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Anthocyanins and other flavonoids

Christine A. Williams a and Renée J. Grayer b

a
Plant Science Laboratories, The University of Reading, Reading, UK RG6 6AS
b
Jodrell Laboratory, Royal Botanic Gardens, Kew, Richmond, Surrey, UK TW9 3AB
Received (in Cambridge, UK) 29th March 2004
First published as an Advance Article on the web 7th July 2004

Covering: January 2001 to December 2003. Previous review: Nat. Prod. Rep., 2001, 18, 310

More than 450 new flavonoid structures, reported from January 2001 until December 2003, are reviewed.
They comprise anthocyanidins, flavones, flavonols, chalcones, dihydrochalcones, aurones, flavanones and
dihydroflavonols, both as aglycones and as glycosides. The biological activity of some of the compounds
is briefly discussed. There are 289 cited references.
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1 Introduction on the assumption that ten carbons of the flavonoid skeleton

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2 Anthocyanins can be substituted by a range of different groups, among which

3 Lipophilic flavones and flavonols
4 Flavone and flavonol glycosides
5 Chalcones, dihydrochalcones and aurones
6 Flavanones and dihydroflavonols
7 References
1 Introduction
Flavonoids continue to capture the interest of scientists from
many different disciplines because of their structural diversity,
biological and ecological significance (e.g. as the coloured
pigments in many flower petals), and health-promoting and
anti-cancer properties. The number of different flavonoid
structures that are theoretically possible is astronomical, based
are hydroxyl, methoxyl, methyl, isoprenyl and benzyl substit-
uents. Furthermore, each hydroxyl group and some carbons
can be substituted by one or more of a range of different
sugars, and in turn, each sugar can be acylated with a variety
of different phenolic or aliphatic acids. According to our
assessment, approximately 9000 different flavonoids have
already been reported from plant sources, but no doubt many
more remain to be discovered. Here we review more than 450
newly reported compounds belonging to eight different classes
of flavonoids recorded in the literature from January 2001 until
December 2003. Brief mention is made of relevant data on the
biological activity of these flavonoids as cited in the original
papers. This article is a continuation of three previous reviews
in Natural Product Reports on the same subject.

Christine Williams was born in Newport, South Wales, and obtained a BSc in Botany at Royal
Holloway College, University of London, in 1960. After a varied career in mycology, plant
physiology and soil science she moved to the Botany Department at the University of Reading in
1968 to work with Professor Jeffrey Harborne in the Phytochemistry Unit. Here, she completed her
PhD on the flavonoids of the grasses and related monocot families under the supervision of Professor
Harborne. Her collaboration with Jeffrey Harborne continued at Reading until his untimely death in
July 2002. Major research projects included the flavonoids and chemosystematics of the Iridaceae,
Cyperaceae, Restionaceae and Velloziaceae and a search for flavonoids with anti-inflammatory
activity in feverfew and related members of the Compositae. Dr Williams was an associate editor of
the journal Phytochemistry for 22 years. The three previous reviews in Natural Product Reports were
co-authored by Professor Harborne and Dr Williams.

Christine Williams

Renée Grayer studied biology with chemistry at the University of Leiden, The Netherlands. She
obtained her PhD at the same university on the occurrence of iridoids and flavonoids in the genus
Veronica, under the supervision of Professor Robert Hegnauer. After her marriage she moved to
Britain and from 1975–1994 did phytochemical research at the University of Reading where she
worked with Professor Jeffrey Harborne on various projects, including the flavonoids and
isoflavonoids of the Leguminosae and the role of rice phytoalexins in the resistance of rice against
fungal diseases. Since 1994 she has worked in the Jodrell Laboratory, Royal Botanic Gardens, Kew,
DOI: 10.1039/ b311404j

where her work has included research on the flavonoids and chemosystematics of the family
Lamiaceae. She was a main contributor to the ‘Phytochemical Dictionary’ and the ‘Handbook of
Natural Flavonoids’, and compiled the Subject Index of the journal Phytochemistry for 15 years.
Currently she is on the editorial board of the journal Biochemical Systematics and Ecology.

Renée Grayer

This journal is © The Royal Society of Chemistry 2004 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 539

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2 Anthocyanins were absent from fresh extracts, and the levels increased grad-
ually with time. They were thought to be formed by a reaction
In the period under review, three new anthocyanidins and more
of the natural Ribes anthocyanins with p-coumaric acid. A
than 50 new anthocyanins have been reported from plants
conjugate of the latter compound, 1-p-coumaroylglucoside,
(Table 1), not only from flower petals, but also from leaves,
is a major constituent in this plant, and this may gradually
stems, roots, tubers, fruits and seeds.1–29 The new aglycones
hydrolyse in the extract to give the free acid. The reaction
include the 3-deoxyanthocyanidins, 6,7,3⬘-trihydroxy-5,4⬘-
was confirmed when Ribes anthocyanins were treated with
dimethoxyflavylium (1) and 6,7,3⬘,4⬘-tetrahydroxy-5-methoxy-
p-coumaric acid at 60 ⬚C over two days to afford the four
flavylium (2). These compounds were isolated from the
pyranoanthocyanins 6–9.5 The methylpyranoanthocyanins,
leaves of the creeper Arrabidaea chica (Bignoniaceae), together
pyranocyanins A and B, and pyranodelphinins A and B,
with the known 6,7-dihydroxy-5,4⬘-dimethoxyflavylium
reported two years earlier by the same authors from the acetone
(carajurin).1,2 The structure of a second known anthocyanidin
extracts of redcurrant seeds,32 were found to be the oxidative
from this species, carajurone, thought to be 5,6,7-trihydroxy-4⬘-
cycloaddition products of the extraction solvent (acetone), and
methoxyflavylium, was revised to 6,7,4⬘-trihydroxy-5-methoxy-
the natural anthocyanins in blackcurrants.33 The authors
flavylium.1 The third new aglycone is rosacyanin B (3), isolated
obtained a corresponding pyranomalvidin glycoside by incub-
from the mauve rose (Rosa hybrida) cultivar ‘M’me Violet’.3
ating the principal grape anthocyanin, malvidin 3-glucoside, for
This is the first C-4 substituted anthocyanidin isolated from
three days at 40 ⬚C with acetone.33
an unfermented plant extract. Biosynthetically it seems to be
formed by a C–C bond formation of the C-4 of cyanidin with
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the C-1 of gallate, also involving two cyclizations between the

flavylium and gallate moieties.3
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Several of the newly discovered anthocyanins also contain

novel 4-substituted anthocyanidin moieties. For example, the
3-O-glucoside and 3-O-(6-O-malonylglucoside) of 5-carboxy-
pyranocyanidin (4 and 5, respectively) were isolated from
acidified methanolic extracts of the scales of red onion, Allium
cepa.4 In addition, two methyl esters of 5 were also obtained,
but these were thought to have been formed during extraction
with acidified methanol.4 The new anthocyanidin moiety in
these four compounds, 5-carboxy-2-[3,4-dihydroxyphenyl]-3,8-
dihydroxypyrano[4,3,2-de]-1-benzopyrylium, is similar to the
carboxypyranomalvidin isolated from red wines.30 Until
relatively recently it was a mystery why the colour of red wine
does not fade over time but intensifies during maturation, as the
anthocyanins present in grape juice are simple 3-glycosides,
which quickly lose their colours.31 This is in sharp contrast to
the complex anthocyanins found in many flower petals, which
are much more stable. In the last ten years research in several
laboratories has revealed that during the maturation of wines
4-substituted anthocyanins are formed by a cycloaddition
process, involving both the C-4 and the hydroxyl on C-5 of
the anthocyanin and an ethylenic bond provided by another
molecule, e.g. pyruvic acid.30 This reaction strongly increases
the stability of the anthocyanin obtained and is probably one of
the mechanisms by which stable red wine pigments are formed.
A free 5-hydroxyl is necessary for the reaction,31 so it would not
occur with an anthocyanidin 3,5-diglycoside as a substrate.
Therefore, grape varieties that contain a high content of
anthocyanidin 3-monoglycosides may produce more superior
wines than grape varieties that contain mainly 3,5-diglyco-
sides.31 It is not only wine in which this type of reaction takes
place; 4-substituted anthocyanins were also found in an extract
of redcurrant seeds (Ribes nigrum) that had been left to stand
for several months at room temperature.5 Four new pyrano-
anthocyanins were formed in this extract: pyranocyanins C and
D, and pyranodelphinins C and D (6–9).5 These compounds
A new acetylated 3-deoxyanthocyanin, luteolinidin 5-O-
(3-O-glucosyl-2-O-acetylglucoside) (10), was isolated from the
fern Blechnum novae-zelandiae.6 The deacylated sugar moiety is
the rather unusual laminaribiose (two molecules of glucose
which are (1 3) linked). A known 3-deoxyanthocyanidin,
apigeninidin, was isolated from soybean cotyledons exposed
to UV-C (190–280 nm) irradiation. In tests using up to 200 µg
of compound, this anthocyanidin showed radical scavenger
activity towards ascorbyl and lipid radicals, but not against
hydroxyl radicals, quinones or NO.34
One of the most exciting new anthocyanins discovered in the
last three years is 8-C-glucosylcyanidin 3-O-(6-O-malonyl-
glucoside) (11), the first C-glycosylanthocyanin in nature.7
It was isolated from the deep purple perianth with dark spots of
Tricyrtis formosana cultivar Fujimusume (Liliaceae), a common
ornamental plant in Japan. The UV/Vis spectrum of the
aglycone, 8-C-glucosylcyanidin, has a λmax at 541 nm in MeOH/
HCl, in between that of cyanidin (at 535 nm) and delphinidin
(at 546 nm). Therefore, 8-C-glycosylation appears to represent
another blueing factor of flower colour in addition to hydroxyl-
ation of the B-ring, acylation, co-pigmentation and metal
complexation.7

540 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3
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Table 1 New anthocyanidins and anthocyanins reported in the period 2001–2003

Compound a Source Reference

ANTHOCYANIDINS
6,7,3⬘-Trihydroxy-5,4⬘-dimethoxyflavylium (1) Arrabidaea chica leaves (Bignoniaceae) 1, 2
6,7,3⬘,4⬘-Tetrahydroxy-5-methoxyflavylium (2)
Rosacyanin B (3) Rosa hybrida flowers (Rosaceae) 3

ANTHOCYANINS
4-Substituted anthocyanins
5-CarboxypyranoCy 3-glucoside (4) Allium cepa scales (Alliaceae) 4
5-CarboxypyranoCy 3-(6-malonylglucoside) (5)
Pyranocyanins C and D (6, 7) b Ribes nigra seeds (Saxifragaceae) 5
Pyranodelphinins C and D (8, 9) b

