphisquinone, (549,693)
graphislacto ne A- D
Lecanora dispersa Pan nar in, dechlorop ann arin (497)
Pseudephebe pubescens Usnic acid (757)
Ramatina duriaei Usnic acid (757)
Ramatina siliquosa 4-0-Demeth ylbarbatic acid, norbarbatic acid, (98,344,
norob tusatic acid, norisoobtu satic acid, 346)
hypop rotocetr aric acid, 4-0-Demethylbar-
batic acid, norisonotatic acid, convirensic
acid, virensic acid, prot ocetraric acid, hypo-
salazinic acid, connorstictic acid, nor stictic
acid, cryp tostictic acid, stictic acid, salazinic
acid, hypostictic acid, hypoconstictic acid,
consalazinic acid, constictic acid,
menegazzianic acid, usnic acid
Ramalina subbreviuscula 4-0 -Demethylbarbat ic acid (343)
Usnic acid (757)
Ramalina subcomplanata 4-0-Demethylbarbat ic acid (343)
Ramatina yasudae Usnic acid (748)
Stereocaulon curtatum Lecanoric acid (347)
Usnea jilipendula Usnic acid (455)
Usnea jiexilis Usnic acid (455)
Protocetrar ic acid, salazinic acid (758)
Usnea hirta Usnic acid, atranorin (455, 457,
757)
Usnea mont is-fuji Usnic acid (757)
Usnea orientatis Isostrepsilic acid, hypostrepsilic acid (469)
Usena roseola Usnic acid (455)
Usnea rubescens Usnic acid (748)
Usnea rubicunda Usnic acid (455)
Xanthoria elegans Parietin (757)
Xanthoriafallax Parietin (757)
Xanthoria mandschurica Par ietin (757)
Xanthoria mawsonii Parietin (757)
216 S. Huneck
5. Culture and Chemistry of Lichen Symbionts

and Cell Culture of Lichens
5.1. Culture of Mycobionts
Crittenden and Porter (87) have stressed the value of lichen-forming

fungi as potential sources of novel metabolites; the same group (86) has
studied preparation of pure cultures of 1183 species of lichen-forming
and lichenicolous fungi covering 77 families and 280 genera . Cell growth
and pigment production in suspension cultures of the mycobiont from
the lichen Cladonia cristatella was investigated by Yamamoto et al.
(742) while Hamada et al. (345) studied different media for growing the
mycobionts of Lecanora bicincta, Lecidea tessellata, Rhizo carpon
cupreoatrum and Usnea mutabilis. Metabolites found in lichen myco-
bionts are summarized in Table 12.
5.2. Lichen Tissue Cultures and their Metabolites
The use of lichen tissue cultures and the development of lichen thalli
in vitro have been discussed by Japanese workers (741, 745, 759). The
method for cultivating lichen tissue (Yamamoto method) is demon-
strated in Fig. 11 . The cultivated lichens and the corresponding
references are summarized in Table 13.
rl&
(3;4,=- y
.....""
.... ~
'"
Original thalli Rinse Homogenization
/-- ~--
Inoculation
~
Selection
0
1 .....
q
2nd Filtration
J
o·." " '. '. q
1st Filtration
Fig. 11. Yamam oto method for cultivating lichen tissue

Table 13. Cultiva ted lichens
Lichen Ref.
Alectoria lata (747)

A. ochroleuca (747, 749)
Evernia esorediosa (747, 749)
E. prunastri (747, 749)
Peltigera aphthosa (760)
P. canina (760)
P. malacea (760)
P. praetextata (760, 76/ )
P. pruinosa (760)
Ramalina boninensis (747, 749)
R. pacifica (747, 749)
R. yasudae (747, 749)
Rhizocarponjla vum (756)
Umbilicaria aprina (749, 756)
U. caroliniana (753)
U. cylindrica (753)
U. decussata (749, 756)
U. esculenta (753)
U. hyperborea (753)
U. kisovana (753)
U. muehlenbergii (749, 756)
U. pensylvanica (756)
U. polyrrhiza (753)
U. proboscidea (753)
U. vellea (753)
Usnea bayleyi (749)
U. bismolliuscula (747, 749)
U. difJracta (747, 749)
U. jlexilis (749)
U. /ongissima (747, 749)
U. misaminensis (749)
U. rubescens (747, 749)
U. rubicunda (747, 749)
5.3. Culture of Lichen Phycobionts
Yoshimura and Kurokawa (753) isolated the phycobionts (Tre-

bouxia) from Umbilicaria caroliniana, U. esculenta, U. hyperborea ,
U. muehlenbergii and U. pensylvanica . Harmala et al. (354) have culti-
vated the phycobionts of Cetraria islandica, Cladina mit is, C. stellaris,
Cladonia cornuta, C. gracilis and C. pleurota but found no phenolic
acids in the algae when these were analyzed by HPLC. The phycobionts
of Anzia colpota, A . hypoleucoides, A . japonica, A. opuntiella, A . ornata,
and A . stenophylla were studied taxonomically by Ihda et al. (434).
218 S. Huneck
Kinoshita et al. (454) have described improved conditions for the

isolation of protoplasts from the lichens Cladia aggregata, Cladonia
bellidiflora, C. boryi, C. pleurota and C. stellaris.
5.4. Metabolites from Lichen Phycobionts
It is generally assumed that it is only the mycobiont which synthesize

the typical lichen substances. Culberson et al. (94) examined the
hypothesis that the algal partner in a lichen regulates the chemotype
of the fungal partner and used Cladonia chlorophaea and Trebouxia erici
from Cladonia cristatella as symbionts. They found that the production
of cryptochlorophaeic acid or grayanic acid, which are typical metab-
olites of Cladonia chlorophaea, was not regulated by the phycobiont.
Avalos and Vicente (22) reported the occurrence of usnic acid, atranorin
and chloroatranorin in the phycobiont of Evernia prunastri. The group
of Feige (personal communication of H .T. Lumbsch, Essen) repeated
the procedure given by these workers and were unable to confirm their
results . Because it is very important to know the eventual influence of
lichen phycobionts of lichen metabolites further analyses of phy-
cobionts should be performed.
Two chlorine-containing metabolites, nostoclide I (600) and II (601)
have been isolated from the culture of a symbiontic blue-green alga
(Nostoc spec.) in Peltigera canina, a common lichen. Their structures
were determined by spectroscopy and X-ray diffraction (750).
CI
600 : NostoclideI , R = CI,mp 186-187°C
601 : NostoclideII ,R = H, mp 132-133°C
6. Biosynthesis of Lichen Substances
Only a few papers concerning the biosynthesis of lichen substances

have been published between 1984 and 1998. Biogenesis of the diphenyl
derivative contortin (see Scheme 183) very likely proceeds by phenolic
coupling of two molecules of C-methylphloracetophenone; methyla-
tion could occur before or after diphenyl fomation (222). In lichens

containing lecanoric and gyrophoric acids (e.g. Lasallia pensylvanica,
Parmelia tinctorum , Roccella canariensis, Umbilicaria caroliniana and
U. muehlenbergii) small amounts of orsellinic acid are always present, an
observation which confirms that this compound is a biogenetic
precursor of both depsides (754). According to Elix (236, 211) para-
depsides can undergo acyl migration to the corresponding meta-
depsides which can be converted into diaryl ether by an intramolecular
Smiles rearrangement; subsequent cyclization leads to a depsidone. The
1{-
*
°
Me Me
o! I ~ ~
HO A OH
~.
I
HO
A
~I
• H TO
Me Me Me
e-Melhylphloracelophenone
Me Me
OH OMe
Methylation
~
TO
co
Me
I
Me
Me Me
Contortin
Scheme 183. Biosynthesis of contortin
Me
*
CI ~ co-0'¢c:OH
Hydroxylation at pes.lon 5'
I b I A ~
H
HO Me
~~I~
CI COOH
MeJ¢c
HO
COOMe
:
yt::I A
co-o~Me
~ I
COOMe
H
HO Me
Cyclographin
Scheme 184. Assumed biosynthesis of the depsidone cyclographin

220 S. Huneck
Oxidati.... nngopening
•
~
Methylation
Chlorination
: O l: a
.0 .0
Me I
Thiemelin
Scheme 185. Possible biosynthesis of the xantho ne thiomelin
/
:~i5¢&M' 0 7-Chloroemodin
/ ~:;:::ro:eVigatum
OH 0 OH
OH~Me
~
o
Emodin
J Fungal
chloroperoxidase
~
OH 0 OH
CI@
I
:O
I
:
CI 0
+
OH~Me
CI 0 OH --:; --:; Me
5-Ghloroemodin 5,7-Dichloroemod in
Scheme 186. Enzymatic chlorinatio n of emodin

biosynthesis of cyclographin could follow such a route (see Scheme

184). Elix et al. (218) have also proposed the route shown in Scheme 185
for biosynthesis of the lichen xanthone thiomelin. By supplying acetate
or gluco se to Pseudevernia furfuracea thalli , it has been found that the
accumulation of atranorin is independent of the photosynthetic acti vity
but is repre ssed by gluco se; lecanoric acid is produced with glucose
(316). Orsellinate dep side hydrolase has been isolated from E vernia
pruna stri (331).
N ephroma laevigatum from British Columbia contained the following
anthraquinones: emodin , 7-chloroemodin, 7-chloro-I-O-methylemodin,
7-chloro-I-O-methylcitreorosein, 5-chloroemodin, 5-chloro-I-O-methyl-
emodin, 5-chloro-I-O-methylcitreorosein and 5-chlorocitreorosein. Feed-
ing experiments with Na[2-l4C]-acetate and Na[1-13C]-acetate showed
that these anthraquinones are biosynthesized via the polyketide path-
way (75).
The chlorination of emodin and 7-chloroemodin was studied by
Cohen and Towers (76) with an enzyme from N ephroma laevigatum and
a fungal chloroperoxidase. The lichen enzyme chlorinated emodin only
at C-7 while the fungal enzyme converted emodin to a mixture of
5-chloro-, 7-chloro- and 5,7-dichloroemodin (see Scheme 186).
7. Chemotaxonomy of Lichens
The use of chemotaxonomy in classification of lichen s has been
discussed frequentl y (88, 496, 185, 44, 45, 91). Vainshtein (704) has
published a guide to lichen chemotaxonomy. After a short introduction
and a chapter on analytical methods for identification of lichen
substances the main part of the booklet contains the name s of lichens
and their secondary products. Use of metabolites in taxonomy of
lichens has been discussed by Lumbsch (514). According to Carlin (57)
lichen chemistry and lichen biology need to be studied more thoroughly
before use of lichen compounds in taxonomy can be properly evaluated.
This author questions whether chemical diversity in lichens is caused by
selection pressure and whether metabolic regulatory effects may be
operating. It cannot be concluded with certainty whether or not the
presence of different lichen compounds reflects genetic or metabolic
differences. Rogers (622) ha s expressed the op inion that no taxonomic
status should be accorded to entities which differ onl y in products from
a single biosynthetic pathway, but varietal status should be given to
tho se which have different biosynthetic pathways. Species status is
j ustified if chemistr y is correlated with morphological or physiological
222 S. Hun eck
differences or ifmore than one major biosynthetic system is involved. So

far, so good , but the problem is that the biosynthesis of man y lichen
substances is known only insufficiently. Feige and Lumbsch (290)
distingui sh three types of chemical variation in lichens: 1) in morpho-
logically well defined species (e.g. Hypogymn ia bitteri, H. j arinacea,
H. laminisorediata, H. physodes, H. tubulosa, H. vittata) the qualitati ve
occurrence and relat ive concentrations of lichen substances are stable,
2) other taxa contain chemosyndromes (e.g. the Lecanora subj usca
group), 3) variat ion of metabolites occur s within a thallus (e.g. Lasallia
and Roccella species). A selection of papers on the chemos ystematics of
lichens arranged by taxa is listed in Table 14.
Table 14. Chemosystematic studies of lichen taxa
Family or genus Contents Ref.
Basidiolichenes Eleven analysed Basidiolichenes were free of lichen (298)

substances
Buellia Chemistry of xanthone-containing species of the (504)
genus Buellia
Canoparmelia The genus Canoparmelia was segregated from (187)
Pseudoparmelia for chemical reasons
C1adonia Ana lysis of 18 species of Cladonia, sect. Helopodium (423)
and 5 species of subsect. Fo liosae
Analysis of 32 species of the genus Cladonia, sect. (421)
Perviae
Coccifera
Clado nia and 14 species of the sect. Fuscata
Dimelaena Dimelaena australiensis contained the depside (506)
sulphurellin
Diploicia Diploicia canescens proved to be a complex of (229)
D. canescens, D. subcanescens and D. canescens ssp.
australasica
lla ematomma Chemistry of 35 species of the genus Haematomma (665)
Hypogymnia Analysis of 6 species from Turkey (762)
Lecanactis Analysis of 51 specimens of Lecanactis latebrarum (487)
from Central Euro pe
Lecanora Analysis of the Lecanora rupicola group in Euro pe (507)
Analysis of the Lecanora subfusca group in Australasia (513)
Analysis of 2 species of the Lecanora subfusca group (516)
Analysis of the Lecanora subfusca group in Japan (551)
Analysis of 1384 specimens of Lecanora fr ustulosa (706)
a nd L. argop holis
Chemistry of the Lecanora dispersa group from the (578)
Eastern alpine region
Chemistry of Lecanora radiosa (359)
Fa mily or genus Con tents Ref.
Lecidella Analysis of 23 species (499)

Analysis of 25 specimens of 9 species (467)
Analysis of 19 saxicolous species from America (465)
Analysis of 170 specimens of Lecidella carpathica and (50l)
18 specimens of L. viridans
Chemistry and distr ibuti on of the saxicolous species (466)
of the genus Lecidella
Analysis of 200 specimens of the Lecidella asema group (500)
Analysis of Euro pean saxicolous Lecidella species (498)
Lepraria Analysis of 183 specimens of Lepraria incana from (485)
Central Europe
Analysis of 362 specimens of Lepraria lobificans (486)
Chemistry and identification of the British species of (568)
Lepraria and Leproloma
Analysis of 2500 specimens of the genera Lepraria (503)
and Leproloma from Central Europe
Analysis of 150 specimens of Lepraria rigidula from (489)
Central Euro pe
Analysis of 22 specimens of Lepraria lesdainii (484)
Leproloma Analysis of 5 Leproloma species (502)
Analysis of 2500 specimens of the genera Lepraria (503)
and Leproloma from Cent ral Euro pe
Ochrolechia Ana lysis of 600 specimens from Europe (350)
Miriquidica Creation of the genus Miriquidica; all known 14 (360)
species con tain miriquidic acid
Parmelia s.l, Classification of Parmelia (187, 188)
Pilocarp aceae Chemistry of the genera Fellhanera and Badimia (517)
Pseudevernia Of 728 analysed specimens of Pseudevernia furfuracea (342)
from Nor way 49% conta ined oliveto ric acid, 50%
physodic and hydroxyphysodic acids and 1%
oliveto ric and physodic acids
Chemistry a nd ecology of Pseudevernia furfura cea (104)
Ramalina Chemistry of the Ramalina americana complex (96)
Chemistry of the Ramalina siliquosa compl ex (98,99)
Rhizoplaca Separati on of Rhizoplaca from the collective genus (508)
Lecanora
Chemotypes of Rhi zoplaca in North America (538)
Rinodina Analysis of 26 species (505, 537)
Roccellaceae Chem ot axonomy of the order Arthoniales (38 7)
Roccella hypomecha compri ses 5 chem ot ypes (293, 299)
Squamarina Analysis of 15 Squamarina species from Euro pe (292)
S tereocaulon Chem ota xonom y on the base of polysaccharides (688)
Umbilicaria Analysis of 11 Lasallia species (583)
Analysis of 56 species of the family Umbilica riaceae (556)
Analysis of II Umbilicaria species from Spain (644)
X.anthoparmelia Chemistry of the genus Xanthoparmelia in Australasia (235)
224 S. Huneck
8. Biological Activities of Lichen Substances and Lichens
8.1. Activity against Microorganisms
8.1 .1. Antiviral Activity

A sulfate prepared by chlorosulfonation of GE-3-, a partially
acetylated ~-(l --+ 6) glucan of the lichen Umbilicaria esculenta,
inhibited the cytopathic effect of human immunodeficiency virus
(HIV) and suppressed the HIV-antigen expression in Molt-4 (clone 8)
cells (371). Emodin, 7-chloroemodin, 7-chloro-l-O-methylemodin and
5,7-dichloroemodin have exhibited antiviral activity (738, 72). Stiibler
et al. (675,676) investigated the antiviral activity of the glucan lichenan.
Seventeen depsides and depsidones have been examined for their
inhibitory activity against HIV integrase (559). Yamamoto et al. (743)
tested the extracts of numerous lichens on their inhibition of Epstein-
Barr virus activation.
8.1.2. Activity against Bacteria and Fungi

The activity of lichen substances and lichens against bacteria and
fungi is summarized in Table 15.
Whiton and Lawrey found that ascospore germination of the lichens
Cladonia cristatella (724), Graphis scripta and Caloplaca citrina (725)
was much reduced in the presence of lichen substances. Spore
germination of Cladonia cristatella and Caloplaca citrina was inhibited
by vulpinic acid, evernic acid and atranorin respectively; stictic acid
showed no activity.
Table 15. Antifungal and antibacterial activities of lichen substances and lichens
Lichen substance Activity against Ref.
Alectosarmentin Staphylococcus aureus, Mycobacterium (327)

smegmatitis
Alranorin Mycobacterium aurum (436a)
I'-Chloropannarin Leishmania (302)
Depside hydroly sis bacteria and fungi (436)
products
Emodin Bacillus brevis (13)
Erythroglaucin Arthrobacter citreus, Bacillus brevis, (12)
B. subtilis, Streptomyces viridochromogenes
Evernic acid Staphylococcus aureus, Bacillus subtilis, (493)
B. megater ium
Leprapinic acid derivatives Gram positive and Gram negative bacteria (601)
Lobaric acid Mycobacterium aurum (436a)
Table 15 (conti nued)
Lichen substance Activity against Ref.
Met hyl haemat ommate Epidermophyton floccosum , Microsporum (366)

canis, M. gypseum, Trichophyton rubrum,
T. mentagrophytes, Verticillium achliae
Methy l and ethyl orsellinate Bacillus subtilis, Staphylococcus aureus, (436)
and methy l ~-orsellinate Pseudomonas aeruginosa, Escherichia coli,
Candida albicans, Aspergillus niger
Norlichexanthone bacteria (43)
Pannarin Leishmania (302)
Physcion bacteria (13)
(+ )-Protolichesterinic acid Helicobacter pylori (431)
Mycobacterium aurum (436a)
Pulvinic acid lactone Drechslera rostrata, Alternariaalternata (601-fJ03,
derivatives 613)
aerobic and anaerobic microorganisms (491)
Salazinic acid Mycobacterium aurum (436a)
Usnic acid and derivatives Staphylococcus aureus, Bacillus subtilis, (493,80,
B. megaterium 585,302)
Mycobacterium aurum (436a)
aerobic and anaerobic microorganisms (491)
Lichen
Alectoria capillaris bacteria, fungi (84)
A. ochroleuca Staphylococcus aureus, Bacillus subtilis, (436)
Candida albicans
Aspicilia gibbosa Bacillus subtilis, B. megaterium (493)
Cetraria islandica Staphylococcus aureus, Bacillus subtilis (436)
Cladia aggregata Candida albicans (436)
Cladia retipora Bacillus subtilis (511)
Cladonia arbuscula Staphylococcus aureus, Bacillus subtilis, (436)
Candida albicans
Cladonia subulata Bacillus subtilis (52)
Cladonia uncialis
Cornicularia aculeata Staphylococcus aureus, Bacillus subtilis, (436)
Candida albicans
Evernia prunastri bacteria and fungi (84)
Flavoparmelia baltimorensis Staphylococcus aureus, Bacillus subtilis, (493)
B. megaterium
Hypogymnia lugubris Bacillus subtilis (511)
Lasallia papulosa Bacillus subtilis, B. megaterium (493)
Nephroma arcticum vario us fungi (489a)
(water extract)
Peltigera aphthosa Staphylococcus aureus, Bacillus subtilis, (436)
Escherichia coli, Pseudomonas aeruginosa,
Candida albicans
P. canina
P. leucophlebia Bacillus subtilis, Escherichia coli, (436)
Pseudomonas aeruginosa
226 S. Hune ck
Lichen substance Activity again st Ref.
Pertusaria oculata Staphylococcus aureus, Escherichia coli, (436)

Pseudomonas aeruginosa
Pseudevernia fu rfuracea bact eria and fungi (84)
Pseudocyphellaria colensoi
P. degelii
P. rufovirescens
Ramalinacelestri
R. geniculata Bacillus subtilis (52)
Stereocaulon alpinum
S. arcticum Staphylococcus aureus, Bacillus subtilis (436)
Stereocaulon colensoi
S. corticulatum
S. ramosum Bacillus colensoi (52)
Stereocaulon vanoyei
Thamnolia subuliformis Staphylococcus aureus, Bacillus subtilis, (436)
Pseudomonas aeruginosa, Escherichia coli,
Candida albicans
Xanthoparmelia Staphylococcus aureus, Bacillus subtilis, (493)
cumberlandii Bacillus megaterium
8.2. Activity against Algae
Sodium roccellate (10- 7 M) increased the growth of Viva lactuca

(Chlorophyta) (314). Some lichen acids stimulated temporarily leakage
of organic substances from Trebouxia erici cells (703). (- )-Usnic acid
inhibited the growth of the green alga Chlamydomonas reinhardii (636).
8.3. Activity on Bryophytes
The lichen Lecidea albocaerulescens inhibited the growth of Porella

platyphylla (liverwort), Hedwigia ciliata and Anomodon attenuatus
(mosses) (358).
8.4. Activity on Higher Plants
Numerous lichen substances and lichen extracts are strong inhibitors

of germination and growth of higher plants. The results of such studies
are listed in Table 16.
Huneck and Schreiber (409) tested 33 lichen substances (aliphatic
acids, depsides , depsidones, dibenzofurans, diphenylbutadienes and
xanthones) for their growth inhibitory activity on the following higher
plants: Lepidium sativum, Pisum sativum , A vena sativa , Cucurbita pepo
Ref erences, pp. 239-2 76
New Result s on the Chemistry of Lichen Subs tances 227
Table 16. Lichen substa nces and extracts as growth inhibitors of higher plan ts
Lichen substa nce and extract Activity Ref.
Barba tic acid Inhibition of growth of lettuce seedlings (565)

4-0 -Demeth ylbarbat ic acid
Diffractaic acid
Evcrnic acid
Lecanoric acid
4-0-Methylorsellinic acid
Orse llinic acid
Ergoc hrome AA Ph ytotoxin (667)
(Secalonic acid A)
Evernic acid Decreases the chlorophyll contents in (614)
spinac h leaves
Lecanoric acid Prod uces abnormalities in Allium cepa (677)
Root tips
Lichen phe no ls Allelopathic activity (494)
Quinone from Pyxine spec. Inhibition of mitosis in Allium cepa roo ts (554)
(-)-Usnic acid Inhibition of germination and growth of (25)
Lepidium sativum
Usnic acid Inhibition of mitosis in Allium (427)
Antitranspirant (56)
Usnic acid (K-sa lt) Inhibition of germination and growth of (/57)
Phaseolus mungo and Triticum aestivum
Cladonia gracilis Inhibition of germination of Pinus sylvestris (608)
C. impexa
Cornicularia muricata
(water extracts)
Evernia prunastri Inh ibition of germina tion of (609)
Nigella damascena seeds
In hibition of germination of seeds of (6/0 , 611)
Agropyrum rigidum , Agrostis sto lonifera,
Festuca rubra, Lepidium sativum, Poa
trivialis, Polygonum lapathifolium, Silene
vulgaris, Sinapis alba
Letharia vulpina Inhi bition of germination and grow th of (/61)
Triticum sativum and Allium sativum
Parmelia conspersa Stimu lation of the formation of new (50)
(water extract) radicular cells of Peperomia magnoliaefolia
and Phaseolus coccineus. Roccellic acid, atranori n, evernic acid,

dichloroorsellinic acid, fumarprotocetra ric acid, psoromic acid, virensic
acid, o-collatolic acid, (-)-usnic acid, (- )-isousnic acid, vulpinic acid,
leprapinic acid, rhizocarpic acid, and thioph anic acid were strong
growth inhibitors at concentrations between 10- 3 and 10- 5 M. The
influence of usnic acid on sunflower and maize plantlets was investigated
by Lasceve et al. (490).
228 S. Hun eck
8.5. Acitivity on Animals
Cap erat ic acid defend ed the lichen Cetraria oaks iana aga inst attack
by the slug Pal/if era varia (492). Flavoparmelia baltimorensis and
Xanthoparmelia cumberlandia also contained compo unds acting as
antiherbivores (493). Meth yl ~- o rcinolcarboxy la te , ethyl haemat om-
mat e and ethyl 5-chloro haema to mma te showe d stro ng nemato cidal
activity against the second-stage larvae of the dog roundworm (Toxo -
cara canis) (4). G iez et al. (324) and Emmerich et al. (278) studied the
effect of numerous lichen substa nces on grow th and developm ent of
the polyphageous herb ivore insect Spodoptera litt oralis (No ctuidae).
Th e following compo unds were studied: evernic acid, atranorin,
psoromic acid, ph ysodic acid, 3-hydrox yph ysod ic acid, fum arprotocetr-
aric acid, stictic acid , nor stictic acid, salazinic acid, vulpinic acid,
pulvinic acid dilactone, calycin, rhizocarpic acid, pari etin , and usnic
acid. Whereas lar val survival was usually not affected most of the
compounds studied cau sed pr on ounced reduction of larv al growth in
chro nic feeding experim ent s with neon ate lar vae. Usnic acid, vulpinic
acid and 3-hydroxyphysodic acid were the mo st act ive compo unds.
Hesbacher et al. (363) ana lysed 103 imagi nes caught in the wild and
representing 8 different genera and 16 different species of Arctiidae
(insects) for the pr esence of lichen compo unds. Pari etin, atra nor in and
meth yl ~- orcin o lcarboxyla te were the most frequ ently detected com-
po unds. The ecological ro le of the sequestered lichen compo unds is
unknown. Th e linear hom oglucan PC-2 from Parmelia caperata
enhanced the hipp ocampal long-term potent iat ion in rats (654). Some
lichens such as Nephroma arcticum , Peltigera canina, P. malacea,
Placynthium asperellum, Psoroma hypnorum , S tereocaulon vesuvianum
and Xan thoria candelaria contain lectin s (352).
8.6. Acitivity on Man
Schindl er (638) has publ ished an article on the history of the medical
use of lichens and Han ssen and Schadler (351) have described the use of
lichen s and lichen substances in Chinese medicine. (+ )- Usnic acid effected
pr oliferati on of pol ychrom atic erythrocytes in mice (8) and was identified
togeth er with diffract aic acid as the analgesic and antipyretic compo nent
of the lichen Usnea diffracta (567). Numerous lichen substa nces are
allergenes and cause co ntac t dermatitis; among them are atrano rin,
barbatic acid, diffractaic acid, evernic acid, fumarprot ocetraric acid,
lob ar ic acid, perlat olic acid, ph ysodic acid, physodalic acid, pr otoliches-
terinic acid, salazinic acid, stictic acid, and usnic acid (39,286,696).
New Result s on the Chemistry of Liche n Substances 229
8.7. Tumor and Anti-Tumor Activity
Physodalic acid exhibited mutagenicity on Salmonella typhimurum

(646). The following lichen substances have shown anti-tumor activity:
acetylated pustulanes (564, 716), lichenan derivatives (171, 172), bar-
batic acid , 4-0-demethylbarbatic acid, diffractaic acid, evernic acid ,
lichesterinic acid , methyl gyrophorate, solorinic acid (746), nephroster-
inic acid, (+ )-protolichesterinic acid (372), chrysophanol and emodin
derivatives (471), usnic acid and derivatives (575, 689, 746) and an
extract from Usnea fasciata (575). Orcinol, olivetol , l-n-heptyl-3,5-
dihydroxybenzene, l-n-tridecyl-3,5-dihydroxybenzene (19) and scabro-
sin esters (283, 732) were found to exhibit cytotoxic activity.
8.8. Inhibition of Enzymes

A number of lichen substances listed in Table 17 are enzyme
inhibitors.
Table 17. Lichen substances and lichen s as inhibitors of enzyme s
Lichen substance and lichen Inhibited enzyme Ref.
4- and 5-Alkylresorcinols tyro sina se (535)

Atranorin tr ypsin and pankreaselastase (584)
pho sphorylase (1)
Baeomycesic acid 5-lipoxygena se (439)
Bis-(2,4-dihydroxy-6-n-propyl-phenyl) tyrosina se (535)
methane
9-cis-Octadecenamide enzymes involved in (436b)
arachidonate met abolism
Chrysophanol glut athione reductase (33)
Confluentic acid monoamin oxidase B (280)
Divarinol tyro sinase (453)
Lichen acids HIV -I integrase (559)
Lichen cultures of Cetrariajuniperina, tyro sinase (368)
Hypogymnia physodes and Letharia
vulpina
Lichens superoxide dismutase (743)
4-0-Methylcryptochlorophaeic acid pr ostaglandin synthetase (648)
2'-O-Methylperlatolic acid monoamin oxidase B (280)
(+ )-Protolichesterini c acid HIV- l rever se transcriptase (574)
Usnic acid phosphorylase (1)
Vu lpin ic acid pho sphorylase (1)
230 S. Huneck
8.9. Antioxidant Activity
Atranorin, diva ricatic acid, I'-chloropannarin, pannarin and phy-

sodic acid show antioxidant activity (367, 433).
9. Harmful Effects of Lichens
Lichens can deteriorate or destroy ancient frescoes, old buildings

and colored windows of cathedrals. The effect is due to the production
of oxalic acid which converts the calcium carbonate of the substrate
to calcium oxalate, thus changing the structure of the surface . The
topic (biodeterioration) has been thoroughly discussed by Nimis et al.
(563).
10. Commercial Uses of Lichens and Lichen Substances
10.1. Uses in Perfume Production and in Cosmetics
Large amounts of two lichens are processed for production of

essential ingredients in the perfume industry: thus in 1997 1900 tons of
Pseudevernia furfuracea and 700 tons of Evernia prunastri were
processed, mainly at Grasse, the centre of the essential oil industry in
France (447). Usnic acid is used as a preservative in cosmetic creams
(643) and atranorin, diva ric acid , gyrophoric acid, pannarin, and usnic
acid are potential sunscreen materials (294).
10.2. Lichens as Biomonitors
Lichens are useful indicators for monitoring air pollution (312, 361,
362, 446, 458). The literature concerning air pollution and lichens is
summarized continously in the journal " Lichenologist".
10.3. Lichens for Dyeing
Dyeing with lichens, although an old industry, is nowadays

practiced only by amateurs. Booklets by Feddersen-Fieler (289),
Casselman (62, 63) and Fraser (303) contain detailed instructions.
References, pp . 239-276
Acknowledgement
I am grateful to Prof. W. Herz (Tallahassee) for grammatical
help , to Ing . H .G. Konig (Hall e/Saale) for help with the computer, to
Dr. D. Joulain (Grasse) for information concerning the consumption
of lichens in the perfume industry and the "Fonds der Chemi schen
Industrie e. V." (Frankfurt/M ain) for a research grant.
Notes Added in Proof

Chapter 2.7. X-Ray Analysis. H ybocarpone (Ernst-Russell MA , Elix
lA, Chai CLL, Willis AC , Hamada N , Nash III TH (1999) Hybo -
carpone, a Novel Cytotoxic Naphthazarin Derivative from Mycobiont
Cultures of the Lichen Lecanora hybocarpa. Tetrahedron Letters 40:
6321 ).
\
Me Me
OH 0 0 OH
Me Me
OH OH
OH 0 OH
Hybocarpone, orange prisms, mp 167-168'C
[a]o-19.2 (CHCI3)
Chapter 4.1. Nitrogen Containing Compounds. Diacylglyceryl-N,N,N-

trimethylhomoserine was found in Cladonia jimbriata, Parmelia
saxatilis, Peltigera canina, P. collina, and P. horizontalis (Kunzler K,
Eichenberger W (1997) Beta ine Lipids and Zwitterion ic Phospholipid s
in Plants and Fungi. Ph ytochemistry 46: 883),
Chapter 4.2. Phosphorus Containing Compounds. Phosphatidylcholine
and phosphatidylethanolamine (PE) have been detected in Cladonia
jimbriata, Parmelia saxatilis (except PE), Peltigera canina, P. collina,
and P. horizontalis (Kunzler K, Eichenberger W, loc. cit.).
Chapter 4.4.5. y-Lactonic Acids, Mai er et al. isolated from the li-
chen Punctelia microsticta gyrophoric acid, (-)-isomuronic acid and
232 S. Huneck
(- )-dihydropertusaric acid and revised the stereostructure of the latter

compound on the basis of spectroscopic evidence and molecular
modeling to
(-)-[)jhydropertusaric acid
(Maier MS, Gonzalez Marimon 01, Stortz CA, Adler MT (1999) A

Revised Structure for (-)-Dihydropertusaric Acid, a y-Butyrolactone
Acid. 1 Nat Prod 62: 1565).
Total syntheses of racemic protolichesterinic and roccellaric acids
were achieved with the use of a tungsten-n-ally complex in the key step
(see Scheme) (Chen M-l , Liu R-S (1998) Efficient Total Syntheses of
(±)-Protolichesterinic Acid and (±)-Roccellaric Acid via Tungsten-a-
allyl Complexes. Tetrahedron Letters 39: 9465).
1. n-BuLi
2. n-C13 H27CHO OH TBSCI OTBS CpW(CObNa
CH r--:=--« ---.~ ~--==--« •
CI/ = • C( R CI/ R
~W(COb R
CpW(COl2 "
r--:=---<tTBS_T_rifl_ic_a_C1~·d.~- - -r i M e
RAOAO
2. Nal • Da
1. NOBF4 CpW(~?~ ,' Me
R a
HCO-CH2"OTBS
racem. Protolichesterinic acid
Cr03
aooc Me
RJ=:=(O
racem. Rocc:ellaric acid
Scheme: Synthesis of(t)-protolichesterinic and (t)-roccellaric acids via a tungsten-a-allyl
complex

Chapter 4.5.6. Depsides. The tridepsides methyl ovoate, methyl 2"-

O-methylgyrophorate and methyl 2',2"-di-O-methylgyrophorate have
been detected in Pseudocyphellaria billardierei (Elix JA, Me Caffery LF
(1999) Three New Tridepside s in the Lichen Pseudocyphellaria bill-
ardierei. Australasian Lichenology 45: 12).
Me Me
~CO-~OR 1)c~
OHAA,," TCO-o OR
Me
Methyl ovoate : R =Me, R' =H

Methyl2"-o-methylgyrophorate: R =H,R' =Me
Methyl 2',2"·di-C-methylgyrophorate: R = R' = Me
Norbaeomycesic acid is a new depside from Hyp otrachyna orientalis

(Elix JA , Griffin FK, Louwhoff SHJJ (2000) Norbaeomycesic Acid, a
New Depsid e from the Lichen Hypotrachyna orientalis. Australasi an
Lichenology 46: 25).
eo_o~Me
*
Me OH
I ~ ~
OH
// OH
1// eOOH
eHO Me
n
Norbaeomycesic acid, needles , mp 191-192"C
e OOH
Co-l ( 1 : 0 H
OR
I // ~ I
OR CO - O OH
Me
OH
3-Hydroxygyrophoric acid : R = H
3-Hydroxy-4-o-methylumbiUcaric acid : R = Me
234 S. Huncck
In Parmelinopsis species the tridepsides 2,4-di-O-methylhiascic acid

(P. spumosa) , 2,5-di-O-methylhiascic acid (P. neodamaziana), 3-hydro-
xygyrophoric acid (P. subfatiscens) and 3-hydroxy-4-0-methylumbili-
caric acid (P . subfatiscens) have been detected (Elix lA, Wardlaw lH
(2000) Four New Tridepsides from Parmelinopsis species. Australasian
Lichenology 47: 8).
Chapter 4.5.7. Depsidones. The depsidones chalybaeizanic acid and
quaesitic acid have been isolated from the lichens Xanthoparmelia
amphixanthoides and Hypotrachyna quaesita respectively (Elix lA,
Wardlaw lH (1999) The structure of Chalybaeizanic Acid and Quaesitic
Acid , Two New Lichen Depsidones Related to Salazinic Acid . Aust 1
Chern 52: 713).
R'
OH
Chalybaeizanic acid : R = R' = CHO, mp> 300'C , dec.
Quaesttic acid : R = CHO, R' = CH2"().{;O-CH=CH-GOOH, mp> 350'C, dec .
The depsidone 2-methoxypsoromic acid has been identified in Sulcaria

sulcata and a Pertusaria spec. from Papua New Guinea (Elix lA,
Wardlaw lH, Archer AW, Obermayer W (1999) 2-Methoxypsoromic
Acid, a New Lichen Depsidone from Pertusaria and Sulcaria Species.
Aust 1 Chern 52: 717).
Me Me
OMe*=~o~
OH 0 ~
CHO COOH
2-Methoxypsoromic acid, needles, mp > 350'C , dec.
Acarogobien A and B from Acarospora gobiensis (collected near the

lake Ysyk K61, Kyrgyzstan) are the first brominated depsidones found
in lichens (Rezanka T, Guschina IA (1999) Brominated Depsidones
Referen ces, pp. 239-276
from Acarospora gobiensis, a Lichen from Central Asia. J Nat Prod 62:
1675). Interestingly both compounds belong to a group of depsidones
which were known only from fungi, e.g. aurantiacin A and 8, emeguisin
A, 8 and C, nidulin and unguinol from Preussia aurantiaca, Emericella
unguis and Aspergillus nidulans respectively.
R' OR"
Sr
Acarogobien A: R = Me, R' = R" = H; mp 172·C
Acarogobien B: R = CHO,R' = Br, R" = CHz-CHz-CH=C(Me)2; mp 197·C
Chapter 4.5.9. Chromanes and Chromones. Takenaka et al. isolated

from mycobiont cultures of the lichen Graphis scripta (collected in
Japan) the chromones 5-hydroxy-2,3-dimethyl-7-methoxychromone, 5-
hydroxy-3-hydroxymethyl-2-methyl-7-methoxychromone and 5-hydro-
xy-2-hydroxymethyl-3-methyl-7-methoxychromone (Takenaka Y ,
Tanahashi T, Nagakura N, Hamada N (2000) 2,3-Dialkylchromones
from Mycobiont Cultures of the Lichen Graphis scripta . Heterocycles
53: 1589).
S-Hydroxy-2 ,3-dimethy~7-methoxychromone: R = R' = H, R" = Me; mp 120-121·C
5-Hydroxy-3.flydroxymethyl-2·methyl-7·methoxychromone: R = H, R' = OH, R" = Me; mp 147·C
S-Hydroxy·2.flydroxymethyl-3-methyl-7-methoxychromone: R = OH, R'-H, R" = Me; mp 20S·C
Chapter 4.5.10. Xanthones. Cultures of the spore-derived mycobionts

of Pyrenula japonica and P. pseudobufonia synthesized the new
236 S. Huneck
xanthones 1,5,8-trihydroxy-3-methylxanthone and 1,8-dihydroxy-5-

methoxy-3-methylxanthone beside the known 1,7-dihydroxy-3-methyl-
xanthone (Tanahashi T, Takenaka Y, Ikuta Y, Tani K, Nagakura N,
Hamada N (1999) Xanthones from the Cultured Lichen Mycobionts
of Pyrenula japonica and Pyrenula pseudobufonia. Phytochemistry
52: 401).
R'" 0 OR
R"~
~O~Me
R'
1,S,8-Trihydroxy-3-methylxanlhone: R =R" =H, R' =R''' =OH; yellow needles, mp 276.S-27S'C
1,8-Dihydroxy-5-melhoxy-3-methylxanlhone: R =R" =H, R' =OMe, R" =OH; yellowneedles, mp 214-21S'C
Chapter 4.5.14. Naphthopyranes. Euplectin and coneuplectin are new

naphthopyrones from Flavoparmelia euplecta. (Ernst-Russell MA , Chai
CLL, Wardlaw JH, Elix J A (2000) Euplectin and Coneuplectin,
New Napthopyrones from the lichen Flavoparmelia euplecta . J Nat Prod
63: 129).
Me
Euplectin, red-orange needles, mp 320'C, dec.
Me
Coneupleclin, yellowneedles, mp 29SoC

Chapter 4.5.17. Isocoumarins. From cultures of the spore-derived

mycobionts of the lichen Graphis scripta var. pulverulenta the
isocoumarins graphislactone A-C and the 6H-dibenzo jb,djpyran-6-
one graphislactone D were isolated (693).
OR a
OH
Mea
OMe
GraphislacloneA: R = R' = H; mp 236-237°C Graphislaclone 0 ; mp 11D-112'C
Graphislaclone B: R = Me, R' = H; mp 65-e7°C
Graphislaclone C: R = H, R' = OH; mp 214-216 °C
Tanahashi et al. found in the cultured lichen mycobiont of a Graphis

species from the Philippines two further isocoumarins, 8-methyldi-
chlorodiaportin and 6,8-dimethylcitreoisocoumarin (Tanahashi T,
Takenaka Y, Nagakura N , Hamada N, Miyawaki H (2000) Two
Isocoumarins from the Cultured Lichen Mycobiont of Graphis sp.
Heterocycles 53: 723)
CI
Mea Mea
CI CI
OMeO OMeO
8-Q-Methyldichlorodiaportin (mixtureof lOR : lOS =19: 1); mp 155'C, [etID" + 36 (CHC!,)
Mea Me
OMeO
6,8-Di.Q.melhylcitreoisocournarin: mp 142-142'C , [etID" + 3 (CHe!,)
238 S. Huneck
Chapter 5.4. Metabolites from Lichen Mycobionts. The volatile

compounds (ca. 130) produced by a Nostoc species from a Collema
lichen were separated and identified by GC-MS; most abundant were
cyclohexane and cyclopentane derivatives (Dembitsky VM, Shkrob I,
Dor I (1999) Separation and Identification of Hydrocarbons and other
Volatile Compounds from Cultured Blue-Green Alga Nostoc spec. by
Gas Chromatography - Mass Spectrometry Using serially coupled
Capillary Columns with consecutive Nonpolar and Semipolar Sta-
tionary Phases . J Chromatogr A 682: 221).
Chapter 7. Chemotaxonomy of Lichens. Lumbsch (Lumbsch HT (1999)

Biodiversitat und Verbreitungsmuster tropischer Gruppen der Flech-
tengattung Lecanora Ach. (Lecanorales, Ascomycota). Cour Forsch-
Inst Senckenberg 215: 143) described the biodiversity and distribution
patterns of tropical groups in the lichen genus Lecanora with special
reference to Australasian species.
Rambold and Triebel (Rambold G, Triebel D (1999) Generic
Concepts in Lichenized and Lichenicolous Ascomycetes since 1950 - a
Historical Approach. Symb Bot Ups 32: 2) discussed the generic
concepts in lichenized and lichenicolous ascomycetes , including
chemical characters.
Crespo et al. (Crespo A, Gavilan R, Elix JA , Gutierrez G (1999) A
Comparison of Morphological, Chemical and Molecular Characters in
some Parmelioid Genera. Lichenologist 31: 451) analysed the morpho-
logical and chemical data (cell-wall chemistry and medullary chemistry)
from 64 genera of Parmeliaceae.
Chemical and morphological analyses of the critical lichen taxa
Pentagenellafragillima Darb. and Ro ccellodea nigerrima Darb. resulted
in the new combinations Roccella fragillima (Darb.) Follm. and
Ro ccella nigerrima (Darb.) Follm. The externally similar lichens
Pentagenella fragillima and Roccella nigerrima are described as new:
Ingaderia friabillima Follm. et M. Schulz and Roccella obscurissima
Follm. et B. Wern . (Follmann G , Schulz M, Werner B (1998) On the
Identity and Position of Pentagenella fragillima . Roccellodea nigerrima,
and some Related Species (Roccellaceae, Opegraphales). J Hattori Bot
Lab 85: 245).
Chapter 8.7. Tumour and Antitumour Activity. Hybocarpone (Ernst-

Russell MA , CLL et al., loc. cit.) showed cytotoxicity against the
murine P-815 mastocytoma cell line (IC so ca. 0.27 /lM and 1.67 /lg/mL
respectively).