3-Deoxyanthocyanins
Luteolinidin 5-(3-glucosyl-2-acetylglucoside) (10) Blechnum novae-zelandiae fronds 6
(Pteridophyta)
C-Glycosyl anthocyanins
8-C-GlucosylCy 3-(6-malonylglucoside) (11) Tricyrtis formosana flowers (Liliaceae) 7
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6-Hydroxylated anthocyanins
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6-OH Pg 3-glucoside (12) Alstroemeria flowers (Alstroemeriaceae) 8

6-OH Pg 3-(6-rhamnosylglucoside) (13)
6-OH Cy 3-(6-malonylglucoside) Alstroemeria flowers (Alstroemeriaceae) 9
6-OH Dp 3-glucoside Alstroemeria flowers (Alstroemeriaceae) 10
6-OH Dp 3-(6-malonylglucoside)

Pelargonidin, Cyanidin and Delphinidin glycosides

Pg 3-[2-(6-feruloylglucosyl)glucoside]-5-glucoside Raphanus sativus roots (Cruciferae) 11
Pg 3-[2-(6-feruloylglucosyl)-6-caffeoylglucoside]-5-glucoside (14)
Pg 3-[2-(6-caffeoylglucosyl)-6-p-coumaroylglucoside]-5-glucoside
Pg 3-[2-(6-caffeoylglucosyl)-6-feruloylglucoside]-5-glucoside
Pg 3-[2-(6-feruloylglucosyl)-6-p-coumaroylglucoside]-5-glucoside
Pg 3-[2-(2-feruloylglucosyl)-6-feruloylglucoside]-5-glucoside
Pg 3-(2-xylosyl-6-malonylgalactoside) Anemone coronaria flowers (Ranunculaceae) 12
Pg 3-(2-xylosyl-6-methylmalonylgalactoside)
{6⬙-(Pg 3-[2⬙-(xylosylgalactosyl)])}{[4-(glucosyl)caffeoyl]-tartaryl}malonate
(15)
Cy 3-[2-(2-caffeoylglucosyl)-6-malonylgalactoside]-7-(6-caffeoylglucoside)-3⬘- Anemone coronaria flowers (Ranunculaceae) 13
glucuronide (16)
Cy 3-[2-(2-caffeoylglucosyl)galactoside]-7-(6-caffeoylglucoside)-3⬘-glucuronide
Dp 3-[2-(2-caffeoylglucosyl)-6-malonylgalactoside]-7-(6-caffeoylglucoside)-3⬘- Anemone coronaria flowers (Ranunculaceae) 14
glucuronide
Dp 3-[2-(2-caffeoylglucosyl)galactoside]-7-(6-caffeoylglucoside)-3⬘-
glucuronide
Dp 3-[2-(2-caffeoylglucosyl)-6-(2-tartarylmalonyl)galactoside]-7-(6-
caffeoylglucoside)-3⬘-glucuronide
Cy 3-[2-(2-caffeoylglucosyl)-6-(2-tartarylmalonyl)galactoside]-7-(6-
caffeoylglucoside)-3⬘-glucuronide
Cy 3-(2-galloyl-6-rhamnosylgalactoside) (17) Acalypha hispida flowers (Euphorbiaceae) 15
Cy 3-[2-(2-sinapoylxylosyl)-6-(4-glucosyl-p-coumaroyl)glucoside]-5-(6- Arabidopsis thaliana leaves and stems 16
malonylglucoside) (18) (Cruciferae)
Cy 3-(3-glucosyl-6-malonylglucoside)-4⬘-glucoside Allium cepa scales (Alliaceae) 17
Cy 7-(3-glucosyl-6-malonylglucoside)-4⬘-glucoside (19)
Cy 3-[2-(6-caffeoylglucosyl)-6-{4-(6-3,5- Ipomoea asarifolia flowers (Convolvulaceae) 18
dihydroxycinnamoylglucosyl)}caffeoylglucoside]-5-glucoside (20)
Cy 3-[2-(6-p-coumaroylglucosyl)-6-{4-(6-p-
coumaroylglucosyl)}caffeoylglucoside]-5-glucoside
Cy 3-(6-acetylgalactoside) Nymphaea alba leaves (Nymphaeaceae) 19
Cy 3-(2-xylosyl-6-malonylglucoside)-7-glucoside Meconopsis grandis flowers (Papaveraceae) 20
Dp 3,5-di-(6-malonylglucoside) Cichorium intybus flowers (Compositae) 21
Dp 3-(6-malonylglucoside)-5-glucoside
Dp 3-(6-p-coumaroylgalactoside) Camellia sinensis flowers and leaves 22
(Theaceae)
Dp 3-(2-rhamnosyl-6-malonylglucoside) Clitoria ternatea flowers (Leguminosae) 23
Dp 3-[2-(6-feruloylglucosyl)-6-p-coumaroylglucoside]-5-(6-malonylglucoside) Ajuga reptans flowers and flower cultures 24
(21) (Labiatae)
Dp 3-[2-(6-feruloylglucosyl)-6-feruloylglucoside]-5-(6-malonylglucoside)
Cy 3-[2-(6-p-coumaroylglucosyl)-6-p-coumaroylglucoside]-5-glucoside
Dp 3,7-di-glucoside-3⬘,5⬘-di-(6-p-coumaroylglucoside) Dianella nigra and Dianella tasmanica 25
Dp 3-glucoside-7,3⬘,5⬘-tri-(6-p-coumaroylglucoside) berries (Liliaceae)
Dp 3,7,3⬘,5⬘-tetra-(6-p-coumaroylglucoside) (22)
Dp 3,7,3⬘,5⬘-tetraglucoside
Dp 3-(6-p-coumaroylglucoside)-5-(4-rhamnosyl-6-malonylglucoside) Muscari armeniacum flowers (Liliaceae) 26
(muscarinin A) (23)

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Table 1 (Cont’d)

Compound a Source Reference

Malvidin, Petunidin and Peonidin glycosides

Mv 3-[6-(4-{4-(6-feruloylglucosyl)-p-coumaroyl}rhamnosyl)glucoside]-5- Petunia hybrida flowers (Solanaceae) 27
glucoside (24)
Mv 3-[6-(4-{4-(6-p-coumaroylglucosyl)-p-coumaroyl}rhamnosyl)glucoside]-5-
glucoside
Pn 3-[6-(4-caffeoylrhamnosyl)glucoside]-5-glucoside (25) Solanum tuberosum tubers and sprouts 28
Pt 3-[6-(4-caffeoylrhamnosyl)glucoside]-5-glucoside (26) (Solanaceae)
Pn 3-(6-malonylglucoside)-5-glucoside Allium cepa scales (Alliaceae) 17
Pn 3-(6-malonylglucoside)

Anthocyanin–catechin dimers
Diastereomers of a dimer consisting of cyanidin 3-galactoside and Rosé cider, prepared from the fruits of 29
(⫺)-epicatechin linked by a CH3-CH bridge at C8 and differing Malus (Rosaceae)
in the configuration of the asymmetric methine carbon (27)
a
Abbreviations: Pg, pelargonidin; Cy, cyanidin; Dp, delphinidin; Mv, malvidin; Pn, peonidin; Pt, petunidin. The linkages between anthocyanidins
and sugars, and between sugars and other sugars or acyl groups, are all -O-, unless specified as -C-. Sugar linkages are β for glucose, galactose and
xylose and α for rhamnose. Sugars are all in the pyranose form. Where hydroxycinnamic acids are the acyl groups, they are assumed to be in the E-
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form. b Pyranocyanins C and D and pyranodelphinins C and D are artefacts, thought to be formed by a reaction of the natural Ribes anthocyanins
with p-coumaric acid present in the extract5 (see text).
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facilities at the time were not sufficient to elucidate the full

Flowers of Alstroemeria continue to be the source of new
6-hydroxylated anthocyanins, after their first discovery nearly
20 years ago.35 Now another five new glycosides have been
identified from the petals of various Alstroemeria cultivars,8,9,10
including two 6-hydroxypelargonidin (aurantinidin) glycosides
(12,13) from cultivars Oreiju, Mayprista and Spotty-red, which
have orange-red flowers.8 This is the first time that aurantinidin
has been found in glycosidic combination; previously it had
only been recorded as an aglycone (from Impatiens aurantiaca,
fam. Balsaminaceae).36
structures. Now three complex acylated pelargonidin glycosides
containing lathyrose have been reported from the petals of
Anemone coronaria ‘St Brigid Red’, including 15, the sub-
stituents of which include the unusual tartaric acid.12 This
compound also contains malonic acid as an acyl group, both
carboxyl groups of which are esterified, with hydroxyl groups
of galactose and tartaric acid, respectively. However, both
carboxyl groups of the tartaric acid are free, but both the
hydroxyl groups are involved in ester formation. Tartaric acid is
also present attached to malonic acid in the same way in some
of the new complex polyacylated anthocyanins reported from
purple-red and violet-blue flowers of A. coronaria, which are
based on cyanidin and delphinidin.13,14 Many of these are
3,7,3⬘-triglycosides, with [2-O-(2-O-caffeoylglucosyl)galactose]
attached to the 3-hydroxyl, 6-O-caffeoylglucose to the 7-
hydroxyl and glucuronic acid to the 3⬘-hydroxyl groups, e.g. 16.
Furthermore, in some of the compounds the galactose is
acylated with malonic acid or tartarylmalonic acid.14

The remainder of the new anthocyanins reported from

2001–2003 are almost all acylated glycosides of the common
anthocyanidins, pelargonidin, cyanidin and delphinidin, and
their methylated derivatives peonidin, petunidin and malvidin.
It has been known for four decades that radishes (the red
swollen roots of Raphanus sativus, Cruciferae) contain complex
mixtures of acylated 3-O-sophoroside-5-O-glucosides of pelar-
gonidin and cyanidin,37 but their complete characterisation has
only recently been achieved. Eleven acylated pelargonidin 3-O-
sophoroside-5-O-glucosides and one corresponding cyanidin
glycoside have now been isolated and identified, six of which
are new, e.g. pelargonidin 3-O-[2-O-(6-O-feruloylglucosyl)-6-O-
caffeoyl]glucoside-5-O-glucoside 14.11 The scarlet flowers of
Anemone coronaria have equally attracted the attention of
anthocyanin chemists for many decades. Back in the 1960s they
were shown to contain glycosides of pelargonidin with the
unusual sugar lathyrose (2-O-xylosylgalactose),37 but again the