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216. Elix JA, Gaul KL , Kantivilas G, James PW (1993) Siphulellic Acid, a New
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218. Elix JA, Gaul KL, Sterns M, Samsudin MW (1987) The Structure of the Novel
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219. Elix JA, Jayanthi VK (1986) Synthesis of the Lichen Depsides Miriquidic Acid and
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226. Elix JA, Jenie VA, Arvidsson L, Jorgensen PM , James PW (1986) New Depsidones
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227. Elix JA, Jenie VA, Jenkins GA (1987) Three New Depsidones from the Lichen
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228. Elix JA , Jenie VA, Parker JL (1987) A Novel Synthesis of the Lichen Depsidones
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229. Elix JA , Jenkins GA , Lumbsch HT (1988) Chemical Variation in the Lichen Genus
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237. Elix JA , Kennedy JM (1985) Synthesis of the Lichen Dibenzofuran Subdidymic
Acid. Aust J Chern 38: 1857
238. Elix JA , Lajide L (1984) The Identification of Further New Depsidones in the
Lichen Parmelia notata. Aust J Chern 37: 857
239. Elix JA , Lajide L (1984) Synthesis of the Lichen Depsides Pseudocyphellarins A and
B. Aust J Chern 37: 2153
240. Elix JA , Lajide L, Galloway DJ (1982) Metabolites from the Genus Psoroma. Aust
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241. Elix JA , Lajide L, Wardlaw JH (1995) The structure of Echinoca rpic Acid.
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242. Elix JA , Lumbsch HT , Lucking R (1995) The Chemistry of Foliicolous Lichens. 2.
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244. Elix JA , Mahadevan I, Wardl aw I, Wardl aw JH , Arvidsson L, Jorgensen PM (1987)
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245. Elix JA , Mayrhofer H, Wippel A (1995) 5-Chlorodivaricatic Acid, a New Depside
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246. Elix JA , McCaffery LF (1997) Epiphorellic Acid 3, a New Lichen Diphen yl Ether.
247. Elix JA , Naidu R (1995) Identification of some Minor Diben zofurans in the Lichen
Combea californica. Bibl Lichenol 57: 117
248. Elix JA , Naidu R, Laundon JR (1992) A Synthesis of the Lichen Dibenzofuran
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249. Elix JA , Naidu R, Laundon JR (1994) The Structure and Synthe sis of 4-
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diffusum. Aust J Chern 47: 703
250. Elix lA, Na idu R, Thor G (1995) Cyclographin, a New Depsidone from the Lichen
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251. Elix lA, Parker IL, Tearne PD , Wardlaw JH (1985) Synthesis of Further Divarinol
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252. Elix JA , Portelli VI (1990) A Synthesis of the Lichen Xanthone Thiomclin. Aust I
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253. Elix lA , Pratt Sl , Laundon JR (1990) A Synthes is of the Lichen Dibenzofuran
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254. Elix JA, Robertson F, Wardlaw IH, Willis AC (1994) Isolation and Structure
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255. Elix lA , Senanayke BS, Kalb K (1998) The Structure of Isoplacod iolic Acid and
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256. Elix lA, Venables DE (1993) 4-0-Methyllividic Acid, a New Lichen Depsidone.
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257. Elix lA, Venables DA , Archer AW (1994) Further New Depsones from the Lichen
Pertusaria truncata. Aust J Chern 47: 1345
258. Elix JA , Venables DA , Brako L (1990) New Chlorine-containing Depsidones from

the Lichen Phyllopsora coral/ina var. ochroxantha. Aust J Chern 43: 1953
259. Elix JA, Venables DA , Lumb sch HT , Brako L (1994) Further New Met abolites
from Lichens. Aust J Chern 47: 1619
260. Elix JA, Venables DA , Wedin M (1994) New Dibenzofurans and Dep sides from the
Lichen Bunodophoron patagonicum. Aust J Chern 47: 1335
261. Elix JA , Wardlaw JH (1986) The Synthesis of New meta-Depside s from Rama/ina
Lichens. Aust J Chern 39: 227
262. Elix JA, Wardl aw JH (1987) Synthesis of Lichen pa ra-Sph aerophorol Depsides.
263. Elix JA, Wardl aw JH (1996) The Stru cture of Dissectic Acid, a p-Orcinol meta-
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264. Elix JA , Wardl aw JH (1996) Hypoalectorialic Acid and Conechinocarpic Acid, Two
New Benzyl Esters from Lichens. Aust J Chern 49: 727
265. Elix JA, Wardlaw JH (1996) Synth esis of Dep sides Present in the Lichen Porpidia
g/aucophaea. Aust J Chern 49: 917
266. Elix JA, Wardl aw JH (1997) Synthe sis of Further p-Ket oalk yl Lichen Depsides.
267. Elix JA , Wardl aw JH (1997) New Depsides from the Lichen Neof usce/ia depsidella.
268. Elix JA, Wardlaw JH (1998) Meth yl Pseudoalectoronate, a New Depsidone from
the Lichen Parmotrema poo/ii. Austral asian Lichenol 43: 12
269. Elix JA, Wardlaw JH , Archer AW (1999) New Depsides from Pertusaria Lichens.
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Author Index
Abo -Khatwa, A.N . 239 Arup , U. 6, 240

Abros cheit, G. 270 Arvidsson, L. 249, 250
Adamcova , J. 267 Asakawa, Y. 275
Addiso n, J .B. 9, 239 Ascaso , C. 268
Adler, M.T. 232, 247, 249 Aslam, N. 269
Ageta , H . 259, 270 Avalos, A. 218, 240
Ageta, T. 270
Aghoramurthy, K. 239 Bachelor, F.W. 240
Ahad, A.M . 239 Bachet, B. 240
Ahmadjian, V. 5, 239, 260, 262, 275 Baddeley , G.V . 273
Ahti, T. 246, 255, 258, 260 Bai Bulat ova, N.E. 245
Akimenko, V.K . 240 Baig, E.S.A. 84, 268
Akin niyi, J.A. 257 Band eira, E. 266
Alagna, L. 190, 239 Barb alic, L. 240
Al-Bekairi, A.M. 239 Barbe ro, M. 247
Alessio, F. 266 Ba rclay, C.E . 248
AI-Jaw hari, D .A. 239 Barn s, G . 263
Allemand, P. 10, 239, 272 Baron , M. 240, 245, 254, 259
Allen, T.M. 274 Barrera, J .B. 254
AI-Robai, A.A. 239 Ba rtlett, A.J . 240
Alstrup , V. 244, 245, 258 Bar ua, A.K. 266
Ammann, K. 243 Batcho, E. 241
Amma nn, W. 239 Bats, J.W. 267, 268
Ana stasia , M. 239 Beck, M.L. 255
Andersen, D. 274 Becker, H. 267
Andersen, R.J. 274 Beckett , R.P. 244
Ando , T. 253 Behrens, U. 180, 240
Anke, H . 239 Beisler, J.A. 272
Anthonsen, T. 9, 264 Beisner, K . 262
App a Rao, A.V.N. 239, 268 Bend iksen, E. 255
Apsimon , J.W. 254 Benelt s, S.A. 248
Aptroot , A. 239 Benn , M .H . 240
Arai , y. 270 Bennett, S.A. 248
Archer, A.W . 51, 234,239, 248, 250, 251 Berendsen, W. 239
Ard itti, J. 239 Berglund , D .L. 272
Argay, G . 269 Beriel, H . 266
Arisawa, M . 239 Bernicke, D . 270
Armaleo, D . 243 Bertram , C. 270
Armstrong, P.A. 249 Besl, H. 271
Arno ne, A. 195, 239 Bhattiprolu, K.R . 254
Arriag a-Gi ner , F.J . 274 Bilger, W. 262
Arroyo, R. 270 Billhardt, U.-M . 268
278 Author Index
Bird, P.W. 274 Ca nonica, L. 241

Birgisdottir, M. 259 Carbonni er, 1. 241
Birkbeck, A.A. 240 Carlin, G . 221,241
Biron aite, D.A. 240 Carlson, R.M . 33, 241
Bishop , W.R . 242 Carn ey, R .L. 255
Blank , 1.E. 273 Ca rpenter, R.C. 241
Blaser, D. 240 Ca rvalho, CF. 241
Bloomfield , S.F. 259 Casares, M. 244
Bodo, B. 240, 254 Cascio, O. 241
Bohlmann, F. 258 Casselman , K .L. 230,241
Boitard, M. 266 Cenas, N.K . 240
Bol, L. 240 Cha i, C.L.L. 231,236,252
Boll, P.M . 259 Chamy, M.C 241, 253
Bolt, E. 253 Cha n, T .-M . 242
Bombuwala, K . 274 Chandrasenan , K. 188, 242
Boohene,l . 256 Chapma n, R E. 8, 242
Brako , L. 251 Chappell, H.-M . 248
Brandange, S. 240 Chatte rjee, T.K. 266
Brasch, 1. 240 Chaudh ry, M.A. 239
Brassy, C 240 Chawla, H.M . 196,242
Braun , M . 240 Chen, M.-l . 232
Breton , 1.L. 266 Chenevert, R. 49, 242
Broadbent, D. 241 Cheriyan, U.O. 240
Brod o, I.M . 241 Chester, D .O. 242, 248
Broomhead , 1.A. 267 Chiarello, 1. 242
Brossi, A. 252 Chibber, S.S. 242
Brouers, M.B. 268 Chiong, K .G . 274
Browne, J.C 264 Cho u, T .-C 261
Bruun, T . 241,259 Chri stensen, S.N. 244, 246
Bryant, T. 256 Chung, G .A.C. 259
Brynjolfsdotti r, A. 259 Cifuentes, B. 244
Bubrick , P. 244 Clardy, 1. 272, 274, 275
Buchen auer , H . 271 Cleaver, L. 242
Buckingham , 1. 241 Cogt, U. 245
Buemi, G . 180, 241 Co hen, 1.0. 252
Buffard, Y. 241 Co hen, P.A. 221,242
Burfitt , l.R. 273 Cole, A.L.J. 241,256
Buschmann, 1. 265 Co le, WJ. 269
Bychek, LA. 246, 247 Colt antes, G . 253
Comber, M .F . 81, 242
Caccamese, S. 241, 244 Compagnini, A. 241
Cai , L. 266 Connolly, 1.0. 242, 257, 267, 269
Ca lanasa n, C A. 248 Co nover, M .A. 242
Ca lder, V.L. 241 Constant , H . 266
Calvelo, S. 244 Cooper, A.B . 242
Cambon, M.C 253 Coppins, BJ. 250
Cam eron, A.F. 257 Corbett, R.E. 242
Campbell, A.C 197,241 Core ll, G .A. 266,275
Ca mpbell, F .S. 243 Co rey, EJ . 199,200,243
Ca nnon, l .R . 241 Co rvisier, M. 268
Author Index 279
Cosar, G. 243 Drtina, G .J. 266, 274

Cova l, S.J. 242, 272 Duffley, R.P. 247
Cresp, T.M. 241,243 Diirner, G. 267, 268
Crespo , A. 238 Durrani, A.A. 247, 273
Criffin, F.K . 248 Dyke, H.J. 247
Crittenden, P.O. 216, 243 Dzae, R.J. 245
Croft , J .A. 242
Crook, c.s. 248 Ebizuka , Y. 270
Culberson, c.r. 5,6,218,243,244,257, Eckes, P. 267
262, 263, 265, 266 Eckhardt, G. 264
Culberson, W.L. 243, 244, 257, 265, 266 Edwar ds, R.L. 247
Czeczuga, B. 214, 244-2 46 Egan, R.S. 247
Czerpak, R. 245 Egea, J.M . 244
Czygan, F.-e. 262 Eglinton , G . 253
Eichenberger, W. 231
Dallacker, F. 186, 246 Eichhorn, M. 267, 268
Dalvi, R.R. 246 Ejiri, H . 247
Dalzell, H .e. 247 Ekman, S. 240
Damon , R.E. 33, 246 Elix, J.A. 4, 5, 21, 81, 84, 123,15 1, 171,
Darsynkiewicz, Z. 261 219,22 1,23 1,233,234,236,238,240-
Da Silva, M .L.e. 246 243, 246-252, 255, 257, 261, 263-265 ,
Dasser, M. 242 267, 269, 274, 276
Dauriac, H. 246 Elkin, J .N . 247
David, F. 246,248,251 Embac her, G. 256
David , J.e. 243 Emmerich, R. 228, 251
De Azevedo, M .B.M. 265 Enders, D. 44,50,25 1
Degraeve, N. 268 Endo , A. 260
De Kok , J. L. 247 Endo , Y. 251
Dembitsky, V.M . 26,28,238,246,247,269 Engel, P. 269
Demleitne r, S. 247 Engkanian, U. 248
Denise nko , W.A. 261 Engler, T.A. 243
De Pava, ov. 239 Epstein, E. 28, 252
Dertien, B.K . 247 Ernst -Russell, K. D. 248
Desai, M .C. 243 Ernst -Russell, M.A. 231,236 ,238,248,
Deslandes, Y. 273 252
Devlin, J.P. 247 Espinoza , A. 253
Dietz, S. 247 Estevez, M .P. 182, 252
Dilip de Silva, E. 274 Etayo , J. 244
Din, L.B. 255 Evans, A.e. 263
Ditgens, K . 186, 246 Evans, F.J. 252
Djarm at i, Z. 269 Evans, J.E. 248, 252
Djur a, P. 247 Eversman, S. 245
Dmitrenok, P.S. 247, 271
Doll, R. 244 Fa hselt, D. 252
Deller, U. 267, 268 Falshaw, c.r . 247
Domon , B. 247 Fa nta, E.S. 240
Dar, I. 238 Farnswort h, N.R. 274
Dornhagen, J. 247 Feddersen-Fieler, G. 230, 252
Drake, S.D . 254 Feige, G .B. 218,222,248,252,254,256,
Dreiding, A.S. 263 257, 263, 267, 276
280 Author Index
Fernandez , E. 252, 256 Gaul , K.L. 248,249,267, 274

Fernandez, L 271 Gavilan, R. 238
Fernholz , E. 252, 267 Gavin, J. 253, 266
Ferraro, I. 245 Gawn, S. 243
Ferraro de Corona, L. 245 Gelbard, G. 263
Ferreira, M.-E. 252 Gerstner, E. 269
Feuerer, T. 254 Geyer, M. 252, 254
Fiecchi, A. 239 Ghogomu , R.T. 254
Fiedler, K. 256 Giammatteo, P.J. 271
Fiedler, P. 252 Giez, I. 228,251,254,256
Fisch, R.E.M.H . 239 Giles, R.G.F. 254
Fleming, A. 256 Gill, M. 247
Flick, B.H. 239 Giralt, M. 244, 247
Focella, A. 252 Girard , M. 254
Follmann , G. 24, 252, 257 Girijallabhan, V. 242
Fong , H.H.S. 266, 274 Gissurarson, S.R. 259
Fontana, J.D. 259 Glenneberg, J. 268
Forster, M.O. 252 Gloer, J.B. 267
Foster, L.M. 263 Goldsmith , S. 255
Fournet, A. 252 Gollapudi , S.R. 254
Franke , P. 270 Gonzalez, A. 253, 254, 273
Fran z, G. 247 Gonzalez, A.G. 254, 266, 274
Fraser , J. 230, 253 Gon zalez, C.M. 276
Fraser-Reid , B. 205, 263 Gonzalez, I. 252
Freer, A.A. 242 Gonzalez Marimon , D.I . 232
Fujikawa , F. 21, 253, 256 Gorin, PAJ . 240, 246, 254, 259, 264,
Fujisawa, M. 253 265,272
Fujiwara, T. 253 Gorschkova, P.P. 264
Fukuda, M. 253 Goto , Y. 239,269
Fukumori, Y. 253 Gowan , S.P. 254
Fukuoka, F. 266 Gray , G. 272
Furukawa, Y. 256 Greene, A.E. 265
Furuya, K. 260 Griffin, D.A. 254
Fuska, J. 267 Griffin, F.K. 233, 254
Fuzikawa , F. 253 Griffiths, G.J. 268
Grigsby, R.D. 254
Gabriel , R. 269 Grill, D. 261
Gagnaire, D. 7, 253 Groh, E.M. 242
Galloway, D.J. 250 Groves, C. 271
Galun , M. 5, 253 Gruezo, W.S. 245
Gambaro, V. 241,252, 253, 273 Gudjonsdottir, G.A. 254, 259
Gambhir, I. 242 Guerrini , M. 264
Ganguly , A.K . 242 Gunzinger, J. 240,254,255,267
Garbarino, J.A. 241,252,253,273 Guschina, LA. 234
Garcia , F. 253 Gutierrez, G. 238
Garcia-Junceda, E. 253 Gutkowski , R. 245
Garty, J. 252
Gaskell, S.J. 253 Hahnel, G. 263
Gaucher, G.M. 253 Hale, M.E. 243, 255
Gaugain , F. 262 Halvorsen, R. 255
Author Index 281
Hamada , N. 216,231 ,235-237 ,255,265, Hirose, Y. 256

272 Hjalmarsdottir, M.A. 259
Hamade, R. 253, 275 Hockless, D.C. 249,252
Hamat , A.L.B. 255 Hoder, D. 10,264
Hammer, S. 245 Holle, G. 9, 256
Handong , S. 133, 240, 255 Hogge, L. 259
Handrick , G.R. 247 Holker, J.H. 240
Hangac, H.H. 263 Holland, P.T. 256
Hanko, B. 255 Holzmann , G. 9,256
Hanson , A. 263 Hong, H. 266
Hanssen, H.-P. 228, 255 Hori, H. 259
Harada, H. 245, 253 Hostettmann, K. 247
Hardman, J.T. 255 Hostettmann, M. 247
Hardman, P.K. 255 Hozumi, T. 260
Hareed, A.M. 127, 255, 272 Hudlicky, T. 200, 202, 256
Harmala, P. 217,255,258 Hudson , J.B. 242
Harris, T.M. 255, 269 Huffman, J. 274
Hartl , H. 265 Hughes, B. 274
Hartung, W. 247 Hughes, S.H. 266
Haruyama , H. 260 Huneck, S. 5,9, 21, 23, 24, 42, 84, 132,
Hase, T.A. 255 188,226, 239, 242, 245, 252, 256-258,
Hashimoto, T. 275 260, 267, 269, 270, 272, 275
Hata , T. 260 Huovinen, K. 258,259
Hawksworth, D.L. 243 Hurne, A.M. 252
Hayase, S. 260 Hveding-Bergseth, N. 259
Hayashi, H. 251 Hylands, P.J. 259
Hebrard, P. 240
Heide, R. 255 Iacomini, M. 27, 240, 246, 254, 259, 264,
Heilman, A.S. 255 265,272
Heim, N. 268 Ichinose, T. 259
Heinen, H.J. 273 Igarashi, M. 269
Hencken, G. 240 Ihda, T.-A. 217, 259
Henssen, A. 269 Iitaka, Y. 169, 270, 272
Hermann, S. 255 Ikuta , Y. 236
Hershenhom, J. 242 Inayma, S. 259
Hertel, H. 255,261,263 Inchausti, A. 252
Herzig, R. 255, 256 Ingolfsdottir, K. 254, 259, 266
Herzschuh, R. 271 Ito, K. 253
Hesbacher, S. 228, 256 Ito, M. 256
Hesse, O. 42, 256 Iwai, K. 273
Hickey, B.J. 256 Iwashina, T. 261
Hidalgo, M.E. 252, 256 Iwata, S. 256
Higuchi, M. 256, 260, 275 1watsuki, Z. 259
Hill, A.M. 248
Hill Jr., W.B. 263 Jablonski, E. 246
Hiltunen, R. 255, 258, 259 Jacobsen, J.P. 259
Himmelreich, U. 256,257,269 Jacobsen, P. 240, 245
Hirabayashi , K. 256 Jacques, E. 259
Hirai, K. 253 Jager, P.M. 274
Hirayama , T. 253, 256 Jakupovic, J. 9, 257, 260
282 Author Index
James, P.W. 6, 249, 250, 274 Kennedy, J.M. 242, 250

Jamieson , W.D. 254 Kennewell, P.D. 260
Jampani, H.B. 254 Kessler, H. 268
Jankov, R.M . 269 King, A. 242
Jaxa-Chamiec, A.A. 260 King, G.G. 240
Jayanthi, V.K. 84, 249 Kinghorn, A.D . 266
Jenie, U.A. 81,245,249 Kinoshita, K. 260, 264, 275
Jenkin s, G.A . 249 Kinoshita, Y. 218, 253, 256, 260, 264,
Jerris, P.J. 196,260 266, 275, 276
Jiang, H. 248, 249, 260 Kirschb aum, U. 260
Jin, Y. 249 Kitahara, N . 260
John , E.A. 245 Kiuchi, F. 239
John , V. 257, 260, 276 Kjaer, A. 260
Johnson, A. 243, 244, 262, 265 Kjaer, D.K . 260
Johnson, A.T. 274 Kjelberg, O. 27, 261
Johnson, F . 264 Kjesen, H. 239, 259
Johnston, J. 249 Knoph , J.-G. 261-263
Jones, AJ. 249 Kobayashi, A. 239
Jones, A.L. 248, 250 Kobayashi , Y. 44, 50, 261
Jones , D. 274 Kojitani , K. 253
Jones , G.c. 267 Kolthoum, 1. 239
Jon sdottir, S. 259 Kon , T. 272
Jorgensen , P.M. 249, 250 Kon , Y. 261
Josephson, S. 240 Kondo , K. 239
Joulain , D. 260 Koon Tan, T. 245
Joullie, M.M. 242 Kopf, J. 240
Korte, F. 261
Kalb, K. 242, 250, 271 Koshimizu , K. 275
Kan , Y. 275 Koyama , K. 260, 264, 275
Kand a, H. 275 Koyama, M. 253,261
Kantivilas , G. 249 Kranner, I. 261
Kapadi, A.H. 267 Kraus , J. 247
Kapor, A. 269 Krause , W. 261
Kapuscinski , J. 261 Krishna, D.R . 239
Karunaratne, V. 274 Krishnamurthy, H.G . 261
Kasahara, T. 256 Kristinsson , H. 245
Kasai , R. 270 Krivoshchekova,O.E. 195,247,261,264,
Kashin , A.G . 246 265, 271
Kashiwadani, H . 245,261 Kiiber, F. 267
Kasu ya, A. 272 Kudratov, 1. 245
Kathuria, L. 242 Kuiper, PJ.c. 247
Kato, H. 270 Kulka , K. 261
Kato, T. 260 Kiimmerling, H. 32, 262, 263
Kattner, L. 265 Kundu, A.P. 264
Kauppi, M. 12, 260 Kiinzler, K. 231
Kauppinen, V. 255 Kuroishi, M. 272
Kawahara, N. 260 Kurokawa, T. 217, 260, 262, 275, 276
Kawa i, K.-I. 260, 264 Kutney , J.P. 178,262
Keinan , E. 44, 49, 270 Kuwahara, A. 272
Kelly, T.R. 261 Kvernheim, A.L. 27,261
Author Index 283
Laatsch, H. 239 Maass, W.S.G. 254, 263, 269

Lajide, L. 123, 250 Mabelis, R.P. 241
Lallement, R. 245 Mac Donald, A.L. 178, 264
Lambert, G. 247 Machado , M.J. 264
Lamon t, Y.M. 269 MacMillan , J.G. 264
Lampero, M. 259 Maestro , C. 271
Lamvik, A. 241 Maffei, M. 266
Land, CJ. 262 Mahadevan, L 250
Lange,O.L. 251,254,256,262 Mahato , S.B. 264
Larsen, R.D. 272 Mahler, P. 265
Lasceve, G. 227,262 Maidment, M.S. 241
Laund on, J.R. 250 Maier, M.S. 231,232
Lauterwein, M. 262 Makhija, U. 244
Lavoie, M. 242 Malleshwar, D. 271
Lawrey, J.D. 224, 262, 274 Malterud , K.E. 9, 264
Leete, E. 267 Manoharachary, C. 265, 271
Legaz, E. 252 Manrique , E. 270
Legaz, M.E. 254, 262, 266, 273 Marchessault, R.H. 253, 273
Lehmann , C. 265 Marcuccio, S.M. 21,247,264
Lehner, H. 270 Marre, It 262
Leisner, J.M.R. 214, 262 Martin, J. 33, 264
Leman, J.D. 262 Mart inez, E. 264
Lennard, CJ . 249 Mar uno, M. 251
Leuckert, C. 9,255,256,26 1-264,267 Masuda, K. 270
Levin, A. 276 Ma teos, J.L. 273
Li, L.-Q. 256 Mathey, A. 10, 12, 263, 264, 273
Liebendorfer, L. 256 Mato ba, C. 253
Lim, G . 245 Matsuami, N. 253
Lima, R.C. 266 Ma tsubara, H. 260, 264, 275
Lin, L.-Z. 266 Matsui, R. 253
Lindblom, L. 240 Mattson, J.-E. 240
Liptaj, T. 267 Max, W. 256
Lissi, E. 256 Maximov,O. R 245, 246, 261, 264, 265,
Liu, R.-S. 232 271
Llera, J.M. 205, 263 May, R C.H. 263
Lobkovsky, E. 274 Mayrhofer, H. 250, 263, 264
Lochmuller, C.H. 263 Mazumder, A. 266
Loebenberg, D. 242 Mazurek, M. 259
Loffler, A. 33, 263 McCaffery, L.F. 84, 233, 247, 249, 250
Lopez, J.L. 265 McConnell, D.R 248
Lorimer, S.D. 240, 263 McCoy, K. 255
Louwhoff, S.H.JJ. 233 McCune, R 264, 272
Lucking, R. 250, 263 McDonald, LA. 9, 265
Luger, P. 265 Mcinn es, A.G . 254
Lumbsch, H.T. 221,222,238,244,246-- McLean, S.M. 265
252, 256, 257, 263, 265, 276 McPhail, A.T. 242
Lumsden, AJ. 256 Medentsev, A.G . 240
Lundstrom, H. 262 Meier, S. 273
284 Author Index
Mendez, A.M. 257,265 Nagai , M. 253

Meneses, 1. 252 Nagakura, N. 235-237,272
Mestres, R. 264 Nagasawa , H. 259
Metcalf, B.W. 241 Naidu , R. 250, 257
Meyama, K. 266 Naik , D.G . 267
Meyappan, A. 265 Nakai, T. 253
Miceno, A.M. 265 Nakajima , S. 260, 273
Mierzawa , R. 242 Nakamura, 1. 253
Mies, B. 248 Nakamura, N. 253
Mietzsch, E. 12, 265 Nakamura, T. 253
Miller, M. 259 Nakano, M. 261
Milne, G.W.A. 266 Nakano, T. 259, 270, 275
Minami , K. 265 Naranjo, O. 253
Mirhom, Y.W. 254 Narui , T 9, 256, 265, 266, 270, 273
Mishchenko , N .P. 261, 264, 265, 271 Nascimento, S.c. 266
Mitra, A.K . 266 Nash III, TH. 231,248,255
Mitscher, L.A. 254 Nasini, G. 239
Miura, Y. 256, 260, 264, 275 Neamati, N . 266
Miyagawa, H. 186, 265 Neelakantan, S. 242, 265
Miyakawi , H. 275 Negron , E. 265
Miyawaki , H. 237, 265 Nenninger, A. 259
Mizuguchi, R. 275 Nestler, H.P. 267
Mizuno , D. 256 Neszmelyi, B. 259
Mizutami , J. 266 Neumann, D. 267
Mo, F. 239 Nicholson, B.K. 242
Moberg, R. 245, 273, 274 Nicholson , G. 257
MOder, M. 271 Nicklaus, M.C . 266
Moir , D.B. 254 Nicoletti, T.M. 266
Molho, D. 240,241 Nicollier, G. 253, 266
Molho, L. 240 Nimis, P.L. 230, 266
Molina, X. 252 Nishida, N. 256
Mi:irch, L. 240 Nishikawa , Y. 266
Moreno, L.N . 273 Nishimaki, T. 253
Mori, T. 253, 256 Nishimura, H. 266
Morita, N. 239 Nishio, S. 253
Moritani, K. 253 Nishitoba, Y. 266
Motoda, y. 253 Nishiyama, N. 270
Moutschen, J. 268 Nishiyama, T 266
Movkulich , P.M . 260 Niwas, S. 242
Mukainaka, H. 253 Noguchi , H. 270
Mukhopadhyay, A.K . 266 Norrestam, R. 178, 266
Mula ikrishna , K. 271 North, J. 274
Mulholland, A.G. 257 Nozawa, K. 260
Mulzer, J. 39, 265 Nozoe , S. 251
Murakami, A. 275 Nyburg , S.C. 265
Murakami, T. 256
Muralikrishna, K. 265 Obermayer , W. 234, 245
Murphy, D.P.H. 243 O'Brien, E. 240
Murray, B. 274 Oethinger, M. 262
Murta, M.M. 34, 265 Ogawa, K. 273
Author Index 285
Oh, H.-I. 273 Pina, D. 266

Ohashi, T. 253 Pliimper, M. 251
Ohigashi, H. 275 Plasse, N. 255
Ohmura, K. 239 Poch, G.K . 267
Ohta, T. 251 Poelt, 1. 255, 263, 267
Ojima, N. 272 Polborn , K. 51,267
Oksman-Caldentey, K.-M. 255 Pommier, Y. 266
Okui, H. 261 Portelli, V.J. 249, 250
Oku yama, E. 266 Porter, N. 216, 243
Okuyama, T. 266,270 Port er, R.M. 263
Olech, M. 245 Porwoll,l.P. 267
Oliveira, A.F .M. 266 Porzel, A. 23, 257, 258
Ollis, W.O. 247 Posner, B. 257, 267
Olmeda, L. 252 Prasad, U. 265
Orange, A. 266 Pratt, R.D. 263
Oschkinat, H. 268 Pratt, S.l . 250
Oshima, Y. 274 Preiss, A. 257
Osorio, H.S. 245 Prokopenko, O.F. 44, 50, 251
Otsuka, M. 256 Proksa, B. 266, 267
Ott , S. 28, 266 Proksch, P. 251, 254, 256
Otto, C.A. 274 Pronayova, N. 267
Ottoila, P. 258 Prosperi, T. 239
Oyler, A.R. 33, 241 Provatorolf, N. 255
Ozer, A. 243 Puar, M. 242
Pucknat ,l. 263
Padr on, C.E.H. 254 Pueyo, G. 27,267
Pang, G.-M . 259 Pulgarin, C. 84, 123, 267
Paquette, L.A. 200, 201 , 266, 269, 274 Puntambekar, H.M. 21,267
Park , Y.S. 244 Purvis,O.W. 249,267
Parker,l.L. 248-250
Passadore, M.V. 244 Quereshi, S. 239
Patel, M. 242 Quilhot, W. 241,252, 253, 256, 273
Patra, A. 266 Quinkert, G. 42, 267, 268
Pattenden, G. 195, 266
Patwardh an, P.G. 244 Radesca, L. 256
Pedrosa, M.M. 273 Radesca-Kwart, L. 256
Pendery,1.1 . 274 Raghava Raju, K. 268
Pengsuparp , T. 266, 275 Raju, K.R . 268
Pereira, E.C. 266 Ram a, M. 127,268
Perez, C. 274 Rama, N.H. 268
Perez, E.M.R. 254 Ramage, R. 197,268
Perez, F.J. 252 Ramaut ,l.L. 6, 268
Perry, N.B. 240, 263 Rambold , G. 238, 255
Peters, T. 262 Ramesh, P. 84, 265, 268
Pezzuto,l.M. 266, 274, 275 Rao, P.S. 239, 268
Pfiitzner, P. 273 Rapsch, S. 268
Pick,l.H. 241 Raston, c .r, 248, 266
Pienaar, R.N. 244 Ravinskaja, A.P. 273
Piervittori, R. 266 Razdan, R.K. 247
Pignata, M.L. 276 Relfstrup , T. 259
286 Author Index
Remedios , G. 271 Sankawa, U. 247, 270

Renner, B. 269 Santaniello, E. 241
Rettig, SJ. 264 Santesson, 1. 269
Reynaud, P.A. 244 Sargent , M.V. 240--243,247,248,251 ,
Rezanka, T. 28, 234, 246, 247, 269 254, 266, 269
Ribar, B. 180, 269 Sassa, T . 269
Richardson, D.H.S. 245 Sato , M. 265
Richardson, 1. 240 Sato , T. 239, 251
Richarz, R. 239 Sato, Y. 270
Rindone, B. 241 Saville, W.B. 252
Rios, V. 253 Sawada, K. 266
Ritchie, E. 242 Sawyer,l .F . 265
Roberts, R.A. 204, 266, 269, 274 Schade, A. 28, 269
Robertson, F. 250 Schadler , M. 228, 255
Robeson, D.l. 271 Scharf, H.-D . 247
Robie, S.B. 271 Schimmer, O. 270
Robinson, W.T. 242 Schindler, H. 228, 270
Rogers, R.W. 221 ,269 Schlessinger, R.H. 33, 246
Rojas de Arias , A. 252 Schmalz, H.-G. 270
Ronaldson, KJ . 274 Schmidt , 1. 257, 258, 270
Rondon , Y. 241 ,246 Schmidt , R. 261
Ronen , R. 253 Schmidt , RJ. 252
Roser, DJ. 242 Schneider, c .i, 259
Roser , G. 252 Scholler, H. 5, 270
Roux , C. 267 Schreiber, K. 226, 258
Rozentsvet , O.A. 246 Schroder, C. 265
Ruef, B.D. 269 Schull, V. 269
Rundel, P.W. 271 Schulz, H. 270
Ryall, R.R. 263 Schulz, M . 252
Rycroft , D.S. 269 Schutte , H.R . 273
Schwarz, C. 268
Sanchez-Pinto, 1. 252 Scolastico, C. 241
Safe, L.M . 269 Scott , F.E. 270
Safe, S. 269 Seifert, P. 270
Sagee, O. 252 Senanayke, B.S. 250
Said, M. 269 Seppelt, R.D. 242
Saita, T. 271 Serifia, E. 270
Saito , H. 270 Serusiaux , E. 268
Saksena , A.K. 242 Seshadri , T.R . 239,242
Sakurai, A. 269 Seto, S. 272
Salema, R. 244 Shah, A.H . 239
Salimi, N. 265,269 Shaker-Bazarnov, H. 241
Salisbury, P.l . 262 Shapiro, LA. 273
Salunkhe, D.K . 246 Sharma, L.R . 245
Salvadori , O. 266 Sharnoff, S. 5, 270
Sammes, P.G. 260 Sharnoff, S.D. 5, 270
Samsudin, M .W. 246, 249, 255, 269 Sharp, AJ. 255
Sanchez, l.H. 178, 262 Shchelkunova, R.P. 245
Sancho , L.G. 270 Shepherd, M.G. 253
Sandifer , R.M . 269 Shibamoto, T. 259, 270
Author Index 287
Shibata, S. 169,247,256,265,266,270, Stephenson, N .L. 271

272,273 Sterns, M. 249
Shibuya, M. 270 Stevenson, D.F.M. 241
Shigeta , S. 256 Stipanovic, A.J . 271
Shimizu, Y. 275 Stockli-Evans, H . 240
Shin, e.-G. 21,270 Stortz, ex. 232
Shiojima, K. 10,270 Stout, T .J. 272
Shkrob, I. 238 Strecker, A.R. 265
Sholichin, M. 270 Streimann, H . 245
Short, R.P. 256 Strobel, G . 272
Shustov, M.V. 246, 247 Strobel, G.A . 242
Sidwell, R . 274 Strobel, S. 272
Sieper , H . 261 Stuhler, D. 224, 271
Sierakowski, A.F . 265 Sturdikova, M. 267
Sigurdson, A. 259 Sucharita, B. 271
Silva, M.e. 254 · Suehiro, Y. 256
Silva, N .H. 266 Sugawara, H. 272
Simpson, l. 242 Sugawara, T . 272
Simpson, T.J . 240,265, 270 Sultanbawa, M .U .S. 241
Singh, B. 246 Sunder, S. 266
Singh , S.K . 201, 204, 273 Sundholm, E.G . 151,272
Sinha, S.e. 44, 49, 270 Suokas, E. 255
Siva Prasad, l . 261 Sutton, B.M . 273
Skelton, B.W. 242 Suzuki , T. 272
Skirina, I.F. 245, 246 Sweeney, J .N.A. 268
Skulas on , V.G . 259
Skult, H . 246 Tabacchi, R. 9, 84, 133, 240, 253-255 ,
Smith , css. 245 258, 266, 267, 272
Smith III , A.B . 260 Takagaki, Y. 253
Smriga, M. 270 Takagawa, M. 253
Solberg, Y. 21, 28, 259, 270, 271 Takahashi, K . 27,260,261 ,264,272,273,
Solberg, Y.J . 272 275
Solladie, G . 43,48, 271 Takahashi, N . 272
Song-San, S. 271 Takahashi, S. 260
Sotheeswaran, S. 241 Takai, M . 272
Spencer, H . 241 Takani, M . 272
Stach , J. 9, 271 Tak aoka, S. 275
Staiger, B. 271 Takase, Y. 270
Staunton, l . 254 Takatsuki, S. 266
Stecher, B. 273 Takayama, S. 275
Steffen, U.A. 271 Takeda, R . 258
Steffens, J.e. 271 Takenaka, S. 272
Steglich, W . 8, 258, 264, 267, 271 Takenaka, Y. 235-237
Steiner, E. 271 Takeo, K . 272
Steiner, l .R . 275 Tanahashi, T . 235-237,255, 272
Steingrimsson, O. 259 Tanaka, M. 266
Stenhouse, l . 271 Tanaka, O. 270
Stenroos, S. 246, 258 Tangney, R.S. 263
Stepanenko, L.S. 245,247,261 ,264,265, Tani, K. 236
271 Tashiro, T. 273
288 Author Index
Taylor, A. 254 Valois, P.J. 255

Taylor , FJ. 246 Vandervelde, D. 254
Taylor , W.e. 51, 239, 242 Van Roy, W. 264, 273
Tearne , P.D. 250 Vanska, H. 273
Teitel, S. 252 Van Vaeck, L. 264, 273
Teixeira, ALA. 254, 272 Vederas, J.e. 270
Telikepalli, H. 254 Venables, D.A. 249-251
Terna i, B. 241 Venkataramana, D. 273
Thijs, L. 273 Verseghy-Patay, K. 12, 260
Thonar, J. 268 Vicente, C. 182,218,240,252-254 ,262,
Thor, G. 250 266,273
Thune, P.O. 272 Viethen, B. 252
Timdale, E. 272 Vilhelmsdottir, M. 259
Timmer , R. 255 Vincendon, M. 7,253
Titze, E. 272 Vinet, e. 273
Tomisaki, K. 253 Vinliguerra, G. 241
Tomlinson, A.A.G. 239 Vogel, P. 269
Tomoike, S. 253 Vogt , H . 10,273
Tensberg, T. 243,251 , 258 Volk, T. 270
Torres de Ortiz, A. 252 Von Arb, e. 246
Torri, G. 264 Von Glehn, M. 266
Toscano, R.M. 241 Von Schantz, M. 258, 259
Towers, G.H.N. 221,242
Toyota, T. 253 Waanders, P.P. 43,47, 273
Traas, P.e. 255 Wachtmeister , C.A. 266
Trawoger, A. 256 Wadstein , T. 273
Triebel, D. 238 Wagner, H. 259, 266
Trimble , L.A. 270 Walker, J.R.L. 241, 256
Trotter, J. 264 Wang, J. 242
Tsoupras, G. 272 Wang, S. 266
Tsuda, Y. 239, 273 Wardlaw , I. 250
Tsuji, Y. 253 Wardlaw , J.H . 234, 236, 247-251, 261
Tulloch, A.P. 259 Waring, P. 252
Tumbay, E. 243 Watanabe, K. 261
Tiirk, R. 256 Watanabe, M. 253, 273
Turner, E. 268 Watanabe, S. 27'1
Tvaroska, I. 27, 273 Watts , P.e. 264
Tyman, J.H.P. 247, 273 Weber, N. 274
Webster, CJ. 265
Udagawa, S.-I. 273
Wechsung, R. 273
Uehara, Y. 272 Wedin, M. 251
Ueno , T. 255, 265
Wei, e.-I. 270
U1iss, D.B. 247
Weinstock , J. 197,273
Unverricht, A. 273
Wender, P.A. 201, 204, 273
Upreti , D.K. 245, 246
Wendisch, D. 239
Urasaki, M. 253 Wenkert, E. 273
Urech, M. 256
Whalley, W.B. 268,274
Uzawa, J. 273 Wheeler, R. 247
Vainshtein , E.A. 221,273 White, A.H. 242, 248
Vallen, S. 240 White, FJ. 6, 274
Author Index 289
White, J.D. 274 Yamashita, M. 265

Whiton , J .e. 224, 274 Yamazaki, M. 266
Wh itton , A.A. 247,25 1,274 Yan g, X. 275
Wiedemann , B. 259 Yan g, Y. 264
Wilhelm, G. 246 Yasuda, S. 253
Wilkins, A.L. 242,248,251,256,274 Yee, T. 262
Williams, D .E. 274 Yok ota, I. 272
Willis, A.e. 231,250 Yoshida, K. 246
Wilson , M.J . 274 Yoshida, T. 275
Wippel, A. 250 Yos hikawa, T. 253
Wirth , V. 260, 262, 263 Yoshimura, I. 5,217,25 1,253,256,258-
Wirthlin, T. 239 260, 262, 264, 275, 276
Wiseman , J.R. 274 Yu, J. 249, 251
Wobb en, H.J. 255 Yusoff, I. 269
Wollenweber, E. 274
Wolseley, P.A. 5,274 Zahner, H . 239
Wong , J .D . 240 Zak aria, Z. 269
Wong , S.-M . 274 Zanin , S.M .W. 259
Wong Ng , W. 265 Zazula , T . 261
Wood, S. 274 Zeybek, N . 243
Wright , D . 6, 274 Zeybek , U. 257,276
Wright , J . 201- 203, 266, 274 Zhi-Ning, Z. 248
Zhongwan , L. 240, 255
Xavier-Filho, L. 246, 262 Ziegler, H.G . 263
Xiaoy u, S. 255 Zimmermann , G. 267,268
Zipfel, K . 271
Yaluff, G . 252 Zopf, W. 51, 190, 276
Yamad a, Y. 256, 260, 275 Zuccarello, F. 180,241
Yamamo to , Y. 216, 224, 253, 256, 260, Zwanenburg, B. 273
264, 266, 275, 276 Zwoch, I. 28, 266
Yaman ak a, T. 253 Zygadlo, J.A. 276
Yamasak i, K . 270
Subject Index
Abscisic acid 199 3-Acetyltetr onic acids 8