542 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3

It is well-known that the most common acids present as acyl
groups in anthocyanins are the hydroxycinnamic acids, caffeic,
ferulic and p-coumaric acids, and the aliphatic dicarboxylic
acid, malonic acid. Acylation with hydroxybenzoic acids such
as gallic acid is much rarer and tends to occur only in certain
taxonomic groups such as the families Nymphaeaceae and
Aceraceae. However, two galloylanthocyanins have now been
identified in a species belonging to the Euphorbiaceae, Acalypha
hispida (chenille plant). The main anthocyanin (85%) in the
red flowers of A. hispida is the known cyanidin 3-O-(2-O-
galloylgalactose), but a minor pigment (5%) is the new cyanidin
3-O-(2-O-galloyl-6-O-rhamnosylgalactoside) (17).15
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Esters of the less common hydroxycinnamic acid, sinapic
acid, are characteristic constituents of species belonging to the
family Brassicaceae (Cruciferae). It is therefore no surprise
to find sinapoyl as one of the acyl groups in the complex poly-
acylated cyanidin glycoside 18 from the leaves and stems of
Arabidopsis thaliana.18 The deacylated compound, cyanidin
3-O-sambubioside-5-O-glucoside (sambubiose = 2-O-xylosyl-
glucose), is the same as that found in red-violet flowers of
Matthiola incana,38 which belongs to the same family.
Apart from the carboxypyranoanthocyanins discussed above,
some more novel minor anthocyanins have been isolated from
the scales of red onion (Allium cepa).17 Some of these contain
sugars attached to the 4⬘-position, which is very unusual in
anthocyanins. In the past only the 4⬘-O-glucoside and 3,4⬘-di-
O-glucoside of cyanidin have been reported, from the flowers of
Hibiscus esculentus (Malvaceae), but the identifications were
based on very little evidence. These two compounds have now
unequivocally been identified in red onion, together with the
new cyanidin 3-O-(3-O-glucosyl-6-O-malonylglucoside)-4⬘-O-
glucoside and cyanidin 7-O-(3-O-glucosyl-6-O-malonylgluco-
side)-4⬘-O-glucoside (19).17 This 4⬘-substitution with a sugar
leads to a hypsochromic shift (8–12 nm) of the visible λmax
values of cyanidin glycosides, which has a ‘reddening’ effect.
Another unusual feature of these two new onion anthocyanins
is the (1 3) attachment of the two glucose units (lamin-
aribiose) in the sugar chain on the 3- and 7-positions, respect-
ively. Minor amounts of two new but less complex peonidin
glycosides were also detected in the scales of red onion (see
Table 1).
In the last two decades, flowers of Ipomoea species have been
a steady source of complex new polyacylated anthocyanins.
Two more cyanidin glycosides have recently been reported from
I. asarifolia flowers.18 They are tri-acylated and tetra-glucosyl-
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ated (e.g. 20). The much less complex new cyanidin 2-O-(6-O-
acetylgalactoside) was reported from the reddish leaves of the
waterlily, Nymphaea alba.19
It is somewhat ironic that the compound cyanidin is named
after the deep-blue cornflower, Centaurea cyanus (the Greek
word cyanus means dark-blue), as cyanidin is usually associated
with red flowers, whereas delphinidin is usually found in blue
flowers. However, there are more examples of blue flower
pigments which contain cyanidin, e.g. the main anthocyanin
from the sky-blue Himalayan poppy, Meconopsis grandis
(Papaveraceae), which is cyanidin 3-O-(2-O-xylosyl-6-O-
malonylglucoside)-7-O-glucoside.20 This compound, like the
anthocyanins in Arabidopsis and Matthiola, contains the sugar
sambubiose. Two potential flavonol co-pigments in the
Meconopsis flower were identified as kaempferol 3-O-gentio-
bioside and kaempferol 3-O-(6-O-glucosylgalactoside).20 The
main pigments in the equally striking blue petals of chicory,
Cichorium intybus, are based on delphinidin. Many years ago it
was suggested that the acylated sugar moieties on the 3- and 5-
positions of the major anthocyanin were malonylglucose on the
basis of FAB-MS measurements,39 but the positions of the acyl
groups could not be determined. NMR spectroscopy of the
pigment has now shown that the malonyl groups are attached to
the 6-hydroxyl of the glucose moieties.21 Another new antho-
cyanin from the same source is delphinidin 3-O-(6-O-malonyl-
glucoside)-5-O-glucoside.21 An example of a red delphinidin
pigment is the new delphinidin 3-O-(6-O-p-coumaroylgalacto-
side), found in the reddish leaves and flowers of red flower tea
(Camellia sinensis ‘Benibana-cha’).22 This compound has anti-
oxidant activity and is the first natural anthocyanin reported
from unfermented tea. Although some anthocyanins are known
from fermented tea leaves, these are formed as a result of oxid-
ation of (⫺)-epigallocatechin gallate present in these leaves.22
Complex delphinidin glycosides with acylated glucose chains
of various lengths on both the 3⬘- and 5⬘-positions, called
ternatins, are known to occur in blue flower lines of Clitoria
ternatea.40 Recently, a comparative study was carried out of the
anthocyanins and other flavonoids in a number of different
petal lines, using LC-MS-MS. Fifteen different ternatins were
detected in cv. Double Blue, in the wild type and in a blue
mutant. However, a mauve petal line produced delphinidin
glycosides which were not glycosylated in the B-ring, including
the new delphinidin 3-O-(2-O-rhamnosyl-6-O-malonylgluco-
side).23 The authors concluded that glycosylation of the 3⬘- and
5⬘-hydroxyls of the anthocyanins is a critical step for the pro-
duction of true blue pigments in flower petals of C. ternatea.
N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 543

Under certain conditions, cell cultures can be a good source
for the production of anthocyanins, e.g. for natural food color-
ants. An example is the flower culture system of Ajuga reptans
(Labiatae), which produces a number of different acylated
delphinidin and cyanidin glycosides.24 Three new polyacylated
3,5-diglucosides, e.g. 21, have been reported from these cultures
and also from the flowers themselves, whereas two more glyco-
sides have been identified tentatively.24 In a search for stable
blue anthocyanins with potential as colorants for food or
cosmetics, the first four delphinidin 3,7,3⬘,5⬘-tetraglycosides,
e.g. 22, were isolated from the blue berries of the Australasian
Dianella nigra and D. tasmanica (Liliaceae). Three of these new
anthocyanins are poly-p-coumaroylglucosides.25 p-Coumaric
acid is also one of the acyl groups of the delphinidin 3,5-di-
glycoside, muscarinin A (23), from the purplish-blue flowers of
Muscari armeniacum, another member of the Liliaceae.26
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A chemotaxonomic feature of species belonging to the family
Solanaceae is that their flowers often contain pigments based
on the methylated anthocyanidins, peonidin, petunidin and
malvidin.37 Two new diacylated malvidin glycosides including
24 have been reported from violet flowers of Petunia hybrida
cv. Festival, together with known diacylated malvidin and
petunidin glycosides.27 From the purple sprouts of a Norwegian
cultivar of potato, Solanum tuberosum, two new anthocyanins,
the 3-O-[6-O-(4-O-caffeoylrhamnosyl)glucoside]-5-O-gluco-
sides of peonidin and petunidin (25 and 26), have been isolated
together with the known 3-O-[6-O-(4-O-p-coumaroylrhamno-
syl)glucoside]-5-O-glucosides, peonanin and petanin, respect-
ively, which are the major pigments. In the thin violet zone
located in the flesh of the potatoes, 0.5–1 mm from the surface
of the tuber, the same anthocyanins were found, but in different
proportions.28
Apple cider, like wine, contains many phenolics which are
very important for the taste, colour, flavour and longevity of the
drinks. Many of these compounds do not occur in the original
apple or grape extracts from which they are prepared, but
originate during the vinification process. HPLC-DAD and LC-
ESI-MS of rosé cider revealed the presence of anthocyanin
pigments not present in apple juice. These compounds were also
544 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3
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produced in a model cider containing cyanidin 3-galactoside
and (⫺)-epicatechin in the presence of acetaldehyde, and
shown to be two diastereomers of a dimer consisting of the
anthocyanin and the flavan-3-ol linked by a CH3-CH bridge
at the 8-position (27). The diastereomers differ in the configur-
ation of the asymmetric methine carbon.29
Apart from papers that describe the isolation and elucidation
of new anthocyanins, some useful anthocyanin reviews have
been published in the last three years. These include a review of
the recent progress in the chemistry of polyacylated antho-
cyanins as flower colour pigments.41 In it the authors present
the distribution and structures of polyacylated anthocyanins,
their UV/Vis spectral properties in acid and also under neutral
or weakly acidic conditions, and their NMR spectra and stereo-
structures. It is well known that the aromatic acids in polyacyl-
ated anthocyanins play an important role in blueing of the
flower colours and especially in stabilising the flower colours
because of intramolecular copigmentation between aglycone
and the aromatic acids. The polyacylated glycosides were
classified into seven groups and an attempt was made to see
whether there is a correlation between position and numbers of
the acyl groups and stabilisation of the colour. Acylation with
aromatic acids at the 7- and 3⬘-positions seemed to make
the most stable flower colours.41 These anthocyanins make
relatively rigid stacking sandwich structures.
The position of the sugars in flavonoid co-pigments also
appears to be very important for the production of the stable
colour of blue metallo-anthocyanin flower pigments.42 As has
been demonstrated more than a decade ago, this blue colour is
the result of a stoichiometric self-assembled supramolecular
pigment consisting of six molecules of an anthocyanin, six
molecules of a flavonoid glycoside and two metal atoms.43 For
example, protodelphin, the blue pigment from the petals of
Salvia patens (fam. Labiatae), consists of the anthocyanin
malonylawobanin (28), the flavone apigenin 7,4⬘-di-O-β--
glucoside (29) and Mg2⫹ ions. In order to study the role of the
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flavone co-pigment for the development of the colour,
unnatural derivatives of 29 were prepared, in which one or both
the -glucose molecules were substituted with -glucose. These
derivatives were used to see how they affect the chiral recog-
nition on formation of the metallo-anthocyanin. Mixtures
containing the anthocyanin 28 and either the 7,4⬘-di-O--gluco-
side or the 7-O--glucoside-4⬘-O--glucoside of apigenin gave
purple solutions, but the 7-O--glucoside-4⬘-O--glucoside
gave a blue solution with 28 similar to that with the natural 7,4⬘-
di-O--glucoside (29). However, only the solution of 28 with
the natural flavone diglycoside gave a blue colour that was
stable after 40 hours.42 The natural monoglycosides, apigenin
7-O--glucoside (30) and apigenin 4⬘-O--glucoside (31), were
also tested. The 7--glucoside did not give the blue pigment
when mixed with 28 and the metal ions, whereas the 4⬘--gluco-
side did, and the blue colour was more stable than that
generated with the 7-O--glucoside-4⬘-O--glucoside. Apigenin
4⬘-O--glucoside did not generate the metallo-anthocyanin. All
these results suggest that a -glucosyl moiety at the 4⬘-position
Published on 07 July 2004 on http://pubs.rsc.org | doi:10.1039/B311404J
highly O-methylated, C-methylated and isoprenylated flavon-
oids are produced in glands on the surface of leaves, flowers
or fruits, especially in families such as the Labiatae and
Compositae. Simply dipping the tissue in acetone removes the
lipophilic flavonoids separating them from the more polar
constituents, allowing the possibility of two flavonoid profiles
for each tissue. Recent examples of such analyses in the
Labiatae include a leaf surface flavonoids survey of the genus
Ocimum 51 with the isolation of the new flavone, pilosin (5,7,8-
trihydroxy-6,4⬘-dimethoxyflavone) and in the genus Nepeta 56
with the first discovery of 8-hydroxycirsiliol (5,8,3⬘,4⬘-tetra-
hydroxy-6,7-dimethoxyflavone). In Ocimum americanum 51
external flavonoids were used to identify chemotypes across
its geographic range. The leaf exudate of Psiadia punctulata
(Compositae) 61 was found to contain three unusual new
flavones: 5,7-dihydroxy-2⬘,3⬘,4⬘,5⬘-tetramethoxyflavone, 5,4⬘-di-
hydroxy-7,2⬘,3⬘,5⬘-tetramethoxyflavone and 5,7,4⬘-trihydroxy-
2⬘,3⬘,5⬘-trimethoxyflavone. An extensive analysis of the
lipophilic and vacuolar flavonoid constituents of four