Acarogobien A 234, 235 Acetyl-ex-toco pherol 150
Acarogobien B 234, 235 2-Acetyl-3,4,6-trihydroxy-7-methoxy-
Acarospora gobiensis 28, 234, 235 naph th o[2,3-b]furan-5,8-dione 187
Acarospora smaragdula 146 Acetylzeorin 206, 208
Aceta nhydride 15 A ctinogyra muehlenbergii 27
Acetic acid 6, 36 Adip ic acid 28
Acetic anh ydride 36 Agropyrum rigidum 227
Acetone 7, 15 Agrostis stolonifera 227
Acetonit rile 13 Aipolic acid 206, 208
3p-Acetoxyfem -9(l 1)-en-12p-ol 206,208 Air pollution 230
3p-Acetoxyfem -9(l 1)-en-19p-ol 206,208 Alditols 27
3p-Acetoxyfem -9(11 )-en-12-one 206, 208 Aldoses 27
3p-Acetox yhopan-1p,22-diol 206, 208 A lectoria capillaris 225
6ex-Acetoxyhopan-22-o1 206, 208 A lectoria f remontii 29
15ex-Acetoxyhopan-22-o1 206, 208 Alectoria lata 217
6R-Acetoxy-(6-[(lI 'S)-hydrox ydodecyl]-2- Alectoria nigricans 52, 94
(phenylsulfonyl)-2,4-cyclohexadien- l- Alectoria ochroleuca 217, 225
one 44 Alectoria sarmentosa 80, 170
6S-Acetoxy-(6-[( I I 'S)-hydroxydodecyl]-2- p-Alectoronic acid 80, 81
(phenylsulfonyl)-2,4-cyclohexadien- l- Alectosarmen tin 169, 170, 173, 224
one 44 Aliphatic acids 7, 29
7p-Acetoxy-22-hydroxyhopan-27-oic Aliphatic alcohols 16, 28
acid 206 4-Alkylresorcinol 229
19-Acetoxylichesterinic acid 34, 37 5-Alkylresorcinol 229
6-Acetoxyoctadeca-3,5-diene-17-olide 45 Allelopa thic activity 227
2'-Acetoxyo livetol 52, 56, 58 Allium cepa 227
3'-Acetoxyo livetol 52, 56, 58 Allium sativum 227
19-Acetoxypro to lichesterinic acid 34, 37 (- )-Allopertusaric acid 34, 36, 37
Acetylat ed pustulanes 229 Allo-proto lichestcrinic acid 34-36, 38
Acetylchloride 32 Allorhi zin 128, 132, 137
o-Acetylconstictic acid 128, 132 Alternaria alternata 225
7-Acetyl-8, lO-dihydroxy-3,9,1Ob-trirnethyl- Ambewelamide A II , 26
benzofur o[2,3-g]-I,2-benzisoxazol- Ambewelamide B 26
4(I ObH)-one II Amino acids 21
8-Acetyl-5,7-dihydroxy-3,4a,6-trimethyl- Aminocyclitctrol 21
benzofuro[3,2-f]-I,2-benzisoxazol- Aminohexitol 21
4(4aH )-one II Aminopeptidol 21
o-Acetylhypoconstictic acid 128, 132 Ammonia 6
Acetylisoarborinol 206, 208 o-Amyrone 206, 208
5-0-Acetyl-4-0-methylhiascic acid 85, p-Amyron c 206, 208
102, 116 Analgesic activity 228
292 Subject Index
Anaptychia fusca 21 Atranol 52, 55, 56

Angardianic acid 30 Atranorin 6,7,11 ,95,215,218,221 ,224,
Anomodon attenuatus 226 227-230
Anthraquinones 9, 190, 191 Aurantiacin A 147, 235
Antialgal activity 226 Aurantiacin B 147, 235
Antibacterial activity 224 Avena sativa 226
Antifungal activity 224 Averythrin 191
Antiherbivores 228 Azelaeic acid 28
Antioxidant activity 230
Antipyretic activity 228
Antitranspirant activity 227 Bacillus brevis 224
Anti-tumor activity 229, 238 Bacillus co/ensoi 226
Antiviral activity 224 Bacillus megaterium 224-226
Anzia co/pota 217 Bacillus subtilis 224-226
Anzia hypo/eucoides 131, 217 Badimia sp. 223
Anzia japonica 217 Baeomyces rufus 215
Anzia opuntiel/a 217 Baeomycesic acid 90, 229
Anzia ornata 217 Bakkanolide A 199
Anzia stenophylla 217 Barbatic acid 215,227-229
Aotearone 152 Basidiolichenes 222
Arctiidae 228 Bellidiflorin 190, 194
Aromatic aldehydes 15, 18, 19 Benzene 6
Aromatic carboxylic acids 14 Benzofuranoquinones 186
Aromatic compounds 17 Benzofurans 169
Arthogalin 24, 25 Benzoquinones 186
Arthonia endlicheri 21 (-)-N-Benzoxycarbonyl-L-Ieucine 22
Arthonia impolita 51 D-N-Benzoylalanine 23
Arthoniaic acid 85, 102, 117 L-N-Benzoylalanine 23
Arthoniales 223 D-Bcnzoylalaninol 23
Arthonin 21, 25 L-Benzoylalaninol 23
iso-Arthonin 21,25 (-)-N' -Benzoyl-t-phenylalaninol 22
Arthothelin 152, 158, 160, 161 (-)-N-Benzoyl-L-phenyl-a1aninyl-N'-ben-
Arthothelium ga/apagoense 24 zoyl-L-leucinate 22
Arthrobacter citreus 224 (-)-N-Benzoyl-L-valinyl-N'-benzoyl-i.-iso-
Asahinea chrysantha 80, 191 Icucinate 21
Asahinea scho/anderi 80 Benzyl 4-benzyloxy-3-(2',4'-dihydroxy-6'-
Asahinin 191 methylbenzoyloxy)-2-hydroxy-6-
Ascomatic acid 170, 172, 173 methyl benzoate 93
Ascomycetes 238 Benzyl 4-benzyloxy-3-(2',4'-dihydroxy-6'-
Asemone 152 methylbenzoyloxy)-6-hydroxy-2-
Aspergillus nidu/ans 235 methylbenzoate 86
Aspergillus niger 225 Benzylbromide 13, 16
Aspergillus terreus 215 Benzyl 4,6-dibenzyloxy-3-hydroxy-2-n-
Aspicilia gibbosa 225 pentylbenzoate 96
Aspicilia mashiginensis 131 Benzyl 2,4-dihydroxy-3,6-dimethylbenzo-
Aspicilia sp. 42 ate 87,92
Aspicilia transbaicalica 29 Benzyl 2,4-dihydroxy-6-n-heptylbenzo-
Aspicilin 42 ate 91, 95, 99
(+)-Aspicilin 11,42-46,49,50 Benzyl 2,3-dihydroxy-4-methoxy-6-n-pen-
(-)-Aspicilin 43,47,48 tylbenzoate 91, 97
Subject Index 293
Benzyl 2,3-dihydroxy-4-methoxy-6-n-pro- 3-Benzyloxy-2,4-dimethoxy-6-methylben-

pylbenzoate 98, 101 zoic acid 91
Benzyl 2,4-dihydroxy-6-(2'-oxo-n-nonyl)- 3-Benzyloxy-4,6-dimethoxy-2-methylben-
benzoate 100 zoic acid 89
Benzyl 2,4-dihydroxy-6-(2'-oxo-s-pentyl)- 4-Benzyloxy-3,6-dimethoxy-2-methylben-
benzoate 100 zoic acid 89
Benzyl 2,4-dihydroxy-6-n-pentylbenzo- 4-Benzyloxy-2-hydroxy-3,6-dimethylben-
ate 86, 88, 92, 96, 99, 101 zoic acid 98
Benzyl 2,4-dihydroxy-6-n-propylbenzo- 4-Benzyloxy-2-hydroxy-6-n-pentylbenzoic
ate 85, 87, 94, 101 acid 86, 87
Benzyl 2-n-heptyl-4,6-dihydroxybenzo- . 4-Benzyloxy-2-hydroxy-6-n-propylbenzoic
ate 88 acid 88
Benzyl 2-n-heptyl-4-hydroxy-6-methoxy- 4-Benzyloxy-2-methoxy-3,6-dimcthylben-
benzoate 89, 99 zoic acid 87
Benzyl 4-hydroxy-2-methoxy-3,6-dimethyl- 2-Benzyloxy-4-methoxy-6-methylbenzoic
benzoate 97 acid 100, 101
Benzyl 4-hydroxy-2-methoxy-6-methyl- 4-Benzyloxy-2-methoxy-6-n-pcntylbenzoic
benzoate 98 acid 94
Benzyl 4-hydroxy-2-methoxy-6-n-pentyl- 2-Benzyloxy-4-methoxy-6-n-propylbenzoic
benzoate 85, 89, 90, 99 acid 95
Benzyl 4-hydroxy-2-methoxy-6-n-propyl- 4-Benzyloxy-2-methoxy-6-n-propylbenzoic
benzoate 89, 95, 96 acid 101
Benzyllecanorate 89-9 1,93,95 Biatora sorediosa 96, 99
Benzyl lividate 13I Biological activity 178, 224
Benzyl 2-methoxy-4-hydroxy-6-n-heptyl- Biruloquinone 195
carboxylate 91 Blasia pusilla 58
Benzyl 2-0-methyl-4-hydroxy-6-n-pentyl- Borneol 199
benzoate 92 Boron tribromide 15
BenzyI2-0-methyllecanorate 91 Boron trichloride 15
Benzyl-2-0 -methylolivetolcarboxy- Bourgeanic acid 31
late 88, 96 (+)-Bourgeanic acid 30, 31
Benzyl orsellinate 93 Bourgeanic lactone 32
(4S,2E)- I-O-Benzyl-2-pentene-I ,4- Brialmontin I 85, 102
diol 41 Brialmontin 2 85, 102
2-Benzyloxy-5-chloro-4-methoxy-3,6-di- W-Bromodimethylmethylmesconate 33
methylbenzoic acid 97 (5E,17E)-18-Bromo-octa-S, I7-dicn-15-yo-
4-Benzyloxy-3-chloro-6-methoxy-2,5-di- nic acid 28
methylbenzoic acid 97 18-Bromo-octadcca-5,7,17-triyonic
2-Benzyloxy-3-chloro-4-methoxy-6-methyl- acid 28
benzoic acid 155 Bryoria fremontii 212
6-Benzyloxy-2,7-dichlorolichexan- Buellia granulosa 158
thone 155 Buellia sp. 156, 157, 222
4-Benzyloxy-3,5-dichloro-2-methoxy-6-n- Bunodophoron patagonicu m 92, 100, 170,
pentylbenzoic acid 88 171
6-Benzyloxy-2,4-dichloronorlichexan- tert.-B ut anol 19
thone 155 Butlerin A 77, 78
4-Benzyloxy-2,3-dihydroxy-6-n-propyl- Butlerin B II , 77, 78
benzoate 92, 10I Butlerin C 77, 78
2-Benzyloxy-3,4-dimethoxy-6-methylben- Butlerin 0 77, 79
zoic acid 93 Butlerin E 77, 79
294 Subject Index
Butlerin F 77, 79 Chalybaeizanic acid 234

Butlerins 77-79 Chiodectonic acid 188
N-(tert-Butyldimethylsilyl)-N-methyltri- Chlamydomonas reinhardii 226
fluoroacetamide 183 Chlorine 130
y-Butyrolactones 34 Chloroatranorin 6, 218
Byssoloma polychromum 152, 153, 159, 2-Chloro-6-0-benzylnorlichexan-
160 thone 153
Byssoloma subdiscordans 153, 156, 160 5-Chlorocitreorosein 221
Byssoloma tricholomum 153, 156, 160 5-Chlorodivaricatic acid 85, 102
5-Chloroemodin 220, 221
Calcium oxalate 28 3-Chlorodivaricatic acid 85, 117, 102
Caloplaca citrina 224 7-Chloroemodin 215,220,221,224
Caloplaca ferruginea 215 3-Chloro-6-hydroxy-4-methoxy-2-methyl-
Calycin 228 benzoate 156
Camphene 199 3-Chloro-2-hydroxy-4-methoxy-6-n-pentyl-
Camphor 199 benzoic acid 85, 86
Candida albieans 225, 226 3-Chloro-2-hydroxy-4-methoxy-6-propyl-
Canoparmelia sp. 222 benzoic acid 86
Canoparmelia texana 206 3-Chloroimbricaric acid 85, 103
Caperatic acid 228 Chlorolecideoidin 128, 132
Capistratone 152 2-Chlorolichexanthone 152, 161
N,N'-Carbonyldiimidazole 22 4-Chlorolichexanthone 152, 161
2-Carboxy-3 ,5-dibenzyloxyhomophtha- 5-Chlorolichexanthone 152, 161
late 150 7-Chlorolichexanthone 153, 161
Carboxylic acids 12-14, 19 5-Chloro-2'-O-methylanziaic acid 85, 103
Carcinogenic activity 5 5-Chloro-I-O-methylcitreorosein 221
Carotenoids 5,214 7-Chloro-I-O-methylcitreorosein 221
Carvone 199 5-Chloro-I-O-methylemodin 221
~-Caryophyllcnc 199 7-Chloro-I-O-methylemodin 221, 224
Catarraphia dictyoplaca 128 2-Chloro-3-0-methylnorlichexan-
Cathodoluminescence 10 thone 153, 162
Catillaria corymbosa 95 2-Chloro-6-0-methylnorlichexan-
Cercidosporidium henningsii 182 thone 153, 162
Cercosporamide II 4-Chloro-3-0-methylnorlichexan-
(- )-Cercosporamide 182, 184 thone 153, 162
Cercosporidium henningsii 184 4-Chloro-6-0-methylnorlichexan-
Cereal ~-D-glucanes 27 thone 153, 162
Cerevisterol 211,213 5-Chloro-3-0-methylnorlichexan-
Cetraria crispa 28 thone 153, 162
Cetraria cucullata 189 5-Chloro-6-0-methylnorlichexan-
Cetraria delisei 28, 30 thone 152, 153, 162
Cetraria islandica 28,30,36,53, 189, 199, 7-Chloro-3-0-methylnorlichexan-
215,217,225 thone 153, 162
Cetraria juniperina 229 7-Chloro-6-0-methylnorlichexan-
Cetraria nivalis 28, 215 thone 153, 159, 162
Cetraria oaksiana 228 l'-Chloronephroarctin 85, 103, 118
Cetrariastrumin 133 2-Chloronorlichexanthone 154, 161
Cetrelia japonica 99 4-Chloronorlichexanthone 154, 161
Cetrelia sanguiana 99 5-Chloronorlichexanthone 154, 161
Cetrelia sanguinea 87 7-Chloronorlichexanthone 154, 161
Subject Index 295
3-Chloroorse IIinic acid di-O-benzyl Cladonia pleurota 217,2 18

ether 52, 56, 59 Cladonia polycarpia 215
I'-Chloropann ar in 224, 230 Cladonia polycarpoides 51, 215
m-Chloro perbenzoic acid 19 Cladonia pyxidata 28
3-Chloroperlatolic acid 86, 102 Cladonia rangiferina 28
2-Chlorophloroglucino1 155, 156, 160 Cladonia sp. 7, 222
Chlorop hyIIopsori n 128, 132 Cladonia stellaris 218
3-Chloros tenosporic acid 86, 102 Cladonia subulata 225
N-Chlorosuccinimide 194 Cladonia sulfurina 28
Chloro vineto rin 154, 162 Cladonia uncialis 225
5-Chlorovirensic acid 131 Cladonia vulcani 215
Cholesta-3,5-dien-7-one 211 Clemmensen reduction 170
Cholest-Bven-Jp-ol 211 Cocciferae 7
Cho1est-4-en-3-one 211 Coelopogon abraxes 84
Chromanes 150 o-Collatolic acid 227
Chro mium trioxide 16 ~- CoIIatoli c acid 80, 81
Chromones 150 Collema polycarpon 212
Chrysophanol 190, 193, 229 Combea californica 170, 171
1,8-Cineol 199 Conechinocarpic acid 86, 103
Citreorose in 190, 193 Coneuplectin 236
Cladia aggregata 218, 225 Co nfluentic acid 19, 20, 84, 229
C/adia retipora 225 Co nfumarprotocetraric acid 128, 132
Cladina macaronesica 54, 207 Conhypopro tocetraric acid 128, 132, 138
Cladina mitis 217 Connorstictic acid 215
Cladina rangiferina 7 Conphysoda1icacid 128, 132
Cladina sp. 7 Co nprotocetra ric acid 128, 132
Cladina stellaris 7, 217 Co nsalazinic acid 215
Cladonia alpestris 27 Constictic acid 215
Cladonia amaurocraea 27 Consuccinopro tocetraric acid 128, 132
Cladonia arbuscula 28, 225 Contact dermatitis 228
Cladonia bacilliformis 187 Co ntortin 76, 218, 219
Cladonia be/lidiflora 190, 218 Co nvirensic acid 128, 132, 215
C/adonia boryi 2I8 u-Co paene 199
Cladonia chlorophaea 91, 129, 218 Cora pavonia 27
Cladonia confusa 27 Cornicularia acu/eata 225
Cladonia cornuta 28, 217 Cornicularia epiphorella 81
Cladonia crista/ella 190, 216, 218, 224 Cornicu/aria m uricata 227
C/adonia deformis 187 Cristazarin 190
Cladonia didyma 170 18-Crown-6 13
Cladonia fimbriata 23I Crustinic acid 9, 86, 103
Cladoniafl oerkeana 187 Crustose lichens 10
Cladonia f urcata 212 Cryptochlorophaeic acid 218
Cladonia gracilis 217, 227 Cryptostictic acid 215
Cladonia grayi 131, 215 Cucurbita pepo 226
Cladonia impexa 33, 227 Cyclographin 128,1 32, 138, 219, 221
Cladonia macaronesica 206, 207 Cyclohexane 6
Cladonia merochlorophaea 97, 101 p-Cymene 199
Cladonia norvegica 187 Cytochromes 215
Cladonia phyllophora 128 Cytotox ic activity 229, 238
296 Subject Index
(+)-2-Deacylusnic acid 178 Depsides 6-9, 12, 13, 19-21, 84, 85, 127
Decarboxyalectoronic acid 128, 133 Depsidones 7,9, 12, 127, 128, 144, 145,
Decarboxyanziaic acid 86, 103 147,234, 235
Decarboxydivaricatic acid 86, 103 Depsones 9, 147, 148
Decarboxy-2'-O-methyldivaricatic (+)-Desacetyloxymycousnine 184, 185
acid 86, 103 (+)-Desacetylusnic acid 180
Decarboxy-2' -O-methylnorimbricaric (+)-2-Desacetylusnic acid 181
acid 86, 102 Diacetates 15
Decarboxynorimbricaric acid 87, 102 Diacylglyceryi-N,N,N-trimethyihomoser-
Decarboxynorstenosporic acid 87, 104 ine 231
Decarboxyperlatolic acid 87, 104 Diazomethane 12,13,15,36-38,127, 153
Decarboxystenosporic acid 87, 104 Dibaeis arcuatus 87
Decarboxythamnolic acid 84, 126 Dibcnzofurans 9, 169
3-Dechlorogangaleoidin 128, 133 2,2'-Dibenzoxazolyldisulfide 84
2-Dechloro-8-0-methylthiomelin 154, 2,4-Dibenzyloxy-5-chloro-3,6-dimethyl-
163,164 benzoate 97
4-Dechloro-8-0-methylthiomelin 154, 2,4-Dibenzyloxy-5-chloro-3,6-dimethyl-
163,165 benzoic acid 95
Dechloropannarin 128, 133, 139, 215 4,6-Dibenzyloxy-3-chloro-2-n-pentylben-
2-Dechlorothiomelin 154, 163 zoic acid 85
4-Dechlorothiomelin 154, 163, 165 2,4-Dibenzyloxy-3,6-dimethyibenzo-
Deliseic acid 9 ate 97
4-0-Demethylbaeomycesic acid 87, 102 2,4-Dibenzyloxy-3,6-dimethyl-5-chloro-
4-0-Demethylbarbatic acid 215, 227, 229 benzoic acid 94
Demethylchodatin 154, 161 2,3-Dibenzyloxy-4-methoxy-6-methylben-
4-0-Demethyldiffractaic acid 87, 102 zoic acid 91
4-0-Demethylglomellic acid 87, 104, 118 2,4-Dibenzyioxy-3-methoxy-6-methylben-
4-0-Demethylgiomelliferic acid 87, 104, zoic acid 93
118 4,5-Dibenzyloxy-2-methoxy-6-methylben-
4-0-Demethylgrayanic acid 215 zoic acid 95
4-0-Demethylimbricaric acid 87, 104 2,4-Dibenzyloxy-6-methylbenzoic
Demethylleprapinic acid 195, 196 acid 86, 92, 93
4-0-DemethYlloxodellic acid 87, 104, 118 2,4-Dibenzyloxyorsellinic acid 88
4-0-Demethylmicrophyllinic acid 87, 2,4-Dibenzyloxy-6-n-pentylbenzoic
102, 119 acid 87,97
4-0-Demethylperlatolic acid 87, 102 2,4-Dibenzyloxy-6-n-propylbenzoic
4-0-Demethylplanaic acid 87, 102 acid 87, 97, 98
3-0-Demethylscensidin 129, 133 3,5-Dichioro-2,4-dihydroxy-6-n-pentylben-
3-0-Demethylschizopeltic acid 169, 170, zoic acid 89
177 3,5-Dichioro-2,4-dihydroxy-6-n-propylben-
4'-O-Demcthylsekikaic acid 87, 104 zoic acid 89
4-0-Demethyisphaerophorin 88,104,215 Dichlorodimethyl ether 18
4-0-Demethylsquamatic acid 88, 104 5,7-Dichloroemodin 220, 221, 224
4-0-Demethyistenosporic acid 88, 104 2,4-Dichloro-I-hydroxy-7-methoxy-6,8-di-
4-0-Demethylsuperconfluentic acid 88, methylxanthone 154, 165
104,119 7,7'-Dichlorohypericin 194
Depside hydrolysis products 224 Dichloroisoeverninic acid 52, 56, 60
Depsidellin A 88, 103 2,4-Dichlorolichexanthone 154, 161
Depsidellin B 88, 103 2,7-Dichlorolichexanthone 154, 161
Depsidellin C 88, 103 4,5-Dichlorolichexanthone 154, 161
Subject Index 297
4,7-Dichlorolichexanthone 155, 161 (- )-Dihydro-a llo-protolichesterinic

5,7-Dichlorolichexanth one 155, 161 acid 36
3,5-Dichloro-2'-O-meth ylanziaic acid 89, H -Dihydropertusaric acid 34,36,3 7,232
105 (-)-Dihydropr otolichesterinic acid 36,
3,5-Dichloro-2'-O-methyinorhyperiatolic 39,41
acid 89, 105 (+ )-Dihydroprotolichesterinic acid 39, 42
2,4-Dichloro- 3-0-methylnorlichexan- I-Dihyd rou snic acid 181, 182
thone 155, 162 13-Dihydrousnic acid 182
2,5-Dichloro -3-0 -methylnorlichexan- 1,7-Dihydro xy-2,4-dichloro-6,8-dimethyl-
thone 155, 162 xanthone 157
2,5-Dichloro-6-0 -methylnor lichexan- 1,8-Dihydroxy-3,6-dimethoxyxan-
th one ISS, 162 thone 157
2,7-Dichloro -3-O-methyinorlichexan- 2,4-Dihydroxy -3,6-dimethyl-5-chloro ben-
thone 155, 162 zoic acid 94
2,7-Dichloro-6-0-methylnorlichexan- 1,8-Dihydroxy-3,6-di-O-methyl-
4,5-Dichloro-3-0-methylnorlichexan- 2,4-Dihydroxy-3-formyl-5,6-dimethylben-
thone 156, 162 zoic acid 93
4,5-Dichloro-6-O-methyinorlichexan- 3,5-Dihydroxy -n-heptylbenzene 52, 56
thone 156, 162 2,4-Dihydroxy-6-n-heptylbenzoate 98
4,7-Dichloro-3-0 -methylnorlichexan- 1,3-Dihydroxy-6-( I' -hexanoyl)-benzo-
thone 155 furan 169
4,7-Dichloro-6-0-methylnorlichexan- 1,8-Dih ydroxy-5-methoxy-3-methyl-
5,7-Dichloro- 3-O-methyinorlichexan- 2,3-Dihydroxy -4-methoxy-6-n-pentyl-
tho ne 152, 156, 162, 166 benzoate 94
5,7-Dichloro-6-0-meth ylnorlichexan- 3,5-Dihydroxy-4-methylacetic acid 52,
thone 156, 162 56,61
3,5-Dichloro- 2'-O-methylnorstenosporic 5,7-Dihydroxy-6-methylphthalide 52, 56
acid 89, 105 1,7-Dih ydroxy-3-methylxanthone 236
3,5-Dichloro-4-0 -methylplanaic acid 88, 1,3-Dih ydroxy-5-n-pent ylbenzene 87
105 3,5-Dihydroxy -n-pentylbenzene 61
2,4-Dichloronorlichexanthone 156, 161 1,3-Dihydroxy-5-n-pro pylbenzene 87
2,5-Dichloronorlichexanthone 156, 161 2,4-Dihydroxy-6-n-pro pylbenzoa te 98
2,7-Dichlorono rlichexanthone 156, 161 bis-(2,4-Dihydroxy-6-n-pro pyl-phenyl)
4,5-Dichloronorlichexanth one 157, 161 methane 229
4,7-Dichloron orlichexanth one 157, 161 2R,3R-Dihydroxysuccinic acid 43
5,7-Dichloronorlichexan thone 157, 161 Dimelaena australiensis 159,222
3,5-Dichloroolivetolcarb oxylic acid 89 Dimelaena califarnica 86
Dichioroorsellinic acid 227 Dimelaena cf. australiensis 152, 154, 155,
N,N'-D icyclohexylcarbodiimide 13, 19, 158, 159
84 Dimelaena cf. radiata 85
Didechlorolecideoidin 129, 133 Dimelaena citrinum 156
Did ymic acid 11,1 69,1 70,1 73,178 Dimelaena oreina 93, 100
Diethyl ether 6 Dimelaena sp. 158, 159, 222
8',9'-Di-O-ethylsalazinic acid 133, 146 Dimelaena thysanota 101
Diffractaic acid 227-229 1,5-Dimeth oxy-4-chloro-6-methyl-8-hydro-
3,5-D iform yl-2,4-dihydroxy-6-methylben- xyxanthone 157, 163
zoic acid 98 1,2-Dimeth oxyeth ane 128
Diholosides 27 2,4-Dimethoxy-6-n-heptylbenzoic acid 92
298 Subject Index
1,2-Dimethoxy-4,5-methylenedioxyben- Divarinolmonomethyl ether 52, 56

zene 186 Divarol 86
2,4-Dimethoxy-6-n-pentylbenzoic Divaronic acid 129, 133, 139
acid 89, 92, 95, 96 Dolichorrhizin 206, 208
2,4-Dimethoxy-6-n-propylbenzoic Drechs/era rostrata 225
acid 89, 90, 94, 99 Droplet counter-current chromatogra-
2,4-Dimethoxy-3,5,6-trimethylbenzoic phy 7
acid 85 Duff reaction 18
6,8-Di-O-methylcitreoisocoumarin 237
4,2'-Di-O-methylconnorstictic acid 129, Echinocarpic acid 90, 106
133 Eicosa-sphinganin 27
Dimethyl di-O-methylpannarate 169, Elatinic acid 90, 106
170, 177 ~-Elemene 199
Di-O-methyldivaric acid 62 Elsinochrome A 12
2,2'-Di-O-meth yldivaricatic acid 89, 105 Emeguisin A 147, 235
Dimethylformamide 15, 194 Emegu isin B 147, 235
2,4-Di-O-methylhiascic acid 89, 105, 234 Emeguisin C 147, 235
2,5-Di-O-methylhiascic acid 89, 105, 234 Emericella unguis 147, 235
2,2'-Di-O-methylimbricaric acid 89, 105 Emodin 220,221,224
I,I-Dimethylnoneicosyl everninate 52,56 Emodin derivatives 229
Di-O-methylolivetolcarboxylic acid 62 (_)_~2.II-Enaminousnic acid 178,179
2,4-Dimethylolivetolcarboxylic acid 91 Enzyme inhibitors 229
Di-O-methylorsellinic acid 62 Epidermophyton jloccosum 225
Dimethylpicroroccellin 21, 23 Epiphorellic acid I 81,82
Dimethyl roccellate 30 Epiphorellic acid 2 II , 81, 83
Di-O-methylsphaerophorolcarboxylic Epiphorellic acid 3 84
acid 62 Ergochrome AA 227
2,2'-Di-O-methylstenosporic acid 90, 105 Ergochrome BB 157, 163
Di-O-methylstrcpsilin 169, 170, 174 Ergosta-5,22-dien-313-ol 211
Dimethyl sulphate 15 Ergo sta- 7,22-d ien- 3 ~-ol 211
3,6-Di-O-methylthiophanic acid 157, 161 Ergosta-7,24(28)-dien-313-ol 212
Dinorscensidin 129, 133 Ergosta-8,22-dien-313-o1 212
Diospyros kaki 184 Ergosta-3 ,5-dien-7-onc 212
Dioxane 6 Ergosta-4-en-3-one 212
Dip/oicia canescens 129, 130,222 Ergostan-Jfi-ol 212
Dip/oicia canescens ssp. austra/asica 157, Ergosta-5,7,9(11),22-tet raen-313-ol 212
222 Ergosta-5,7,22-trien-313-ol 212
Dip/oicia sp. 222 Ergost-7 -en-313-ol 212
Dip/oicia subcanescens 222 Ergosterol 214,215
Dipl oicin 130 Ergosterol peroxide 212
Dip/oschistes gyrophoricus 95 Ergosterol-So.Sa-peroxide 212, 213
Dip/oschistes oce//atus 131 Ergosterol-Sp.Sjl-peroxide 212, 213
Dip/oschistes sp. 157 Erioderma chi/ense 131
Dipyridyle 14 Erioderma phaeorhizum 130, 150
Disodium edetate 5 Erioderma physcioides 129
Dissectic acid 90, 105 Erioderma sp. 94,95,97, 131
Divaric acid 52, 56, 62, 230 Erioderma wrightii 101
Divaricatic acid 230 Eriodermin 11,129,133,140
Divaricatinic acid 100 Erythroglaucin 190, 192, 224
Divarinol 52, 56, 229 Escherichia coli 225, 226
Subjec t Ind ex 299
Eth an ol 80 Forma ldehyde 33

Ethy l acetate 6 Formic acid 6
Et hyl acetusnetate 181 3-Formyl-2,4-dihydroxy-5,6-dimethylben-
2"'-0-Et hyl -~-alectoronic acid 80 zoic acid 99
Eth yl 5-chlorohaematommate 228 5-Formyl-2,4-dihydroxy-3,6-dimethylben -
Ethyl 3-chloro-6-hydroxy-4-met hoxy-2- zoic acid 96
methy lbenzoate 155, 160 3-Formyl-2,4-dihydroxy-6-methylbenzoic
24-E t hylcho lesta-5 ,22-dien -3~-ol 212 acid 93
Ethyl diazoacetate 37, 38 4-Formyl-5,7-dihydro xy-6-meth ylphtha-
Et hyl 3,5-dimet hoxyorsellinate 63 lide 53, 56, 64
Ethyl 3,5-dimethylorselli nate 52, 56, 62 4-Formyl-5-hydro xy-7-isop ro pyloxyph th a-
Et hyl divaricatin at e 52, 56 !ide 53, 56, 64
Ethylene 28 Fremontol 212,2 13
Ethylenediamine tetr aacetic disodium Friede lanes 9
salt 5 Fuk ina no lide A 199
Ethyl everni na te 17, 52 Fulgensia canariensis 130
Et hyl haemat ommat e 52, 56, 63, 228 Fulgensia f ulgida 129
Ethyl 5-hydrox yeverninat e 17, 52, 56 Ful gidin 129, 133, 141
Et hyl 4- 0-meth ylolivetolcarb oxylat e 52, F uma ric acid 28, 29
56 Fu ma rpro toce traric acid 7, 128, 139,227,
Et hyl orse llina te 225 228
8'-0-Ethylstictic acid 129, 131, 133 Furcatae 7
2-0-(3' -E thyl- I',2',3' ,4'-tet ra hydro-S',7',8'- Furfurace ic acid 169,1 70
trihydroxy-I',2' ,4'-triketo-3'-naphthyl- Furfuric acid 129, 134, 143
3-ethyl -7-hydroxynaphthazarin 189
Euplectin 236 n- Galacto-n- mannans 27
Evernia esorediosa 170, 217 Galactosyl-arabitol 27
Ecernia mesomorpha 29, 212 G alactosyl-ma nn itol 27
Ecernia prunastri 7, 10, 27-29, 52, 54, 55, Galactosyl-pentitol 27
182, 199,206,207,215,2 17,21 8,221, Galactosyl-ribi tol 27
225,227, 230 Galapagin 150
Evernic acid 9, 224, 227-229 G an galeoidin 129, 134
Everni nic acid 53 Gassma n-Amick reaction 18
Gattermann reac tion 18
Fa llacina l 190, 193 G laucop haeic acid 90, 106, 119
Fa llacinol 190, 193 G lomellic acid 90, 106, 118
Farnesane 199 G lomelliferic acid 90, 106, 118
Fatty acids 30 G lomellifero nic acid 129, 134
Fel/hanera sp. 223 G lomellin 53, 57, 65
Fenc ho l 199 G lomellonic acid 130, 134
Fe rn-9(1 1 )-e n -3 ~, 12~-d iol 206, 208 Glu com ann an 27
Ferne nes 9 1-( 0-et-o-Glu cop yran osyl)-3S,25R-hexaco-
Festuca rubra 227 sa nediol 28, 29
F icap renol 206, 211 G lucose 22 1
Flavoparmelia baltimorensis 225, 228 o -G lucose 39, 42
Flavoparmelia euplecta 236 Gl ucosy l-rnanni to l 27
Flavoparmelia springtonensis 128 G lutaric acid 28
Flavoparmelia succinoprotocetrarica 128 Gl utathio ne 21, 22
Fluorescence microscopy 12 Gl utathione disu lfide 21,22
Foliosae 7 G lutat hione reductase 229
300 Subject Index
Glycopeptides 27 Heterodermia dissecta 90

Graciliformin II, 190, 194 Heterodermia obscurata 194
Grammitic acid 53, 57 Heterosides 27
Granulosin 157, 161 (3E)-Hexadeca-1 ,3,15-triene 49
Graphenone 11,51,215 n-Hexane 6
Graphis desquamescens 186, 215 Hiascic acid 9
Graphis scripta 51,215,224,235 Hierridin 53, 57, 65
Graphis scripta var . pulverulenta 237 High performance liquid chromatogra-
Graphis sp. 237 phy 6, 7, 13
Graphislactone A 237 High performance thin layer chroma-
Graphislactone B 237 tography 6
Graphislactone C 237 Himatanthu s sucuuba 84
Graphislactone D 237 HIV-I integrase 229
Graphisquinone 11, 186,215 HIV-I reverse transcriptase 229
Grayanic acid 215,218 Homoheveadride 51,215
Griseoxanthone B 153, 162 Hopanes 9, 10
Griseoxanthone C 158, 162 2Ia-H-Hopanes 9
Growth inhibitory activity 226 Hopan-3p,6a,15p,22-tetrol 206
p-Gurjunene 199 Hopan-6a,7p,22-triol 206, 208
Gyrophoric acid 9, 219, 230, 231 Hybocarponc 231,238
Hydrocarbons 28
Hydrogen peroxide 19
Haematommafiexuosum 184 5-Hydroxy-7-acetoxyphthalide 53, 57
Haematomma matogrossense 184 8-Hydroxybarbatic acid 90, 105
Haematomma nemetzii 191 2-Hydroxy-4-bcnzyloxy-6-n-heptylaceto-
Haematomma ochrophaeum 90, 93 phenone 150
Haematomma puniceum 191 2-Hydroxy-4-bcnzyloxy-6-n-pentylbenzoic
Haematomma sp. 222 acid 88
Haematommic acid 53, 57, 90 8-Hydroxydiffractaic acid 90, 105
Haematommone 191 5-Hydroxy-2 ,3-dimethyl-7 -methoxychro-
Haemophaein 169, 170, 174 mone 235
Haemoventosin 189, 190 2-Hydroxyethoxyacetamide 196
Ifafellia fulgida 130 5-Hydroxyevcrninic acid 53, 57
Hedwigia ciliata 226 3-Hydroxygyrophoric acid 90, 105, 233,
Helicobacter pylori 225 234
Hemibourgeanic acid 31 3p-Hydroxyhopan-29-oic acid 206, 208
(-)-Hemibourgeanic acid 30 5-Hydroxy-2-hydroxymethyl-3-mcthyl-7-
n-Heptane 7 methoxychromone 235
l-n-Heptyl-3,5-dihydroxybenzene 229 5-Hydroxy- 3-hydroxymethyl-2-methyl-7-
2-n-Heptyl-4,6-dihydroxybenzoate 100 methoxychromone 235
6-n-Heptyl-2,4-dihydroxybenzoic acid 53, R-a-Hydroxyisovalerianic acid 24
57 5-Hydroxylccanoric acid 90, 106
2-n-Heptyl-4,6-dimethoxybenzoic 3-Hydroxy-5-methyl-4-6-dimethoxy-2-(tri-
acid 96,99, 101 cos-9'-enyl)-benzene 53, 57
2-n-Heptyl-4-hydroxy-2-methoxybenzo- 3-Hydroxy-4-0-methylgyrophoric
ate 101 acid 91, 105
2-n-Heptyl-6-hydroxy-4-methoxybenzoic 3-Hydroxy-4-0-methylumbilicaric
acid 99 acid 91, 105,233
2-n-Heptyl-4-methoxy-6-hydroxybenzoic 2-Hydroxy-4-methoxy-6-n-heptylbenzoic
acid 96 acid 92,93
Subject Index 301
2-Hydroxy-4-methoxy-6-methylbenzoic Hypogymnia farinacea 222

acid 100 Hypogymnia laminisorediata 222
2-Hydroxy -4-methoxy-6-methyl-3-formyl- Hypogymnia lugubris 225
benzoic acid 90 Hypogymnia physodes 222, 229
2-Hydroxy-4-methoxy-6-n-pentylbenzoic Hypogymnia sp. 222
acid 87,91,96 Hypogymnia tubulosa 222
2-Hydroxy-4-methoxy-6-n-propylbenzoic Hypogymnia vittata 222
acid 86-88, 99 Hyponephroarctin 92, 107
4-Hydroxy-2-methoxy-3,5,6-trimethyl- Hypophysciosporin 130, 134
benzoate 96 Hypoprotocetraric acid 215
2-Hydroxy-4-methoxy-3,5,6-trimethylben- Hyposalazinic acid 215
zoic acid 85 Hypostictic acid 137, 215
3~-Hydroxy-30-norhopan-22-one 206, Hypostrepsilalic acid 170, 172
208 Hypostrepsilic acid 11 , 170, 172,215
W-Hydroxyolean-12-en-II-one 206, 208 Hypothallin 22, 26
5'-Hydroxyolivetoric acid 145, 146 Hypotrachyna chicitae 100
5-Hydroxyorsellinic acid 53, 57, 66 Hypotrachyna gracilescens 128
3-Hydroxyovoic acid 91, 105 Hypotrachyna hypoalectorica 92
2-Hydroxypalmitic acid 27 Hypotrachyna livida 131
4-Hydroxypannaric acid 9-methyl- Hypotrachyna orientalis 233
ester 169, 170, 174 Hypotrachyna quaesita 234
3'-Hydroxy-5'-n-pentyl-4-benzyloxy-2-hy-
droxy-6-n-pentylbenzoate 88 Indolylacetic acid 26
(2S)-12-(2'-Hydroxyphenyl)- 2-dodeca- lngaderia friabillima 238
nol 42 Inhibitory activity 224
Hydroxyphysodic acid 223 Insignin 53, 57, 67
3-Hydroxyphysodic acid 228 3-Iodoorsellinic acid 53, 57
2-Hydroxypulvinic acid dilactone 195, 5-Iodoorsellinic acid 53, 57
196 lrismissouriensis 206
22ex-Hydroxy-3,4-secostictan-3-oic Isidiophorin 130, 134
acid II , 206, 208 Islandicin 190, 192
2Iex-Hydroxyserrat-14-en-3-one 207,209 Islandoquinone 189
3~-Hydroxyserrat-14-en-21-one 207,209 Isoadiantone 207, 209
22ex-Hydroxystictane 10 Isoarthonin 25
3-Hydroxy-4,4,6-trimethoxy-2,5-di-(p- Isoarthothelin 157, 166
methoxyphenyl)cyclohexa-2,5-dien-l- Isocontortin 76, 77
one II Isodidymic acid 170, 172, 175
2S,3S,4R,6R-3-Hydroxy-2,4,6-trimethyloc- Isofulgidin 130, 134
tanoic acid 30 Isohyperlatolic acid 92, 107
3-Hydroxyumbilicaric acid 91, 120, 105 Isohyperpicro1ichenic acid 148, 149
4-Hydroxyvulpinic acid 195, 196 Isohyperplanaic acid 92, 107
Hyperconfluentic acid 91, 106, 117 Isohypocrellin 194, 195
Hyperhomosekikaic acid 91, 106 Isolecanoric acid 92, 107
Hypericin 194 Isolichenan 27
Hyperlatolic acid 91, 105 Isomegapicrolichenic acid 148, 149
Hyperpicrolichenic acid 148, 149 Isomerochlorophaeic acid 92, 107
Hyperplanaic acid 91, 105 Isomultiflorenone 207, 209
Hypoa1ectorialic acid 92, 107 (-)-Isomuronic acid 36,37,231
Hypoconstictic acid 128,215 (+ j-Isomycousnine 184, 185
Hypogymnia bitteri 222 Isonorobtusatic acid 92, 107
302 Subject Index
Isonorpannarin 130, 134 Lecanora contractula 152, 153, 155