of the flavone co-pigment is a necessity for the development European Pulicaria species 85 resulted in the identification of
of a blue metal complex pigment. A -glucose residue at the two new flavonols from P. odora, both 6-hydroxykaempferol
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7-position may be required for stabilising the molecular derivatives. Thus, the 3,7,4⬘-trimethyl ether was found on the
association, whereas an -glucose might destabilise the complex surface of the inflorescence and the fully methylated 3,5,7,4⬘-
by steric hindrance.42 pentamethyl ether on the surface of both the leaf and
inflorescence.

Recently more and more papers have reported interesting

biological and medicinal properties of anthocyanins. A useful
review of these studies has been published,44 in which the
antioxidant activities and free radical scavenging properties of
this group of compounds and anthocyanin–DNA interaction
are also included. However, the authors point out that in
comparison with other flavonoid groups relatively little work
has been done on anthocyanins and much more research could
be carried out, especially on structure–activity relationships
and the in vivo antioxidant efficacy of anthocyanins.

3 Lipophilic flavones and flavonols

During the period under review some 63 new flavones and
27 new flavonols have been reported, which are listed in Tables
2 45–83 and 3,84–95 respectively. These entries bring the total
number of known flavones to 535 and of known flavonols to
593. The new compounds have been isolated from a variety of
plant tissues including leaves, twigs, fruits, stem bark, heart-
wood, roots, root bark, root cortex and rhizomes, usually in the
free state. Despite the fact that different plant tissues generally
have different flavonoid profiles, a significant number of workers
do not specify which plant tissue they have extracted. Also it is Amongst the simple flavones listed in Table 2 are reports of
still unusual for authors to indicate the location of lipophilic two previously known methyl ethers of known aglycones. These
flavonoids or to specifically test for surface constituents. Many are 6-hydroxyluteolin 5,6,7,3⬘-tetramethyl ether, which has been

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Table 2 New flavones reported in the period 2001–2003

Flavone Source Reference

Tri-O-substituted flavones
5-Hydroxy-7,2⬘-dimethoxyflavone Andrographis rothii whole plant (Acanthaceae) 45
5,7,2⬘-Trimethoxyflavone Andrographis viscuosula whole plant (Acanthaceae) 46
7,2⬘,4⬘-Trimethoxyflavone Albizia odoratissima root bark (Leguminosae) 47

Tetra-O-substituted flavones
5,2⬘,6⬘-Trihydroxy-7-methoxyflavone Andrographis elongata whole plant (Acanthaceae) 48

Penta-O-substituted flavones
4⬘-Hydroxy-5,6,7,3⬘-tetramethoxyflavone (6-hydroxyluteolin Bauhinia guianensis (Leguminosae) 49
5,6,7,3⬘-tetramethyl ether)
5,8-Dihydroxy-7,3⬘,4⬘-trimethoxyflavone (hypolaetin 7,3⬘,4⬘- Conyza blinii aerial parts (Compositae) 50
trimethyl ether)
5,7,8-Trihydroxy-6,4⬘-dimethoxyflavone (pilosin) Ocimum americanum var. pilosum leaf surface (Labiatae) 51
5,7,2⬘-Trihydroxy-6,8-dimethoxyflavone Scutellaria baicalensis roots (Labiatae) 52
5,7,2⬘,6⬘-Tetrahydroxy-8-methoxyflavone Scutellaria radix (Labiatae) 53
5,2⬘,4⬘-Trihydroxy-7,8-dimethoxyflavone Urtica dioica roots (Urticaceae) 54
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5-Hydroxy-7,8,2⬘,5⬘-tetramethoxyflavone Andrographis affinis whole plant (Acanthaceae) 55

5,7,2⬘,4⬘,6⬘-Pentamethoxyflavone Andrographis viscuosula whole plant (Acanthaceae) 46
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Hexa-O-substituted flavones
5,8,3⬘,4⬘-Tetrahydroxy-6,7-dimethoxyflavone (8-hydroxycirsiliol) Nepeta cataria & N. isaurica leaf surface (Labiatae) 56
5,8,4⬘-Trihydroxy-6,7,3⬘-trimethoxyflavone Mentha longifolia (Labiatae) 57
8,3⬘-Dihydroxy-5,6,7,4⬘-tetramethoxyflavone Vernonia saligna (Compositae) 58
6,2⬘-Dihydroxy-5,7,8,6⬘-tetramethoxyflavone Scutellaria baicalensis roots (Labiatae) 52, 59
5,6⬘-Dihydroxy-6,7,8,2⬘-tetramethoxyflavone Toona sinensis leaves (Meliaceae) 60
5,7,4⬘-Trihydroxy-2⬘,3⬘,4⬘-trimethoxyflavone Psiadia punctulata leaf exudate (Compositae) 61
5,7-Dihydroxy-2⬘,3⬘,4⬘,5⬘-tetramethoxyflavone
5,4⬘-Dihydroxy-7,2⬘,3⬘,5⬘-tetramethoxyflavone

Hepta-O-substituted flavones
5,7,3⬘,6⬘-Tetrahydroxy-6,8,2⬘-trimethoxyflavone Scutellaria planipes root (Labiatae) 62

Isoprenylated, methylenedioxy, pyrano- and furanoflavones

5,7,2⬘,4⬘-Tetrahydroxy-8-(3⬙,3⬙-dimethylallyl)-5⬘-(1⵮,1⵮- Dalea scandens var. paucifolia roots (Leguminosae) 63
dimethylallyl)flavone
Artocarpol H (32) Artocarpus rigida root bark (Moraceae) 64
5,7-Dimethoxy-3⬘,4⬘-methylenedioxyflavone Neoraputia magnifica var. magnifica fruits (Rutaceae) 65
5-Hydroxy-7,5⬘-dimethoxy-3⬘,4⬘-methylenedioxyflavone Ficus gomelleira leaves (Moraceae) 66
5-Hydroxy-7,3⬘,5⬘-trimethoxy-4⬘-(3⬙,3⬙-dimethylallyloxy)flavone
7,8-Dimethoxy-3⬘,4⬘-methylenedioxyflavone Albizia odoratissima root bark (Leguminosae) 47
7,2⬘-Dimethoxy-4⬘,5⬘-methylenedioxyflavone (millettocalyxin A) Millettia erythrocalyx stem bark (Leguminosae) 67
6-(3⬙,3⬙-Dimethylallyloxy)-7-methoxy-3⬘,4⬘-methylene-
dioxyflavone (millettocalyxin B)
2⬘,5⬘-Dimethoxy-[2⬙,3⬙:7,8]furanoflavone (millettocalyxin C)
5⬘-Methoxy-[2⬙,3⬙:7,8]furanoflavone (pongol 5⬘-methyl ether)
Moralbanone (33) Morus alba root bark (Moraceae) 68
5,4⬘-Dihydroxy-5⬙-isopropenyldihydrofurano[2⬙,3⬙:7,6]flavone Dorstenia ciliata aerial parts (Moraceae) 69
(ciliatin A) (34)
7,4⬘-Dihydroxy-3⬘-methoxy-6⬙,6⬙-dimethyldi-
hydropyrano[2⬙,3⬙:5,6]flavone (ciliatin B) (35)
(⫹)-5,4⬘,5⬙ξ-Trihydroxy-6⬙,6⬙-dimethyldi- Dorstenia dinklagei twigs (Moraceae) 70
hydropyrano[2⬙,3⬙:7,6]flavone (dinklagin B) (36)
(⫹)-6-(2ξ-Hydroxy-3-methyl-3-butenyl)-5,7,4⬘-trihydroxyflavone
(dinklagin C) (37)
Artocommunol CA (38) Artocarpus communis root cortex (Moraceae) 71
Artocommunol CB (39)
Artocommunol CC (40)
Artocommunol CD (41)
Artocommunol CE (42)
Artelastocarpin (43) Artocarpus elasticus wood (Moraceae) 72
Carpelastofuran (44)
5,4⬘,4⬙,5⬙-Tetrahydroxy-6⬙,6⬙-dimethyldi- Retama raetam aerial parts (Leguminosae) 73
hydropyrano[2⬙,3⬙:7,8]flavone (45)
5,4⬘-Dihydroxy-3⬘-methoxy-6⬙,6⬙-di- Lonchocarpus xuul & L. yucatanensis stem bark and root 74
methylpyrano[2⬙,3⬙:7,6]flavone (46) (Leguminosae)
5,4⬘-Dimethoxy-6⬙,6⬙-dimethylpyrano[2⬙,3⬙:7,6]flavone
14-Hydroxyartonin E (47) Artocarpus lanceifolius (Moraceae) 75
Artoindonesianin L (48) Artocarpus rotunda root bark (Moraceae) 76
Artoindonesianin P (49) Artocarpus lanceifolius tree bark (Moraceae) 77
Artoindonesianin Q (50) Artocarpus champeden heartwood (Moraceae) 78
Artoindonesianin R (51)
Artoindonesianin S (52)
Artoindonesianin T (53)
Ugonin J (54) Helminthostachys zeylandica rhizomes (Ophioglossaceae) 79
Ugonin K (55)

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Table 2 (Cont’d)