Isonotatic acid 130, 134, 143 Lecanora dispersa 128, 131, 154,215,222
Isopannarin 132, 145 Lecanora frustu/osa 222
Isopatagonic acid 92, 107, 121 Lecanora ganga/eoides 129, 130
Isoplacodiolic acid 184 Lecanora intumescens 130, 131
Isopropyl bromide 16 Lecanora jamesii 88, 95, 99
(2S,3E)-1,2-Isopropylidene-5-0-benzyl-3- Lecanora lividocinerea 85, 88, 89
pentene-I,2,5-triol 39,41 Lecanora myriocarpoides 128
Isopseudocyphellarin A 93, 107 Lecanora pachysoma 154
Isopseudoplacodiolic acid 184 Lecanora p/anaica 91, 92, 101
(+)-Isorangiformic acid 32 Lecanora populicola 153, 154, 157
Isoschizopeltic acid 170, 172, 177 Lecanora radiosa 222
Isosphaeric acid 93, 107 Lecanora rupico/a 33, 222
Isostrepsilic acid 171,172,215 Lecanora salina 153-155 , 157
Isosubpicrolichenic acid 148, 149 Lecanora sp. 152, 222, 223, 238
Isousnic acid 7 Lecanora stenotropa 32,211,212
(-)-Isousnic acid 227 Lecanora subfusca 222
Isovicanicin 130, 134 Lecanora su/phurata 152, 158, 160
Itaconic acid 33 Lecanora sulphurella 89
Lecanora sulphurescens 128
Jackinic acid 33 Lecanora vinetorum 153, 156, 158
Jones' reagent 16, 30 Lecanoric acid 9,215,219,221 ,227
Lecidea albocaerulescens 226
Keto acids 30 Lecidea cyanosarca 96
Koerberiella wimmeriana 85 Lecidea /actea 146
Konigs-Knorr condensation 27 Lecidea plana 87
Lecidea russula 191
y- Lactonic acids 33 Lecidea tessellata 216
Lactose 27 Lecide/la asema 152, 157, 159,223
Lanosterol 207, 209 Lecidella bullata 146
Lasallia asiae-orientalis 93 Lecidella carpathica 223
Lasallia brigantium 7 Lecidella cr. cyanosarca 100
Lasallia hispanica 7 Lecidella elaeochroma 154, 159
Lasallia papulosa 225 Lecidella elaeochromoides 158
Lasallia pensylvanica 219 Lecide/la fia visorediata 159
Lasallia pustulata 7 Lecidella leuckertiana 159
Lasallia sp. 222, 223 Lecidella meiocarpa 158, 160
Lasallic acid 9, 93, 108 Lecidella meiococca 152, 156-159
Laser microprobe mass spectrometry 10, Lecidella pataoina 158
12 Lecidella sp. 223
Laurera benguelensis 10 Lecidella stigmatea 158
Laurera sanguinaria 12, 194 Lecidella subalpicida 152, 157, 159
Lecanactis latebrarum 222 Lecidella viridans 223
Lecanactis sp. 222 Lecidella vorax 152, 156-158
Lecania brialmontii 85 Lecideoidin 128, 129
Lecanora alina 153 Leishmania sp. 224, 225
Lecanora argopholis 222 Leoidin 130, 134
Lecanora behringii 154, 155, 157, 159 Lepidium sativum 226, 227
Lecanora bicincta 216 Leprantha impolita 51
Lecanora broccha 152, 156, 157, 159, 160 Lepranthin II , 51
Subject Index 303
Leprapinic acid 196, 227 Loxodellic acid 93, 108, 118

Leprapinic acid derivatives 224 Loxodellonic acid 130, 135
Lepraria incana 223 Loxospora elatina 90
Lepraria jackinii 33 Lupanes 9, 10
Lepraria lesdainii 206, 223 Lupeone 207, 209
Lepraria lobificans 223
Lepraria rigidula 223 Malonic acid 28
Lepraria sp. 195, 223 Manganese oxalate 28, 29
Leproloma angardianum 30 D-Mannose 42, 46
Leproloma diffusum 170 Mannosyl-mannitol 27
Leproloma sp. 223 Manool 199
LeproIomin I I Mass spectrometry 9, 10
Leptogium saturninum 212 Megapicrolichenic acid 148, 149
Lesdainin 206, 208 Melacarpic acid 171,172,175
Letharia vulpina 7,27, 169, 195, 199,227, Menegazzia dispora 128
229 Menegazzia platytrema 128
Lichen acids 229 Menegazzianic acid 215
Lichen depsides 2I Metabolites 215
Lichen glycosides 26 Methanol 6, 7, 184, 186
Lichen mycobionts 215 2-Methoxy-4-benzyloxy-6-n-heptylbenzoic
Lichen phenols 227 acid 98
Lichen substances 4-7 ,9, II , 12 2-Methoxy-4-benzyloxy-6-n-pentylbenzoic
Lichen triterpenes 9 acid 98
Lichen triterpenoids 9 (+ )-2S-Methoxycarbonyl-3S-heptadecane-
Lichen xanthones 6 dicarboxylic acid 32
Lichenan 27, 224 1-Methoxy-4-chloro-5,8-dihydroxy-6-
Lichenan derivatives 229 methyl xanthone 158, 163
Lichenin 27 2-Methoxy-3,6-dimethyl-4 -benzyloxy-5-
Lichens 5, 6, 10, 12, 26-28 , 52, 76, 84, 85, ehlorobenzoic acid 94
128, 148, 151, 152,206 bis-(2-Methoxyethyl)ether 131
Lichesterinic acid 229 3-Methoxygyrophoric acid 93, 108
(- )-Lichesterinic acid 36 3-Methoxy-4-0-methylgyrophoric
Lichesterol 211, 214 acid 93, 108
Lichesterylic acid 36 Methoxymicareic acid 80, 82
Lichexanthone 10, 158, 161 3-Methoxy-5-n-propylphenol 86
Limonene 199 2-Methoxypsoromic acid 234
(-)-S-Limonene 200-202 21o-Mcthoxyserrat-Ia-en-Jp, 16~-
Linalool 199 diol 207, 209
Lindgren-Nilson reaction 19 Zlo-Methoxyserrat-l q-en-Jji-ol 207,209
5-Lipoxygenase 229 3~-Methoxyserrat-14-en-2Icx-ol 207,209
Lithium propylmercaptide 13 3~-Methoxyserrat-14-en-21-one 207,209
Lobaria isidiophora 130 3-Methoxy-2,5,6-trimethylphenol 85
Lobaria oregana 133 3-Methoxyumbilicaric acid 93, 108, 120
Lobaria pulmonaria 9,28, 129, 130,211, Methyl acetoacetate 54
212 Methyl aipolate 207,209
Lobaria retigera 199 Methyl alectorialate 84, 93, 108, 125
Lobaria scrobiculata 100,211,212 Methyl alloprotolichesterinate 33
Lobaric acid 224, 228 (±)-Methyl alloprotolichesterinate 34
Lobodirin 150 Methylanhydropicroroccellin 21, 23
Longifolene 199 2-0-Methylanziaic acid 93, 108
304 Subject Ind ex
6-0 -Methylart hothelin 158, 162 Meth yl 2,2'-di-O-methyldivaricatate 94,

Meth yl ascomata te 171-1 73 109
3-0-Methylasemo ne 160, 162 Meth yl 2,2'-di-O-methyleriodermate 94,
6-0-Met hylasemone 160, 162 109
2'-O -Methylatranorin 93, 108 Met hyI2',2" -di-O -methylgyropho-
Methyl baeo mycesate 95 rat e 233
2-0-Methylbaeo mycesic acid 99 Methyl di-O-methylhypost repsilalate 170
Met hyl bar batate 93, 109 Methyl di-O-methylhypost repsilate 170
Methyl bar bat olate 84, 94, 125 5- Met hyl-2,4-d i-O~me t hylo rselli nic
3-Me thyl-2-benzothiazo lone hydrazo ne acid 53, 57, 68
hydrochlorid e 6 Methyl di-O-methylporphyrilate 171,
Meth yl-(2R S,3R ,4E)-3-benzyloxy-5-hydro- 172, 176
xy-oxo lan-3-one 39 Meth yI 2,2'-di- O-meth ylstenosporate 94,
Meth yl 3-bro moevernina te 53, 57, 67 109
Meth yl 5-brom oevernin ate 53, 57 4-0-Methyldiploicin 130, 135
Methyl tert.-but yl ether 6 2-0-Methyldivar icatic acid 94, 109
Methylc alycin 195, 196 2'-O-Methyldivaricatic acid 95, 109
(+)-8-Methylcercosporamide 182-1 84 Meth ylenechloride 16
Methyl 5-chloro-4-0 -demethyl-barba- o-Methylene-j- lactonecarboxylic acids 13
tr ate 94, 109 4ex-Meth ylergosta-7,24(28)-dien-3p-
Meth yl 3-chloro -6-hydroxy-4-methoxy-2- 01 2 12,2 13
meth ylbenzoat e 153 4ex-Methylergost-7-en-3p-ol 212,213
Methyl 5-chloro no ro btusa te 94, 109 Meth yl erioder mate 95, 109
Meth yl 3-chloroo rsellina te 53, 57 Methyl ethers 15
2'-O- Methylcono rstictic acid 130, 135 Meth yl evernate 9, 84
6-Methy lcristaza rin 190 Methyl everninate I I, 58
4-0 -Methylcryptochloro phaeic acid 229 2-0-Methy lglomelliferic acid 95, 110, 117
4'-O-Methylcryptochlo rophaeic acid 94, Methyl gyro phorate 9, 84, 229
109 2"-O-Methylgy rophoric acid 95, 110,
4-0-Methyl-5-dechlorovicanicin 130, 135 122
24-Me thyl-23-dehydrolopheno l 2 12,213 4-0-Methylgyro phoric acid 9
Met hyl 2'-O-demethylpsorom ate 130, Methyl haemat ommate 53,57,225
135 2-0-Methylhiascic acid 95, 110
8-Methyldichlorodia por tin 237 2'-O-Met hylhiascic acid 95, 110
Meth yI 5,1'-d ichloron orpsoromate 130, 4-0-Methylhiascic acid 95, 110
135 Meth yl 8-hydroxybarbatate 95, 110
Meth yI 5,1'-d ichloropsorom atc 130, 135 Meth yl 8-hydroxy-4-0-demethylba rba-
(- )-Methyl dih ydro-allo-pr otolichesteri- ta te 95, 110
na te 38, 39 Meth yl 5-hydroxyevernin ate 53, 57
(-)-Methyl dihydroprotolichesteri- 2-0 -Methyl-4-hydro xy-6-n-heptylbenzo-
nat e 38, 39 ate 80
Meth yl 2,4-dihydroxy-3,6-dimethylbenzo- Methyl 4-hydroxy-2-methoxy-3,6-di-
ate 90 meth ylbenzoate 93
Meth yl 2,3-dihydroxy-6-hydroxy -5'-meth- Methyl 4-hydroxy-2-methoxy-3,5,6-tri-
oxy-4-(3-oxopentyl)-3,3'-dioxo-I 'p- pen- methylbenzoate 97, 98
tylspiro- [benzofura n-2,2'-oxabicy- Methyl 3-hydroxyo rsellinate 54, 57, 68
clo[4.1.0]-hept-5-ene]-6'p -car boxy- Meth yl 5-hydroxyo rsellinate 54, 57, 68
late II 2-0-Me thylhyperla tolic acid 95, 110
Methyl 2,4-dihydroxy-3,5 ,6-trimethyl- 2'-O-Met hylhyperlatolic acid 95, 110
benzoate 93, 95, 97, 99 4-0 -Meth ylhyperolivetoric acid 95, 110
Subject Index 305
2'- 0 -Methylhyperphyllinic acid A 95, (-)-Methyl nephr omopsinat e 38,39

110,11 7 6-0 -Methylnorascomat ic acid 171-1 73
2'-0 -Methylhyperphyllinic acid B 96, 2'-0-Methylnorba rbatic acid 97, III
110, 11 7 4'-0- Meth ylnorcryptochlorophaeic
Methyl hyperplanaiate 96, I II acid 97, I II
4-0 -Methylhypoph ysciosporin 130, 135 2-0 -Methylnor divaricatic acid 97, 112
Methyl hypop rotocetrar ate 130 4'-0-Methylnorh omosekikaic acid 97,
2'-0 -Methylimbricaric acid 96, III 112
Meth yl iodide 13, 15, 36 2-0 -Methylnori mbricaric acid 98, 11 2
4-0-Methylisocryptochlorophaeic 3-0 -Methylnorlichexant hone 158, 162
acid 96, III 2'-0 -Methylnorobtusatic acid 98, 112
2-0 -Methylisohyperlato lic acid 96, III 4'-0-Methylnorsekikaic acid 98, 112
2'-0 -Methylisohyperlatolic acid 96, III 2-0 -Methylnorstenosporic acid 98, 112
Meth yl isohyperpl anaiate 96, III 2-0 -Methylnorsuperlato lic acid 98, 112
2'-0-Methylisopseudo cyphellarin A 96, 2'-0-Methylnorsuperph yllinic acid 98,
III 112, 117
Methyl isorhizonate II Meth ylolivetolcarb oxylate 54, 57, 69
Methyl lecanorate 9 4-0-Methylolivetolcarboxylic acid 54,57,
3-0-Methyllividic acid 131, 135 91
Methyl meth oxymagnesium carbo- 4-0-Methylolivetonide 19
nate 33, 34 Meth yl ~- orcinolcarboxyl ate 54, 57, 70,
Methyl 2-meth oxy-3,5,6-trimethyl-4-hy- 228
dr oxybenzoate 94 Methyl orsellinat e 54, 57, 58, 94, 225
Methyl 4-0-methyldeliseate 9 Methyl ~-orsellinate 94, 225
Methyl 2-0 -methyldivaricata te 96, III 4-0-Methylorsellinic acid 227
MethyI2-0-methyleriodermate 97, III Methyl ovoa te 233
MethyI 2'-0-methyleriodermate 97, III 4-0- Methyl-2"-oxocryptochlorophaeic
MethyI4-0-methyleriodermate 97, II I acid 98, 11 2
Methyl 2"- 0 -methylgyrophorate 233 3-0 -Met hylpannar ic acid 171, 172, 176,
Methyl 4-0-methylhaematommate 54, 177
57,67 4-0 -Methylpannarin 131, 135
Methyl 2-methyl-3,4-methylenedioxy-6-hy- 2'-0 -Methylperlatolic acid 84,229
droxybenzoate 58 2'- 0 -Methylphenarc tin 98, 112
Methyl 2-methyl-3,4-methylenedioxy-6- C-Methylphloraceto phenone 218,219
metho xybenzoate 58 2'-0 -Methylphysodic acid 129, 133
Methyl 2'-0 -methylmicro phyllinate 97, 2'-0 -Methylphysodo ne 80
III Meth yl planaiate 99, 11 2
Methyl 6-0 -methylnorascomata te 171- Methyl protolichesterinate 33, 36
173 (±)-Methyl prot olichesterinate 34
Methyl 2-0-methyl- ~-orcinolcarboxy Methyl pseudoalectoronate 131, 136
late 54, 57 2'-0-Methylpseudocyphellarin A 99, 112
Methyl 3-0-methyl-~-orcinolcarb o xy- Methyl pseudon orstictat e 131, 136
late 70 Methyl pseudosalazinate 131, 136
Meth yI 2-0-methylperlat olate 97, III Methyl psoromate 130, 131, 136
MethyI4-0-methylprot ocetrarate 130 (-)-Methyl retigeranate A 200,201
Methyl O-methylpsoromate 131 (-)-Methyl roccellarate 38, 39
Methyl 2-methyl-3,4,6-tri- 0-meth ylbenzo- Meth yl sekikate 99, 113
ate 58 2-0-Methylsquamatic acid 99, 113
2'-0-Methylmicro phyllinic acid 97, II I, 2-0 -Methylstenosporic acid 99, 113
117 2'-0 -Met hylstenospo ric acid 99, 113
306 Subject Index
Methylstictic acid 133 Nemetzone 191

8'-0-Methylstictic acid 133, 146 Neofusce/ia depsidella 86-88
2-0-Methylsulphurellin 99, 113 Neofusce/ia loxodes 87
2-0-Methylsuperlatolic acid 99, 113 Neofusce/ia pulla 88
2'-0-Methylsuperlatolic acid 99, 113 Neofusce/ia subincerta 129, 130
4-0-Methylsuperolivetoric acid 99, 113, Neofusce/ia verruculifera 100
117 Neophyllis melacarpa 171
2'-0-Methylsuperphyllinic acid 99, 113, Nephrin 206, 208
119 Nephroma arcticum 92, 225, 228
Methyl thielavinate B 126, 127 Nephroma helveticum 212
8-0-Methylthiomelin 158, 163 Nephroma laevigatum 194,220,221
(tris-(Methylthio)methyl)lithium 33 Nephroma parile 206
3-0-Methylthiophanic acid 158, 162 Nephroma sp. 206
6-0-Methylthiophanic acid 157, 158, 162 (-)-Nephromopsinic acid 36,39,40
3-0- Methyl- 2,5,7-trichloronorliche- Nephrosterinic acid 34, 229
xanthone 10 (-)-Nephrosterinic acid 35
Methyl tri-O-methyldesoxyfurfurate 129, Neuropogolic acid 34
142 Neuropogon aurantiaco-ater 27
O-Methylvicanicin 131, 136 Neuropogon trachycarpus 34
Micarea austroternaria var. isabellina 160 Nidulin 235
Micarea isabellina 152, 157, 158 Nigella damascena 227
Mi carea prasina 80, 100 p-Nitrophenol 13
Micareic acid 80, 82 p-Nitrophenyl esters 13, 14
Microphyllinic acid 99, 113, 117 NMR spectroscopy 7
Microsporum canis 225 Noctuidae 228
Microsporum gypseum 225 NOE difference spectroscopy 9
Migrated hopanes 9 Norargopsin 131, 136
Miriquidic acid 99, 114, 122, 223 Norascomatic acid 171-173
Miriquidica /eucophaea 99 Norbaeomycesic acid 233
Miriquidica sp. 223 Norbarbatic acid 215
Mollin 150, 151 Norcaperatic acid 32
Mollugo pentaphylla 206 Nordechloropannarin 130, 131, 136
Monoamin oxidase B 229 Norhaemoventosin 189, 190
Monoterpenoids 199 30-Nor-hopan-3,22-dione 207, 209
Moretenone 207, 209 30-Nor-2IexH-hopan-3,22-dione 207,209
Mosher's IH method 28 30-Nor-2IexH-hopan-22-one 207,209
Mucor g/obosus 180, 181 30-Nor-21 exH-7~-hydroxyhopan-22-
o-Muurolene 199 one 207, 210
Mycobacterium aurum 224, 225 Norisonotatic acid 131, 136,215
Mycobacterium smegmatitis 224 Norisoobtusatic acid 99, 114, 215
Mycosphaerella nawae 184 Norlichexanthone 12, 151 , 168, 225
Mycosphaerella rubella 195 Normiriquidic acid 99, 114, 122
(-)-Mycousnine 184, 185 Norobtusatic acid 100, 114,215
Myristic aldehyde 33 Norpannarin 131, 136
Myrothecium sp. 55 (+)-Norrangiformic acid 32
Norschizopeltic acid 171, 172
Naphthopyrans 186 Norstictic acid 127, 132, 146, 215, 228
Naphthoquinones 9, 187 Northiomelin 158, 163
bis-Naphthoquinones 187 Nostoc sp. 218, 238
Nematocidal activity 228 Nostoclide I 218
Subject Index 307
Nostoclide II 218 Parmelinopsis schindleri 95

Parmelinopsis sp. 234
Ochrolechia sp. 223 Parmelinopsis spumosa 234
9-cis-Octadecenamide 26, 229 Parmelinopsis subfatiscens 234
Octa-I,8-dienedioic acid 28 Parmotrema demethylmicrophyllinum 87
Oleic acid 27 Parmotrema poolii 131
Oligosaccharides 27 Parmotrema praesorediosum 38
Olivetol 54, 57, 70-73, 86, 88, 229 Parmotrema tinctorum 92
Olivetolcarboxylic acid 54, 57 Pastuska mixture 6
Olivetoldimethyl ether 54, 57, 73 Patagonie acid 100, 114, 121
Olivetolmonomethyl ether 54, 57 Peltigera aphthosa 207, 217, 225
Olivetoric acid 223 Peltigera canina 217,218,225,228,231
Ophioparma ventosa 189 Peltigera collina 231
Optical activity 32 Peltigera horizontalis 231
Orcinol 52, 54, 57, 229 Peltigera lactucifolia 28
p-Orcinol 54, 57 Peltigera leucophlebia 225
p-Orcinolcarboxylic acid 55, 57, 215 Peltigera malacea 217,228
Orcinol p-depsides 6 Peltigera praetextata 217
Oropogon loxensis 93 Peltigera pruinosa 217
Oropogon loxodensis 95 Pentaacetylnorstictic acid II
Orsellinate depside hydrolase 221 Pentacyclic triterpenoids 9, 10
Orsellinic acid 51,55,57,73-76,219,227 Pentagenella fragillima 238
Ovoic acid 9 2,2',4,4',6'-Pentahydroxybenzophe-
Oxalic acid 28, 230 none 168
Oxolobaric acid 131, 136 2,2',4,4',6'-Pentahydroxy-6-methylbenzo-
Oxostenosporic acid 100, 114 phenone 151
(+)-Oxymycousnine 184, 185 l-n-Pentyl-2-methoxycarbonyl-3 ,6-di-
methoxalyldibenzofuran 178
Pallifera varia 228 l-n-Pentyl-2-methoxycarbonyl-3 ,6-
Palmitic acid 27 dimethoxy-8-methoxalyldibenzo-
Pankreaselastase 229 furan II
Pannaric acid 9-methylester 171 , 172, 177 Peperomia magnolifolia 227
Pannaric acid 10-methylester 171 , 172, Perlatolic acid 8, 228
177 (- )-Pertusaranic acid 36, 37
Pannarin 132, 145,215,225,230 Pertusaria albescens 36
Papulosic acid 9 Pertusaria amara 148
Parietin 12,215,228 Pertusaria cicatricosa 152-155 , 159
Parmelia birulae 195 Pertusaria corallina 29
Parmelia butleri 77 Pertusaria falklandica 131
Parmelia caperata 228 Pertusaria follmann iana 95, 96, 99
Parmelia conspersa 227 Pertusaria manamensis 96, 99
Parmelia norcrambidiocarpa 90 Pertusaria oculata 226
Parmelia notata 131 Pertusaria oraraensis 94, 96
Parmelia omphalodes 211,212 Pertusaria paradoxica 96
Parmelia saxatilis 231 Pertusaria pycnothelia 152, 157, 158, 160
Parmelia sp. 223 Pertusaria sp. 234
Parmelia tinctorum 219 Pertusaria squamatica 88
Parmeliaceae 238 Pertusaria subplanaica 89, 90, 94
Parmelinopsis bonariensis 91,93 Pertusaria truncata 148
Parmelinopsis neodamaziana 95, 234 Pertusaria velloziae 95
308 Subject Index
Pertusaria xenisomata 97 Pisum sativum 226

Perviae 7 (-)-Placodiolic acid II, 182
Perylenequinones 195 Placynthium asperel/um 228
Phaeographina chrysocarpa 12 Plagiochila killarniensis 58
Phaseolus coccineus 227 Platismatia glauca 207
Phaseolus mungo 227 Poa trivialis 227
Phenacylbromide 13 Polygonum lapathifolium 227
Phenacyl esters 13, 14 Polyporic acid 10, 186, 187
Phenanthroperylenequinones 194 Porel/a platyphyl/a 226
Phenanthroquinones 194 Porpidia diversa 97
Phenol carboxylic acids 7 Porpidia glaucophaea 53, 88, 90, 99, 101
Phenol-benzyl ethers 16 Porpidia leptocarpa 97
Phenol derivatives 9 Potassium carbonate 15, 16
Phenol-isopropyl ethers 16 Potassium hydrogen carbonate 13
Phenols 16, 19 Potassium peroxodisulphate 17
S-Phenylalanine 24 (+)-Praesorediosic acid 38, 39
Phenyldiazomethane 13 Prasinic acid 100, 114
p-Phenylenediamine 5 Preussia aurantiaca 147, 235
Phlebiarubron 187 Prostaglandin synthetase 127, 229
Phlebic acid C 206, 207, 210, 211 Protocetraric acid 128, 138, 143, 144,215
Phlebic acid D II , 206, 207, 210, 211 Protolichesterinic acid 7, 13,33,35,36,228
Phloroglucinol 153 (+)-Protolichesterinic acid 37,38,225,
Phosphatidylcholine 26, 231 229
Phosphatidylethanolamine 26, 231 (-)-Protolichesterinic acid 34,36
Phosphatidylglycerol 26 (±)-Protolichesterinic acid 34, 35, 232
Phosphatidylserine 26 (+)-Protopraesorediosic acid 38, 39
Phosphorylase 229 Protousnea dusenii 99
Photosynthetic activity 221 Protousnea magel/anica 99
Phthalic acid 55, 57 Protousnea malacea 52
Phycobiliproteins 5 Pseudephebe pubescens 215
Phyl/opsora corallina var. ochro- Pseudevernia furfuracea 9, 21, 26, 55, 80,
xantha 128, 130, 131 129,146,211,212,221,223,226,230
Phyl/opsora furfuracea 170 Pseudevernia sp. 223
Phyl/opsora haemophaea 170 Pseudobaeomyces pachycarpa 91,95,96,
Phyllopsorin 128, 131 , 136 99
Physcia aipolia 206, 207 Pseudocyphel/aria aurata 206
Physcidia cylindrophora 99 Pseudocyphel/aria billardierei 233
Physcion 225 Pseudocyphel/aria colensoi 226
Physodalic acid 228, 229 Pseudocyphel/aria degelii 226
Physodic acid 145, 146,223, 228, 230 Pseudocyphel/aria faveolata 128
Phytol 199 Pseudocyphel/aria flavicans 207
Phytotoxin 227 Pseudocyphel/aria norvegica 97,98
Phytotoxins 184 Pseudocyphel/aria pickeringii 85, 93, 96,
Picroroccellin 21, 22 98,99
Picroroccellin diastereomers 21, 24 Pseudocyphel/aria rufovirescens 226
Pilocarpaceae 223 Pseudocyphel/aria sulphurea 207
Pimelic acid 28 Pseudocyphel/aria vaccina 100
a-Pinene 199 Pseudocyphellarin A 100, 114, 123
~-Pinene 199 Pseudocyphellarin B 100, 114, 123
Pinus sylvestris 227 Pseudomonas aeruginosa 225, 226
Subject Index 309
Pseudoparmelia sp. 222 Ramalinaic acid 100, 114

Psoroma allorhizum 128 Rangiformic acid 33
Psoroma athrophyllum 130 (+)-Rangiformic acid 32
Psoroma contortum 76 Reformatsky reaction 33
Psoroma hypnorum 228 Relicina connivens 77
Psoromic acid 146, 227, 228 Relicina samoensis 86
(+)-R-Pulegone 201,202 Retigeradiol 207, 210
Pulvinic acid 196, 198 Retigeranic acid 199,205
Pulvinic acid derivatives 7, 198 (- )-Retigeranic acid 20 I
Pu1vinic acid dilactone 228 (±) -Retigeranic acid 200
Pu1vinic acid lactone derivatives 225 Retigeranic acid A 11, 199,204,205
Pulvinic acids 8, 197 (-)-Retigeranic acid A 199-204
(E)-Pulvinone 197 Retigeranic acid B II, 199
(Z)-Pulvinone 197 (-)-Retigeranic acid B 199
Pulvinones 195-197 Rhizocarpic acid 227, 228
Punctelia microsticta 231 Rhizocarpon cupreoatrum 216
Pustulan 27 Rhizocarpon flavum 217
Pyrazolines 13 Rhizocarpon superjiciale 7
Pyrenula japonica 235 Rhizonic acid 55, 57
Pyrenula pseudobufonia 235 Rhizoplaca chrysoleuca 182, 207
Pyridine 15 Rhizoplaca sp. 223
Pyridinium chlorochromate 16 Rhodocladonic acid 187
Pyxiferin 188 Rimuene 199
Pyxinaceae 28 Rinodina alba 95
Pyxine coccifera 188 Rinodina lepida 158
Pyxine sp . 227 Rinodina sp. 223
Rinodina thiomela 154, 157, 158, 160,207
Quaesitic acid 234 Roccella canariensis 219
Roccella capensis 171
Ramalina americana 87,91-93,95,97- Roccella fragillima 238
101, 130, 131,223 Roccella fuciformis 21
Ramalina asahinae 94 Roccella hypomecha 170, 223
Ramalina boninensis 217 Roccella nigerrima 238
Ramalina celestri 27, 226 Roccella obscurissima 238
Ramalina duriaei 26,28,215 Roccella sp. 222
Ramalina ecklonii 27 Roccellaceae 223
Ramalina farinacea 98 Roccellaric acid 11
Ramalina geneculata 226 (+)-Roccellaric acid 39,42
Ramalina hierrensis 53, 199,211 (-)-Roccellaric acid 39,41
Ramalina luciae 97, 98 (±)-Roccellaric acid 232
Ramalina pacifica 217 Roccellic acid 30, 227
Ramalina paludosa 101 threo-Roccellic acid 30
Ramalina seyreana 85, 94, 99 Roccellin 150, 151
Ramalina siliquosa 7,215,223 Roccellina luteola 170, 171
Ramalina sp. 92, 223 Roccellodea nigerrima 238
Ramalina subbreviuscula 215 Ropalospora oiridis 91, 92
Ramalina subcomplanata 215 Russulone 12, 191
Ramalina subfraxinea 98
Ramalina terebrata 212 Saccharose 27
Ramalina yasudae 215,217 Salazinic acid 127, 132,215,225,228
310 Subject Index
Salmonella typhimurum 229 Squamarina sp. 223

(- )-Sandaracopimaric acid 199 Squamarone 190
Scabrosin acetate butyrate 26 Squamatic acid 215
Scabrosin acetate hexanoate 26 Staphylococcus aureus 224-226
Scab rosin butyrate hexanoate 26 Stenosporonic acid 131, 137, 139
Scabrosin diacetate 26 Stereocaulon alpinum 26, 226
Scabrosin dibutyrate II, 26 Stereocaulon arcticum 226
Scabrosin esters 26, 229 Stereocaulon colensoi 226
Scensidin 129 Stereocaulon corticulatum 226
Schiff's base 18 Stereocaulon curtatum 215
Schismatomma hypothallinum 22 Stereocaulon japonicum 170
Schizopeltic acid 170 Stereocaulon paschale 21
m-Scrobiculin 124 Stereocaulon ramosum 226
p-Scrobiculin 124 Stereocaulon ramulosum 27
para-Scrobiculin 100, 115 Stereocaulon sp. 27, 29, 223
Sebaic acid 28 Stereocaulon tomentosum 28
Secalonic acid A 227 Stereocaulon vanoyei 226
Secalonic acid B 157, 163 Stereocaulon vesuvianum 52, 129, 228
Sekikaic acid II, 84 Steroids 211
~-Selinene 199 Sticta damaecornis 27
Serrat-Ia-en-Sp.Zl o-diol 207,210 Sticta sp. 27
Serrat-14-en-3,21-dione 207,210 Stictan-3~,22cx-diol 207, 210
Sesquiterpenoids 199 Stictane 3~,22cx-diol II
Silene vulgaris 227 Stictic acid 127, 132,215, 224, 228
Simonyella variegata 186 Stigmasta-f.Zz-dien-Jp-cl 212,213
Simonyellin 186 Stigmastan-Jp-ol 212, 214
Sinapis alba 227 Stigmasta-3,5,22-trien-7-one 212,214
Siphula ceratites 28 Stigmast-Sen-Jjl-ol 212
Siphulella coralloidea 131 Stigmast-Z-en-Sfl-ol 212
Siphulellic acid 131, 136 Stigmast-4-en-3-one 212
Siphulin 150 Stigmasterol 212
Smiles rearrangement 127,219 Stirtonia ramosa 98
Sodium borohydride 18, 182 Streptomyces viridochromogenes 224
Sodium chlorite 19 Subconfluentic acid 100, 115, 124
Sodium roccellate 226 Subdidymic acid 171,172,177
Solorina crocea 21,28,80, 191 Subdivaricatic acid 100, 115
Solorinic acid 229 Suberic acid 28
Solorinin II , 21, 22 Sublobaric acid 131, 137
Sphaerophorin 100, 115 Submerochlorophaeic acid 101, 115
Sphaerophorus melanocarpus 88 Subnorstictic acid 131, 137
Sphinganine 27 Subnotatic acid 131, 137, 144
(4E)-Sphingenine 27 Subpaludosic acid 101, 115
Spodoptera littoralis 228 Subpicrolichenic acid 148, 149
Sporopodium antonianum 152, 159 Subsekikaic acid 10I, 115
Sporopodium citrinum 152-154, 156 Subsphaeric acid 101, 115
Sporopodium leprieurii 152, 159 Substictic acid 131, 137
Sporopodium phyllocharis 156, 160 Succinic acid 28
Sporopodium vezdeanum 155, 159 Succinoprotocetraric acid 128
Sporopodium xantholeucum 160 Sulcaria sulcata 234
Squamarina cartilaginea 190 Sulcaria virens 128
Subject Index 311
Sulfamic acid 19 Tornabenia intricata 27

Sulphurellin 222 Toxocara canis 228
Sulphuric acid 15, 19, 132 Trebouxia erici 218, 226
Superconfluentic acid 101,115,119 Trehalose 27
Superlatolic acid 100, 114 Triacetyldemethylchodatin 154
Superoxide dismutase 229 Tri-O-acetyldemethylchodatin II
Superpicrolichenic acid 148, 149 Triacetylrhodocladonic acid II
Superplanaic acid 10I, 115 1,3,5-Tribenzyloxy-2-chlorobenzene 155
2,3,4-Tribenzyloxy-6-methylbenzoic
Tandem mass spectrometry 9 acid 90, 91
Taraxasteranes 9 Tri-O-benzylprotosiphulin 150
Taraxeranes 9 2,4,5-Trichlorolichexanthone 159, 161
Taraxerone 207, 210 2,4,7-Trichlorolichexanthone 159, 161
Tenuiorin 9 2,5,7-Trichlorolichexanthone 159, 161
Tephromela testaceoatra 146 4,5,7-Trichlorolichexanthone 159, 161
p-Terphenyls 77 2,4,5-Trichloro-6-0-methylnorliche-
Terpinen-4-ol 199 xanthone 157, 161
~-Terpineol 199 2,4,7-Trichloro-3-0-methylnorliche-
Tetraacetylsimonyellin II xanthone 159, 162
2,2',7,7'-Tetrachlorohypericin 194 2,4,7-Trichloro-6-0-methylnorliche-
1,3,6,8-Tetrahydroxyanthraquinone 12 xanthone 159, 162
2,4,2',4'-Tetrahydroxy-6,6'-di-n-propyldi- 2,5,7-Trichloro-3-0-methylnorliche-
phenylmethane 80 xanthone 152, 159, 162
1,4,5,8-Tetrahydroxy-3-ethyl-naphthalene- 2,5,7-Trichloro-6-0-methylnorliche-
2,6-dione 188 xanthone 160, 162
7,7'-bis-(I,4,5,8-Tetrahydroxy-3-ethyl- 4,5,7-Trichloro-3-0-methylnorliche-
naphthalene)-2,6-dione 188 xanthone 152, 160, 162
Tetrahydroxy fatty acids 29 4,5,7-Trichloro-6-0-methylnorliche-
1,5,6,8-Tetrahydroxy-3-methylanthraqui- xanthone 159, 160, 162, 167
none 191 2,4,5-Trichloronorlichexanthone 152, 161
3,3',6,6'-Tetrahydroxy-4-methylbiphenyl- 2,4,7-Trichloronorlichexanthone 160, 161
di-p,p'-quinone 188 2,5,7-Trichloronorlichexanthone 157
1,2,4,5-Tetramethoxybenzene 188 4,5,7-Trichloronorlichexanthone 160,161
2,3,5,6-Tetramethoxytoluene 188 Trichophyton mentagrophytes 225
Tetra-saccharides 27 Trichophyton rubrum 225
Thamnolia subuliformis 226 y- Tridecylbutenolide 33
Thelomma mammosum 85 I-n-Tridecyl-3,5-dihydroxybenzene 229
Thielavia terricola 127 Tridecyltriphenylphosphonium bro-
Thielavin A 127 mide 39
Thielavin B 127 Tridepsides 9, 127
Thielavin C 127 Trifluoroacetic anhydride 19, 64, 84
Thin layer chromatography 6 1,5,8-Trihydroxy-4-chloro-6-methyl-
Thiomelin II, 158, 163, 167,220,221 xanthone 160, 163
Thiophanic acid 158, 161 ,227 1,5,8-Trihydroxy-2,4-dichloro-6-methyl-
Thiophaninic acid 159, 162 xanthone 158, 163
a-Thujone 199 2,4,5-Trihydroxy-3,6-dimethylbenzo-
~-Thujone 199 ate 90
Thujopsene 199 2,6,8-Trihydroxy-3-methyl-7-ethyl-I,4-
Thuringione 159, 162 naphthaquinone 190
p-Toluenesulfonic acid 143 1,5,8-Trihydroxy-3-methylxanthone 236
312 Subject Index
4,5,6-Trihydroxyoctade-2-en-1:17- Usnea bismolliuscula 217

olide 42 Usnea diffracta 7, 217, 228
1-(2,4,6-Trihydroxypheny1)-octane-1 ,3,5,7- Usneafasciata 229
tetraone 151 Usneafilipendula 215
1-(2,4,7-Trihydroxyphenyl)-octane-I ,3,5,7- Usneajiexilis 215,217
tetraone 168 Usnea hesperina 207
1,5,8-Trimethoxy-2-chloro-6-methyl- Usnea hirta 28, 215
xanthone 160, 163 Usnea longissima 90, 211, 212, 217
1,5,8-Trimethoxy-4-chloro-6-methyl- Usnea misaminensis 217
xanthone 160, 163 Usnea montis-fuji 215
Trimethylammonium salts 127 Usnea mutabilis 216
1,3,6-Tri-O-methylarthothelin 160, 163 Usnea orientalis 171,215
22,29,30-Trinorhopan-3,21-dione 207, Usnea roseola 215
210 Usnea rubescens 215, 217
Triphenylphosphonium iodide 43 Usnea rubicunda 215,217
Tripterygium regelii 206 Usnea sp. 26-28
Tri-saccharides 27 Usnea trichodeoides 128
Triterpenoids 206 Usnic acid 7,9,10,178,182,215,218,
Triticum aestivum 227 225, 227-230
Triticum sativum 227 (+)-Usnic acid 7, 179-185 ,228
Trypsin 229 (-)-Usnic acid 7, 178, 181, 182, 184,226,
Tylolupenylacetate 207, 210 227
Tylothallia pahiensis 128 (-)-Usnic acid amide 184
Tyrosinase 229 DL-Usnic acid dehydrogenase 182
(+)-Usnic acid oxime anhydride 183
Ullmann reaction 127 (+)-Usnic acid sodium salt 2Y2 hydrate II
Ulva lactuca 226
Umbilicaria aprina 217 S-Valine 24
Umbilicaria caroliniana 217, 219 Vermicularin 84
Umbilicaria crustulosa 86 Verticillium achliae 225
Umbilicaria cy lindrica 211, 212, 217 Vesuvianic acid 129, 131, 133
Umbilicaria decussata 212,217 Vilsmeier-Haack reaction 18
Umbilicaria esculenta 217, 224 Vinetorin 10, 153, 164
Umbilicaria hyperborea 217 Virensic acid 128,215,227
Umbilicaria kisovana 217 Vu1pinic acid 7,11,195-198,224,227-
Umbilicaria muehlenbergii 217,219 229
Umbilicaria pensylvanica 217 Vulpinic acid isopropyl ether 196, 198
Umbilicaria polyrrhiza 217
Umbilicaria proboscidea 217 Wardomyces sp. 190
Umbilicaria pustulata 27 Weddellite 28
Umbilicaria sp. 27, 223 Whewellite 28
Umbilicaria spodochroa 27 Wolff-Kishner reduction 211
Umbilicaria vellea 217 Wrightiin II , 101, 115
Umbilicariaceae 7, 9, 223
Umbilicaric acid 9 Xanthones 10, 127, 151, 152
Unguinol 235 Xanthoparmelia amphixanthoides 234
Usnea antarctica 211,212 Xanthoparmelia cumberlandia 226,228
Usnea articulata 207,212 Xanthoparmelia duplicata 87
Usnea aurantiaco-ater 28 Xanthoparmelia metastrigosa 128
Usnea bayleyi 217 Xanthoparmelia notata 130
Subject Index 313
Xanthoparmelia scabrosa 26 X-ray analysis 10, 11,26

Xanthoparmelia sp. 223 X-ray microanalysis 10
Xanthoria candelaria 228
Xanthoria elegans 215 Yamamoto method 216
Xanthoriafallax 215 4-Ylidenebutenolides 195
Xanthoria mandschurica 215
Xanthoria mawsonii 215 Zeorin 206
Xanthoria parietina 30 Zeorinone 207, 210
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(Fortschritte Der Chemie Organischer Naturstoffe - Progress in The Chemistry of Organic Natural Products 81) S. Huneck (Auth.), Prof. W. Herz, Prof. H. Falk, Prof. G. W. Kirby, Prof. R. E. Moore (Eds.

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(Fortschritte Der Chemie Organischer Naturstoffe - Progress in The Chemistry of Organic Natural Products 81) S. Huneck (Auth.), Prof. W. Herz, Prof. H. Falk, Prof. G. W. Kirby, Prof. R. E. Moore (Eds.

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81

Fortschritte der Chemie

Springer-Verlag Wien GmbH

Prof. H. Falk, Institut für Chemie,

Prof. G. W. Kirby, Chemistry Department,

Prof. R. E. Moore, Department of Chemistry,

This work is subject to copyright.

© 2001 by Springer-Verlag Wien

Typesetting: Scientific Publishing Services (P) Ltd., Madras

Printed on acid-free and chlorine-free bleached paper

List of Contributors VIII

New Results on the Chemistry of Lichen Substances

2. Methods for Identification and Structure Elucidation of Lichen Substances . . . . 5

3. General Methods for Derivatization and Regeneration of Lichen Substances . .. 12

3.4.2. Oxidation of Aldehydes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

4. Structure Elucidation and Synthesis of Lichen Substances . . . . . . . . . . . . . . . . 21

6. Biosynt hesis of Lichen Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218

7. Chemotaxonom y of Lichens " 221

8. Biological Activities of Lichen Substances and Lichens . . . . . . . . . . . . . . . . . . 224

9. Harmful Effects of Lichens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230

10. Commercial Uses of Lichens and Lichen Substances . . . . . . . . . . . . . . . . . .. 230

Notes Added in Proof . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 231

Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277

S. Huneck , Fliederweg 34a, D-06179 Langenbogen/Saalkreis, Germany

2. Methods for Identification and Structure Elucida tion of Lichen Substances . . . 5

3. General Methods for Derivati zation and Regeneration of Lichen Substances . . 12

S. Huneck, Fortschritte der Chemie organischer Nuturstoffe

3.3. Substitution at Aro matic Rings 17

4. Structure Elucidati on and Synthesis of Lichen Substances . . . . . . . . . . . . . .. 21

4.6.3. Diterpenoids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 199

6. Biosynthesis of Lichen Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 218

7. Chemotaxonomy of Lichens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 221

8. Biological Activities of Lichen Substance s and Lichens . . . . . . . . . . . . . . . .. 224

9. Harmful Effects of Lichens . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230

10. Commercial Uses of Lichens and Lichen Substances . . . . . . . . . . . . . . . . . . . 230

Note s Added in Proof 231

The following abbreviations are used in this article: A = " Alcohol"

Culberson and Elix (100) in Harborne's Methods in Plant Biochemistry

2. Methods for Identification and Structure Elucidation

2.1. Spot Tests

Para-phenylenediamine is an excellent reagent for detection of

2.2. Thin Layer Chromatography (TLC)

Thin layer chromatography is still the method of choice for rapidly

2.3. High Performance Liquid Chromatography (HPLC)

Referen ces, pp. 239-276

Table 1. HPLC of lichen substances

Analyzed compounds, groups of compounds or lichen Ref.

Atranorin, vulpinic acid (673)

2.4. Droplet Counter-Current Chromatography

Vulpinic acid has been separated from an extract of Letharia vulpina

2.5. NMR Spectroscopy

tH_ and 13C-NMR spectroscopy and the corresponding special

1600 Perlatolic acid

Fig. 2. NMR differentiation of protons of pulvinic acids

References, pp. 239-276

Jakupovic and Huneck (442) correlated the lH-NMR spectra of

2.6. Mass Spectrometry (MS)

Scheme 2. MS fragment ation of 22ct-hydroxystictane

2.7. X-ray Analysis

X-ray analyses of lichen substances since the last review are

2.8. Cathodoluminescence and X-ray Microanalysis

Mathey and Hoder (530) have applied the technique of cathodolu-

2.9. Laser Microprobe Mass Spectrometry (LAMMA)