Flavone Source Reference

Ugonin L (56)
5-Hydroxy-6,7-dimethoxy-8-C-(2-hydroxy-5-methoxybenzyl)flav- Uvaria macrophylla roots (Annonaceae) 80
one (57)

C-Methylated flavones
5,5⬘-Dihydroxy-6,8-di-C-methyl-7-acetoxy-6⬙,6⬙-di- Elsholtzia blanda whole plant (Berberidaceae) 81
methylpyrano[2⬙,3⬙:4⬘,3⬘]flavone (58)
5,5⬘-Dihydroxy-6,8-di-C-methyl-7-(α-methylbutyroxy)-6⬙,6⬙-di-
methylpyrano[2⬙,3⬙:4⬘,3⬘]flavone (59)
5,5⬘-Dihydroxy-6,7-methylenedioxy-8-C-methyl-6⬙,6⬙-di-
methylpyrano[2⬙,3⬙:4⬘,3⬘]flavone (60)
5-Methoxy-3-methyl-3⬘,4⬘-methylenedioxyfurano[2⬙,3⬙:7,8]flavone Hibiscus rosa-sinensis leaves (Malvaceae) 82
(61)

Flavone–coumarin adducts
6-(8⬙-Umbelliferyl)apigenin (62) Gnidia socotrana leaves and twigs (Thymelaeaceae) 83
8-(6⬙-Umbelliferyl)apigenin (63)
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N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 547
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Table 3 New flavonols reported in the period 2001–2003

Flavonol Source Reference

Penta-O-substituted flavonols
3,5,3⬘-Trihydroxy-7,2⬘-dimethoxyflavone (Iris flavone D) Iris bungei underground parts (Iridaceae) 84
5,7,2⬘-Trihydroxy-3,6-dimethoxyflavone (Iris flavone A)
5,2⬘-Dihydroxy-3,6,7-trimethoxyflavone (Iris flavone B)
3,5,6,7,4⬘-Pentamethoxyflavone (6-hydroxykaempferol 3,5,6,7,4⬘- Pulicaria odora leaf and inflorescence surface 85
pentamethyl ether) (Compositae)
5,6-Dihydroxy-3,7,4⬘-trimethoxyflavone (6-hydroxykaempferol 3,7,4⬘-
trimethyl ether)

Hexa-O-substituted flavonols
7,8,3⬘,4⬘-Tetrahydroxy-3,5-dimethoxyflavone (gossypetin 3,5-dimethyl Eugenia edulis leaves (Myrtaceae) 86
ether)
7,4⬘,5⬘-Trihydroxy-3,5,5⬘-trimethoxyflavone (myricetin 3,5,3⬘-trimethyl
ether)
5,2⬘,6⬘-Trihydroxy-3,6,7-trimethoxyflavone (Iris flavone C) Iris bungei underground parts (Iridaceae) 84

Hepta-O-substituted flavonols
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5,7-Dihydroxy-3,6,8,3⬘,4⬘-pentamethoxyflavone Melicope coodeana syn. Euodia simplex leaves 87

(Rutaceae)
5,7,2⬘,3⬘,4⬘-Pentahydroxy-3,6-dimethoxyflavone (present as the 7- Tridax procumbens aerial parts (Compositae) 88
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glucoside)

Isoprenylated, pyrano-, furano- and methylenedioxy flavonols

5,7-Dihydroxy-3⬘-(2-hydroxy-3-methyl-3-butenyl)-3,6,4⬘-trimethoxyflavone Durantia repens (Verbenaceae) 89
3,7-Dihydroxy-3⬘-(2-hydroxy-3-methyl-3-butenyl)-5,6,4⬘-trimethoxyflavone
3⬘-Hydroxy-3,5,4⬘-trimethoxy-5⬙-isopropenyldi- Vellozia graminifolia whole plant (Velloziaceae) 90
hydrofurano[2⬙,3⬙:7,8]flavone (64)
6,5⬘-Di-C-prenylquercetin (papyriflavonol A) (65) Broussonetia papyrifera root bark (Moraceae) 91
3,5-Dimethoxy-6⬙,6⬙-dimethylpyrano[2⬙,3⬙:7,8]flavone (66) Lonchocarpus latifolius roots (Leguminosae) 92
Broussonol A (67) Broussonetia kazinoki leaves (Moraceae) 93
Broussonol B (68)
Broussonol C (69)
Broussonol D (70)
Broussonol E (71)
4⬙,5⬙-Dihydro-3,5,4⬘-trihydroxy-4⬙,4⬙,5⬙-trimethylfurano[2⬙,3⬙:7,8]flavone Helminthostachys zeylanica rhizomes 79
(ugonin F) (72) (Ophioglossaceae)
3,5,7,4⬘-Tetrahydroxy-6-(2,6,6-trimethyl-2-cyclohexenylmethyl)flavone
(ugonin G) (73)
5,7,3⬘,4⬘-Tetrahydroxy-3-methoxy-2⬘-(2,6,6-trimethyl-2-cyclo-
hexenylmethyl)flavone (ugonin H) (74)
4⬙a,5⬙,6⬙,8⬙a-Tetrahydro-5,7,4⬘-trihydroxy-3-methoxy-5⬙,5⬙,8⬙a-trimethyl-
4H-chromeno[2⬙,3⬙:3⬘,2⬘]flavone (ugonin I) (75)
5,7-Dihydroxy-3,8-dimethoxy-3⬘,4⬘-methylenedioxyflavone (76) Melicope coodeana syn. Euodia simplex leaves 87
(Rutaceae)
5,7-Dihydroxy-3,6,8-trimethoxy-3⬘,4⬘-methylenedioxyflavone

C-Methylated flavonols
5,7-Dihydroxy-3,8,4⬘-trimethoxy-6-C-methylflavone Metrosideros robusta leaf wax (Myrtaceae) 94
5,7,3⬘,4⬘-Tetrahydroxy-3,6-dimethoxy-8-C-methylflavone Vellozia candida leaves (Velloziaceae) 95
5,3⬘,4⬘-Trihydroxy-3,6,7-trimethoxy-8-C-methylflavone

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N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3
549
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recorded from Bauhinia guianensis (Leguminosae) 49 and hypo-

laetin 7,3⬘,4⬘-trimethyl ether from Conyza blinii (Compositae).50
Table 2 includes eight new 6,8-dihydroxyflavone derivatives,
most of which were isolated from members of the Labiatae
e.g. 5,8,4⬘-trihydroxy-6,7,3⬘-trimethoxyflavone from Mentha
longifolia. 57 The new flavones also include an unusually large
number of 2⬘-substituted flavonoids with some 11 simple and
three isoprenylated structures. Flavonoids with 2⬘-substitution
have been found as frequent root constituents of members
of the genus Scutellaria (Labiatae), e.g. 5,7,2⬘-trihydroxy-6,8-di-
methoxyflavone and 6,2⬘-dihydroxy-5,7,8,6⬘-tetramethoxy-
flavone from S. baicalensis 52 and 5,7,3⬘,6⬘-tetrahydroxy-6,8,2⬘-
trimethoxyflavone from S. planipes.62
Isoprenylated flavones form by far the largest group in Table
2 with some 37 new structures. These include a wide variety of
compounds from simple prenyl to ring closed dimethylpyrano,
furano and similar derivatives. Many of the more complex
structures which are illustrated have been reported from the
family Moraceae. For example, artocommunols CA, CB, CC,
CD and CE (38–42) have been characterised from the root

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cortex of Artocarpus communis,71 artoindonesianin L (48) from

the root bark of A. rotunda,76 artoindonesianin P (49) from the
tree bark of A. lanceifolius 77 and artoindonesianins Q, R, S and
T (50–53) from the heartwood of A. champeden.78
Three new isoprenylated C-methylated flavones have been
reported from a whole plant extract of Elsholtzia blanda
(Labiatae).81 Similar compounds, muxiangrines I, II and III,
have been previously isolated from another Elsholtzia species,
E. stauntonii.96 The structure of another 3-C-methylated-5-O-
methylated flavone (61) with an additional furano group at
the 7,8 and a methylenedioxy group at the 3⬘,4⬘-positions,
which has been reported from leaves of Hibiscus rosa-sinensis
(Malvaceae),82 needs careful checking. C-Methylation at the
3-position is very rare with 6- and/or 8-C-methylation being
the norm. The known 3-methylated compounds, 3-C-methyl-
apigenin and 3-C-methyl-luteolin, have only been reported in
glycosidic combination as the 5-O-rhamnosides in the aerial
parts of Eugenia kurzii (Myrtaceae).97
Six unusual novel cyclized geranyl flavonoids, three flavones
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(ugonins J, K and L, 54–56) and four flavonols (ugonins F, G, H

and I, 72–75) have been isolated from the rhizomes of
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Helminthostachys zeylanica (Ophioglossaceae).79 However, two

of the most unusual flavones reported in the period under
review, consisting of a flavone and a coumarin moiety con-
nected by a C–C-linkage, were found in leaves and twigs
of Gnidia socotrana (Thymelaeaceae).83 Here the flavone was
identified as apigenin and the coumarin as umbelliferone and
the structures determined as 6-(8⬙-umbelliferylapigenin) (62)
and its isomer, 8-(6⬙-umbelliferylapigenin) (63).
A further 12 isoprenylated flavonols have been recorded
since the previous review (see Table 3), including five complex
structures, broussonols A–E (67–71), from the leaves of
Broussonetia kazinoki (Moraceae),93 a plant widely used in
Chinese folk medicine. However, none of the new flavonols
showed significant cytotoxicity when tested against several
human tumor cell lines. A simpler diprenylated compound,
papyriflavonol A (6,5⬘-diprenylquercetin, 65) has been isolated
from the root bark of another Broussonetia species used in
Chinese medicine, B. papyrifera.91 The presence of two new
methylenedioxyflavonols (76 and its 6-methyl ether) and other
known highly methylated flavonols in leaves of Euodia simplex
has supported the recent renaming of this species as Melicope
coodeana.87
Four novel 2⬘-substituted flavonols, Iris flavones A–D (see
Table 3) have been identified from the rhizomes of another
medicinal plant, Iris bungei (Iridaceae),84 but no bioassays were
carried out.
Amongst the new reports of simple flavonols are two new
methyl ethers of previously known aglycones. These are
gossypetin 3,5-dimethyl ether and myricetin 3,5,3⬘-trimethyl
ether, both from leaves of Eugenia edulis (Myrtaceae).86 Three
simple C-methylated flavonols are listed in Table 3, namely
6-C-methyl-8-hydroxykaempferol 3,8,4⬘-trimethyl ether from
the leaf wax of Metrosideros robusta (Myrtaceae) 94 and two
8-C-methylated flavonols from leaves of Vellozia candida
(Velloziaceae),95 5,7,3⬘,4⬘-tetrahydroxy-3,6-dimethoxy-8-C-
methylflavone and its 7-methyl ether.

4 Flavone and flavonol glycosides

Some 51 new flavone glycosides and 152 new flavonol glycosides
have been reported during the period 2001–2003. This brings
the total number of known glycosides to nearly 700 flavones
and more than 1400 flavonols, respectively. The new glycosides
are listed in Tables 4 98–124 and 5 125–215 and include acylated
and sulfated derivatives as well as structures with only sugar
substituents. Unless otherwise indicated, all the sugars entered
in Tables 4 and 5 are assumed to be in the pyranose form and
to have the appropriate linkage i.e. β- for glucosides, α- for
rhamnosides etc.

N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 551
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Table 4 New flavone glycosides reported in the period 2001–2003

Flavone glycosides Source References

5,7-Dihydroxyflavone (chrysin)
7-(4⬙-Acetylglucoside) Calicotome villosa aerial parts (Leguminosae) 98
7-(6⬙-Acetylglucoside) 99

5,7,8-Trihydroxyflavone (norwogonin)
7-Galactoside Scutellaria ocellata & S. nepetoides (Labiatae) 100

7-Hydroxy-5,8-dimethoxyflavone
7-Glucoside Scutellaria immaculata aerial parts (Labiatae) 100

5,2⬘-Dihydroxy-7-methoxyflavone (echioidin)
2⬘-(6⬙-Acetylglucoside) Andrographis affinis whole plant (Acanthaceae) 101

Apigenin
7-Glucosyl(1 2)glucuronide-4⬘-glucuronide Medicago sativa aerial parts (Leguminosae) 102
Pinnatifinoside A (77) Crataegus pinnatifida var. major leaves (Rosaceae) 103
Pinnatifinoside B (78)
Published on 07 July 2004 on http://pubs.rsc.org | doi:10.1039/B311404J

Pinnatifinoside C (79)
Pinnatifinoside D (80)
7-(6⬙-E-p-Coumaroylgalactoside) Lagopsis supina whole plant (Labiatae) 104
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7-(3⬙,6⬙-di-E-p-Coumaroylgalactoside)
7-Rhamnosyl(1 6)(4⬙-E-p-methoxycinnamoylglucoside) Chrozophora oblongifolia aerial parts (Euphorbiaceae) 105
4⬘-(2⵮-Feruloylglucuronosyl)(1 2)glucuronide Medicago sativa aerial parts (Leguminosae) 106
7-Glucuronosyl(1 3)[(2⵮-p-coumaroylglucuronosyl)(1 2) Medicago sativa aerial parts (Leguminosae) 102
glucuronide]
7-Glucuronosyl(1 3)[(2⵮-
feruloylglucuronosyl)(1 2)glucuronide]
7-(2⵮-Feruloylglucuronosyl)(1 2)glucuronide-4⬘-glucuronide
7-Glucuronide-4⬘-(2⵮-E-p- Medicago sativa aerial parts (Leguminosae) 106
coumaroylglucuronosyl((1 2)glucuronide
7-Glucuronide-4⬘-(2⵮-feruloylglucuronosyl)(1 2)glucuronide

Apigenin 7-methyl ether (genkwanin)

4⬘-α--Arabinopyranosyl(1 6)galactoside Salvia moorcroftiana whole plant (Labiatae) 107
4⬘-Rhamnosyl(1 2)[rhamnosyl(1 6)galactoside]

Apigenin 4⬘-methyl ether (acacetin)

7-[6⬙⬙-Acetylglucosyl(1 2)][rhamnosyl(1 6)glucoside] Calamintha glandulosa leaves (Labiatae) 108

6-Hydroxyapigenin (scutellarein)
7-Xylosyl(1 2)xyloside Hebe stenophyllum leaves (Scrophulariaceae) 109
7-Xylosyl(1 2)glucoside

Scutellarein 6-methyl ether (hispidulin)

7-(6⬙-E-p-Coumaroylglucoside) Eriocaulon buergerianum capitula (Eriocaulaceae) 110

Scutellarein 4⬘-methyl ether

7-Rutinoside Teucridium parvifolium leaves, stems and fruits (Labiatae) 111

8-Hydroxyapigenin (isoscutellarein)
8-(2⬙,4⬙-Disulfatoglucuronide) Helicteres isora fruit (Sterculiaceae) 112

Isoscutellarein 4⬘-methyl ether

8-(6⬙-n-Butylglucuronide) Helicteres isora fruit (Sterculiaceae) 112
8-(2⬙,4⬙-Disulfatoglucuronide)

6,8-Dihydroxy-7,4⬘-dimethoxyflavone
6-Rutinoside Dicliptera riparia whole plant (Acanthaceae) 113
6-(4⬙-Acetylrhamnosyl)(1 6)glucoside

5,2⬘-Dihydroxy-7,8-dimethoxyflavone (skullcapflavone I)
2⬘-(4⬙-E-Cinnamoylglucoside) Andrographis elongata whole plant (Acanthaceae) 114

Luteolin
7-Glucoside-3⬘-glucuronide Melissa officinalis leaves (Labiatae) 115
7-Glucoside-4⬘-(Z-2-methyl-2-butenoate) Polygonum aviculare whole plant (Polygonaceae) 116
7-Apiosyl(1 2)[glucosyl(1 4)(6-malonylglucoside)] Capsicum annum fruit (Solanaceae) 117
7-(2⬘⬙-Feruloylglucuronosyl)(1 2)glucuronide-4⬘-glucuronide Medicago sativa aerial parts (Leguminosae) 102

Luteolin 3⬘-methyl ether (chrysoeriol)

7,4⬘-Diglucuronide Medicago sativa aerial parts (Leguminosae) 118
7-(3⬙-Z-p-Coumaroylglucoside) Ballota acetabulosa flowering aerial parts (Labiatae) 119
7-(2⬙-Feruloylglucuronosyl)(1 2)glucuronide Medicago sativa aerial parts (Leguminosae) 118
7-Glucuronosyl(1 3)[(2⵮-
feruloylglucuronosyl)(1 2)glucuronide]

552 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3

Table 4 (Cont’d)
Flavone glycosides
Luteolin 4⬘-methyl ether(diosmetin)
7-Xylosyl(1 6)glucoside
6-Hydroxyluteolin
7-Xylosyl(1 6)glucoside
7-(6⬙-E-Caffeoylglucoside)
6-Hydroxyluteolin 4⬘-methyl ether
7-Rhamnosyl(1 2)(6⬙-acetylglucoside)
5,8-Dihydroxy-6,7,4⬘-trimethoxyflavone (8-hydroxysalvigenin)
8-Glucoside
5,7,3⬘,5⬘-Tetrahydroxy-3⬘-methoxyflavone (tricetin 3⬘-methyl
ether)
7-Glucuronide
Published on 07 July 2004 on http://pubs.rsc.org | doi:10.1039/B311404J
Tricetin 3⬘,5⬘-dimethyl ether (tricin)
4⬘-Apioside
7-(2⬙-p-Coumaroylglucuronosyl)(1 2)glucuronide
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7-(2⬙-Feruloylglucuronosyl)(1 2)glucuronide
7-(2⬙-Sinapoylglucuronosyl)(1 2)glucuronide
7-Glucuronosyl(1 3)[(2⵮-
feruloylglucuronosyl)(1 2)glucuronide]
Tricetin 7,3⬘,4⬘,5⬘-tetramethyl ether
5-Xylosyl(1 2)rhamnoside
5,6,7,8,3⬘,4⬘-Hexahydroxyflavone
7-Glucoside
a
A 1992 reference missed out of previous listings.
Three new monosaccharides have been found in combination
with a flavonoid during the review period, namely fructose,
allulose (preferred name, psicose) and lyxose. There has been
one previous report of a tricin 7-fructosylglucoside from
Hyacinthus orientalis (Liliaceae),216 but the structure was never
confirmed. α--Fructofuranose has now been reported from
leaves of Crataegus pinnatifida (Rosaceae),103 where it is linked
in a most unusual fashion to both the 7-hydroxyl and C-8 of
apigenin. Thus, the sugar forms both an O- and a C-glycosidic
link to form a ring structure (pinnatifinoside A, 77). An
acetylated derivative (pinnatifinoside B, 78) and two related
non-acylated structures, pinnatifinosides C and D (79,80),
where fructose is replaced by the sugars β--allulofuranose and
α--allulofuranose, respectively, were identified in the same
plant. α--Lyxopyranose, the C2-epimer of xylose, a sugar that
is rare in nature, has been found attached to the 8-hydroxyl
of the flavonol gossypetin in the aerial parts of Orostachys
japonicus (Crassulaceae).200
Only three new disaccharides were discovered during the
review period. They are all isomers of known sugar combin-
ations. Thus, galactosyl(1 6)glucose, an isomer of the 1 4
linked sugar, lactose, was found at the 3-hydroxyl of
kaempferol, with a feruloyl acylating group at the 2-position
of the galactose, in bulbs of Allium porrum.140 The other two
View Online
Source References
Hebe parviflora & H. traversii leaves (Scrophulariaceae) 109
Hebe stenophylla leaves (Scrophulariceae) 109
Veronica longifolia aerial parts (Scrophulariaceae) 120
Veronica iwanensis aerial parts (Scrophulariaceae) 120
Isodon enanderianus aerial parts (Labiatae) 121
Medicago sativa aerial parts (Leguminosae) 118
Salsola collina aerial parts (Chenopodiaceae) 122 a
Medicago sativa aerial parts (Leguminosae) 118
Bauhinia variegata seeds (Leguminosae) 123
Juniperus zeravschanica fruits (Cupessaceae) 124
disaccharides are glucosyl(1 2)-α--arabinose and galactosyl-
(1 2)rhamnose. The former occurs at the 3-hydroxyl of
quercetin with a galloyl group at the 2-hydroxyl of the glucose
in Euphorbia pachyrhiza (Euphorbiaceae) 176 and the latter
at the 3-position of quercetin 5,3⬘,4⬘-trimethyl ether with an
additional rhamnose at the 7-hydroxyl in aerial parts of the
legume, Alhagi persarum.196 Some 18 new flavone glucuronides
have been characterised during the review period, including six
diglucuronides (all but one acylated), but no new sugar linkages
were present. The previously unknown simple diglycoside,
chrysoeriol 7,4⬘-diglucuronide, has been detected in aerial parts
of Medicago sativa.118 Other new expectable disaccharide
flavone combinations include the 7-xylosyl(1 2)xyloside and
7-xylosyl(1 2)glucoside of scutellarein in leaves of Hebe
stenophyllum 109 and scutellarein 4⬘-methyl ether 7-rutinoside
from leaves, stems and fruits of Teucridium parvifolium.111
Only two linear trisaccharides have been found previously in
combination with flavones. Therefore, the discovery of four new
flavone branched trisaccharides is of some note, although a
branched tetrasaccharide attached to the flavone acacetin is
known.217 The four branched trisaccharide structures are listed
in Table 6. Two of them, 2G-rhamnosyl robinobioside and 2G-
glucosylrutinose, have been reported previously in combination
with flavonols. However, apiosyl(1 2)[glucosyl(1 4)glucose]
(2G-apiosylcellobiose) found in fruits of Capsicum annuum
(Solanaceae) 117 at the 7-hydroxyl of luteolin and
glucuronosyl(1 3)[glucuronosyl(1 2)glucuronic acid] from
the aerial parts of Medicago sativa (Leguminosae),118 which was
found attached to the 7-hydroxyls of apigenin, chysoeriol and
tricin, have not been recorded before in combination with
flavones or flavonols. Both new trisaccharides were only present
in acylated form, the former with a malonyl group at the
6-hydroxyl of the first sugar and the latter with either a
p-coumaroyl or a feruloyl group attached to the 2-hydroxyl of
the second glucuronic acid moiety (see Table 4). This is also the
first time a glucuronosyl(1 3)glucuronic acid linkage has been
found.
N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 553
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Table 5 New flavonol glycosides reported in the period 2001–2003

Flavonol glycosides Source Reference

5,7-Dihydroxy-3,6-dimethoxyflavone
5-α--Arabinosyl(1 6)glucoside Acacia catechu stems (Leguminosae) 125

Kaempferol
3-Xylosyl(1 3)rhamnosyl(1 6)galactoside Astragalus caprinus leaves (Leguminosae) 126
3-Xylosyl(1 6)glucosyl(1 2)rhamnoside Helicia nilagirica leaves (Proteaceae) 127
3-Rhamnosyl(1 3)rhamnosyl(1 6)glucoside Camellia sinensis green tea (Theaceae) 128
3-Rhamnosyl(1 2)glucosyl(1 6)galactoside Cassia marginata stems (Leguminosae) 129
7-(3G-Glucosylgentiobioside) Brassica juncea leaves (Cruciferae) 130
3-Glucosyl(1 4)galactoside-7-α--arabinofuranoside Corchorus depressus whole plant (Tiliaceae) 131
3-Glucosyl(1 6)galactoside-7-α--arabinofuranoside
3-Apioside-7-rhamnosyl(1 6)galactoside Silphium perfoliatum leaves (Compositae) 132
3-Galactoside-3⬘,4⬘-dirhamnoside Astragalus tana aerial parts (Leguminosae) 133
3-Rhamnoside-7,4⬘-digalactoside Warburgia ugandensis leaves (Canellaceae) 134
3-Rhamnosyl(1 2)[xylosyl(1 3)rhamnosyl(1 6)galactoside] Astragalus caprinus leaves (Leguminosae) 135
3-(2G-Glucosylrutinoside)-7-rhamnoside Sophora japonica seeds (Leguminosae) 136
3-(6⬙-Galloylgalactoside) Pemphis acidula leaves (Lythraceae) 137
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3-(4⬙-p-Coumaroylglucoside) Elaeagnus bockii whole plant (Elaeagnaceae) 138

3-(6G-Malonylneohesperidoside) Clitoria teratea petals (Leguminosae) 139
3-(2⬙-E-Feruloylgalactosyl)(1 4)glucoside Allium porrum bulbs (Alliaceae) 140
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3-(2⬙-E-Feruloylgalactosyl)(1 6)glucoside
3-(2⬙-E-p-Coumaroyl-α--arabinofuranoside) a Prunus spinosa flowers (Rosaceae) 141
3-(2⬙-E-p-Coumaroyl-6⬙-acetylglucoside) Quercus dentata leaves (Fagaceae) 142
3-(3⬙Acetyl-6⬙-p-coumaroylglucoside) Anaphalis aureo-punctata whole plant (Compositae) 143
3-(3⵮-Acetyl-α--arabinopyranosyl)(1 6)glucoside Thalictrum atriplex aerial parts (Ranunculaceae) 144
3-(6⬙-E-Feruloylglucosyl)(1 2)galactoside Hedyotis diffusa whole plant (Rubiaceae) 145
3-(2⬙,3⬙-Diacetylrhamnoside)-7-rhamnoside Dryopteris crassirhizoma rhizomes (Filicales) 146
3-(2⬙,4⬙-Diacetylrhamnoside)-7-rhamnoside
3-(3⬙,4⬙-Diacetylrhamnoside)-7-rhamnoside
3-(2⬙-E-p-Coumaroyl-α--arabinofuranoside)-7-rhamnoside Prunus spinosa leaves (Rosaceae) 147
3-(6⬙-E-p-Coumaroylglucoside)-7-glucoside Lotus polyphyllus whole plant (Leguminosae) 148
3-Rhamnosyl(1 3)(4⬙-acetylrhamnoside)(1 6)glucoside Camellia sinensis green tea (Theaceae) 128
3-Glucosyl(1 2)(6⬙-acetylgalactoside)-7-glucoside Trigonella foenum-graecum stems (Leguminosae) 149
3-(4⬙-p-Coumaroylglucosyl)(1 2)rhamnoside-7-glucoside Mentha lavandulacea aerial parts (Labiatae) 150
3-(6⬙-p-Coumaroylglucosyl)(1 2)rhamnoside-7-glucoside Mentha lavandulacea aerial parts (Labiatae) 150
3-(6⬙-p-Coumaroylglucosyl)(1 2)rhamnoside-7-glucoside Ginkgo biloba leaves (Ginkgoaceae) 151
3-Glucosyl(1 2)rhamnoside-7-(6-E-p-coumaroylglucoside) Reseda muricata leaves (Resedaceae) 152
3-Glucosyl-7-(6⬙-E-p-coumaroylglucosyl)(1 3)rhamnoside Aconitum napellus ssp. neomontanum flowers 153
(Ranunculaceae)
3-Glucoside-7-(6⬙-E-caffeoylglucosyl)(1 3)rhamnoside
3-(6⬙-E-p-Coumaroylglucosyl)(1 2)glucoside-7-rhamnoside Aconitum napellus ssp. tauricum flowers (Ranunculaceae) 154
3-(6⬙-E-Caffeoylglucosyl)(1 2)glucoside-7-rhamnoside
3-Apioside-7-rhamnosyl(1 6)(2⬙-E-caffeoylgalactoside) Silphium perfoliatum leaves (Compositae) 132
3-Rhamnosyl(1 2)[glucosyl(1 3)(4⵮-p- Lysimachia capillipes whole plant (Primulaceae) 155
coumaroylrhamnosyl)(1 6)galactoside]
3-Rhamnosyl(1 2)[xylosyl(1 3)rhamnosyl(1 6)(3⬙-p- Astragalus caprinus leaves (Leguminosae) 135
coumaroylgalactoside)]
3-Rhamnosyl(1 2)[xylosyl(1 3)rhamnosyl(1 6)(4⬙-p-
coumaroylgalactoside)]
3-Rhamnosyl(1 2)[xylosyl(1 3)rhamnosyl(1 6)(3⬙-
feruloylgalactoside)]
3-Rhamnosyl(1 2)[xylosyl(1 3)rhamnosyl(1 6)(4⬙-
feruloylgalactoside)]
3-Glucosyl(1 6)[rhamnosyl(1 3)(2⬙-E-p-coumaroylglucoside)]- Planchonia grandis leaves (Lecythidaceae) 156
7-rhamnosyl(1 3)rhamnosyl(1 3)(4⬙-E-p-
coumaroylrhamnoside)
3-Glucosyl(1 6)[rhamnosyl(1 3)(2⬙-E-p-coumaroylglucoside)]-
7-rhamnosyl(1 3)rhamnosyl(1 3)(4⬙-Z-p-
coumaroylrhamnoside)
3-Rhamnosyl(1 6)[rhamnosyl(1 3)(2⬙-E-p-coumaroylgluco-
side)]-7-rhamnosyl(1 3)rhamnosyl(1 3)(4⬙-E-p-
coumaroylrhamnoside)
3-Sulfate-7-α-arabinopyranoside Atriplex hortensis leaves (Chenopodiaceae) 157

Kaempferol 3-methyl ether

7-Glucuronide Centaurea bracteata aerial parts (Compositae) 158

Kaempferol 7-methyl ether (rhamnocitrin)

3-Xylosyl(1 2)[ rhamnosyl(1 6)glucoside] Cestrum nocturnum leaves (Solanaceae) 159
3-Neohesperidoside-4⬘-glucoside Cadaba glandulosa aerial parts (Capparidaceae) 160
3-Apiosyl(1 5)apiosyl(1 2)[rhamnosyl(1 6)glucoside] Viscum angulatum whole plant (Viscaceae) 161
3-[3-Hydroxy-3-methylglutaryl(1 6)][apiosyl(1 2)galactoside] Astragalus caprinus leaves (Leguminosae) 126
3-[6⬙-E-3,5-Dimethoxy-4-hydroxycinnamoylglucosyl](1 2)- Cestrum nocturnum leaves (Solanaceae) 159
[rhamnosyl(1 6)glucoside]

554 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3
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Table 5 (Cont’d)

Flavonol glycoside Source Reference

Kaempferol 4⬘-methyl ether

3-Glucosyl(1 2)[rhamnosyl(1 6)glucoside] Dianthus caryophyllus cv. ‘Novada’ leafy stems and roots 162
(Caryophyllaceae)
3-(6⵮-Acetyl-4⬙-O- α-methylsinapoyl)neohesperidoside Aerva tomentosa (Amaranthaceae) 163

Kaempferol 7,4⬘-dimethyl ether

3-Glucoside Gymnotheca involucrata whole plant (Saururaceae) 164

6-Hydroxykaempferol 4⬘-methyl ether

7-Glucoside Serratula strangulata whole plant (Compositae) 165
7-Galactoside

Quercetin
4⬘-Galactoside Cornulaca monacantha aerial parts (Chenopodiaceae) 166
3-α--Arabinofuranosyl(1 2)glucoside Prunus spinosa leaves (Rosaceae) 147
3-Xylosyl(1 2)rhamnosyl(1 6)glucoside Camellia saluenensis leaves (Theaceae) 167
3-Xylosyl(1 6)glucosyl(1 2)rhamnoside Helicia nilagirica leaves (Proteaceae) 127
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3-Rhamnosyl(1 2)glucosyl(1 6)galactoside Cassia marginata stems (Leguminosae) 129

3-Glucosyl(1 2)[rhamnosyl(1 6)galactoside] Thevetia peruviana leaves (Apocynaceae) 168
3-Rhamnosyl(1 2)-α--arabinopyranoside-7-glucoside Putoria calabrica aerial parts (Rubiaceae) 169
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3-Rhamnosyl(1 4)rhamnoside-7-galactoside Maesa lanceolata leaves (Myrsinaceae) 170

3-Glucosyl(1 2)galactoside-7-glucoside Trigonella foenum-graecum stems (Leguminosae) 149
3-Rutinoside-3⬘-apioside Plantago ovata and P. psyllium seeds (Plantaginaceae) 171
3,3⬘,4⬘-Triglucoside Eruca sativa leaves (Cruciferae) 172
3-Xylosyl(1 4)[xylosyl(1 6)glucosyl(1 2)rhamnoside] Helicia nilagirica leaves (Proteaceae) 127
3-Xylosyl(1 3)rhamnosyl(1 6)[apiosyl(1 2)galactoside] Astragalus caprinus leaves (Leguminosae) 126
3-Rhamnosyl(1 6)[glucosyl(1 2)glucoside]-7-rhamnoside Warburgia ugandensis leaves (Rubiaceae) 134
3-(2⬙-Acetylgalactoside) Hypericum perforatum dried crude drug (Guttiferae) 173
3-(4⬙-Malonylrhamnoside) Ribes alpinum leaves (Grossulariaceae) 174
7-(6⬙-Acetylglucoside) Carthamnus tinctorius leaves (Compositae) 175
3-(6G-Malonylneohesperidoside) Clitoria ternatea petals (Leguminosae) 139
3-(2⵮-Galloylglucosyl)(1 2)-α--arabinofuranoside Euphorbia pachyrrhiza (Euphorbiaceae) 176
3-(2⬙-Galloylglucoside)-4⬘-vinylpropionate Psidium guaijava seeds (Myrtaceae) 177
3-Rhamnosyl(1 6)(2⬙-acetylglucoside) Prunus mume flowers (Rosaceae) 178
3-(2⵮-E-Caffeoyl-α--arabinopyranosyl)(1 6)glucoside Morina nepalensis var. alba whole plant (Morinaceae) 179
3-(2⵮-E-Caffeoyl-α--arabinopyranosyl)(1 6)galactoside
3-(6⬙-Caffeoylsophoroside) Bassia muricata aerial parts (Chenopodiaceae) 180
3-(6⬙-Feruloylsophoroside)
3-α--Arabinopyranosyl(1 6)(2⬙-E-p-coumaroylglucoside) Vicia angustifolia leaves and stems (Leguminosae) 181
3-α--Arabinopyranosyl(1 6)(2⬙-E-p-coumaroylgalactoside)
3-(6⬙-E-p-Coumaroylglucoside)-7-glucoside Lotus polyphyllus whole plant (Leguminosae) 148
3-Rutinoside-7-(6⬙-benzoylglucoside) Canthium dicoccum leaves (Rubiaceae) 182
3-(6⬙-E-p-Coumaroylglucosyl)(1 2)glucoside-7-rhamnoside Aconitum napellus ssp. tauricum flowers (Ranunculaceae) 154
3-(4⵮-Caffeoylrhamnosyl)(1 2)-α--arabinopyranoside-7- Putoria calabrica aerial parts (Rubiaceae) 169
glucoside
3-(6⬙-E-Caffeoylglucosyl)(1 2)glucoside-7-rhamnoside Aconitum napellus ssp. tauricum flowers (Ranunculaceae) 154
3-Glucosyl-7-(6⬙-E-caffeoylglucosyl)(1 3)rhamnoside Aconitum napellus ssp. neomontanum flowers 153
(Ranunculaceae)
3-(6⬙-Caffeoylsophoroside)-7-rhamnoside Aconitum baicalense aerial parts (Ranunculaceae) 183
3-(6⬙-E-Sinapoylsophoroside)-7-rhamnoside Elaeagnus lanceolata leaves (Elaeagnaceae) 184
3-(2⬙-Sinapoylglucoside)-3⬘-(6⬙-sinapoylglucoside)-4⬘-glucoside Eruca sativa leaves (Cruciferae) 172
3,4⬘-Diglucoside-3⬘-(6⬙-sinapoylglucoside)
3-Rhamnosyl(1 6)[rhamnosyl(1 2)(3⬙-E-p-coumaroylgalactos- Rhazya orientalis aerial parts (Apocynaceae) 185
ide)]-7-rhamnoside
3-Rhamnosyl(1 6)[rhamnosyl(1 2)(4⬙-E-p-coumaroylgalactos-
ide)]-7-rhamnoside
3-Rhamnosyl(1 2)[glucosyl(1 3)(4⵮-p- Lysimachia capillipes whole plant (Primulaceae) 155
coumaroylrhamnosyl)(1 6)galactoside]
Diquercetin 3-galactoside ester of tetrahydroxy-µ-truxinic acid Monochaetum multiflorum leaves (Melastomataceae) 186
(monochaetin) (81)
3-Sulfate-7-α-arabinopyranoside Atriplex hortenis leaves (Chenopodiaceae) 157
3-Glucoside-3⬘-sulfate Centaurea bracteata aerial parts (Compositae) 158
7,4⬘-Disulfate Alchornea laxiflora whole plant (Euphorbiaceae) 187

Quercetin 3-methyl ether

7-Galactoside(1 4)glucoside Acacia catechu stems (Leguminosae) 188

Quercetin 7-methyl ether (rhamnetin)

3-α--Arabinopyranosyl(1 3)galactoside Pongamia pinnata seeds (Leguminosae) 189
3-α--Arabinopyranosyl(1 3)[galactosyl(1 6)galactoside]
3-[3-Hydroxy-3-methylglutaryl(1 6)][apiosyl(1 2)galactoside] Astragalus caprinus leaves (Leguminosae) 126

N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 555
 View Online

Table 5 (Cont’d)

Flavonol glycoside Source Reference

Quercetin 3⬘-methyl ether (isorhamnetin)

3-Xylosyl(1 2)galactoside Asclepias syriaca flowers (Asclepiadaceae) 180
3-Apiosyl(1 2)glucoside Vernonia galamensis ssp. galamensis var. petitiana whole 191
plant (Compositae)
3-Xylosyl(1 3)rhamnosyl(1 6)glucoside a Hamada scoparia leaves (Chenopodiaceae) 192
3-(2⬙,3⬙,4⬙-Triacetylglucoside) Warburgia stuhlmannii leaves (Canellaceae) 193
3-Rhamnosyl(1 6)(2⬙-acetylglucoside) Prunus mume flowers (Rosaceae) 178
3-(6⬙-p-Coumaroylglucosyl)(1 2)rhamnoside Ginkgo biloba leaves (Ginkgoaceae) 151
3-(6⬙-E-Sinapoylsophoroside) Elaeagnus lanceolata leaves (Elaeagnaceae) 184
3-(6⬙-E-p-Coumaroylglucoside)-7-glucoside Lotus polyphyllus whole plant (Leguminosae) 148
3-Rhamnosyl(1 6)[rhamnosyl(1 2)(3⵮-E-p-coumaroylgalactos- Rhazya orientalis aerial parts (Apocynaceae) 185
ide)]-7-rhamnoside
3-Rhamnosyl(1 6)[rhamnosyl(1 2)(4⬙-p-coumaroylgalactos-
ide)]-7-rhamnoside
3-Rhamnosyl(1 6)[rhamnosyl(1 2)(4⬙-Z-p-
coumaroylgalactoside)]
3-Rhamnosyl(1 6)[rhamnosyl(1 2)(4⬙-E-feruloylgalactoside)]-7-
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rhamnoside

Quercetin 3,4⬘-dimethyl ether

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7-α--Arabinofuranosyl(1 6)glucoside Punica granatum bark (Punicaceae) 194

Quercetin 7,3⬘-dimethyl ether (rhamnazin)

3-Xylosyl(1 2)glucoside Albizzia julibrissin seeds (Leguminosae) 195

Quercetin 5,3⬘,4⬘-trimethyl ether

3-Galactosyl(1 2)rhamnoside-7-rhamnoside Alhagi persarum aerial parts (Leguminosae) 196

6-Hydroxyquercetin 6-methyl ether (quercetagetin 6-methyl ether,

patuletin)
3-(6⬙-E-Feruloylglucoside) Paepalanthus polyanthus aerial parts (Eriocaulaceae) 197

Quercetagetin 3,6-dimethyl ether (axillarin)

5-α--Arabinosyl(1 6)glucoside Acacia catechu stems (Leguminosae) 198
7-Sulfate Centaurea bracteata roots (Compositae) 199

8-Hydroxyquercetin (gossypetin)
8-α--Lyxopyranoside Orostachys japonicus aerial parts (Crassulaceae) 200

Gossypetin 3,8-dimethyl ether

5-Glucoside Eugenia edulis leaves (Myrtaceae) 201

Myricetin
3-Xylosyl(1 3)rhamnoside Maesa lanceolata leaves (Myrsinaceae) 170
3-Neohesperidoside Physalis angulata leaves (Solanaceae) 202
3-(2G-Rhamnosylrutinoside) Clitoria ternatea petals (Leguminosae) 139
3-(2⬙-p-Hydroxybenzoylrhamnoside) Limonium sinense aerial parts (Plumbaginaceae) 203
3-(2⬙-Galloylglucoside) Geranium pratense aerial parts (Geraniaceae) 204
3-(4⬙-Acetylrhamnoside) Eugenia jambola leaves (Myrtaceae) 205
3-(4⬙-Malonylrhamnoside) Ribes alpinum leaves (Grossulariaceae) 174
3-(6⬙-p-Coumaroylglucoside) Nymphaea lotus leaves (Nymphaeaceae) 206
3-(2⬙,3⬙,4⬙-Triacetylxyloside) Maesa lanceolata leaves (Myrsinaceae) 170
3-(4⬙-Acetyl-2⬙-galloylrhamnoside) Eugenia jambolana leaves (Myrtaceae) 207
3-(3⵮,6⵮-Diacetylglucosyl)(1 4)(2⬙,3⬙-diacetylrhamnoside) Maesa lanceolata leaves (Myrsinaceae) 170
Nympholide A (82) Nymphaea lotus leaves (Nymphaceae) 206
Nympholide B (83)

Myricetin 3⬘-methyl ether (larycitrin)

3-(4⬙-Malonylrhamnoside) Ribes alpinum leaves (Grossulariaceae) 174

Myricetin 4⬘-methyl ether (mearnsetin)

3-(4⬙-Acetylrhamnoside) Eugenia jambolana leaves (Myrtaceae) 207

Myricetin 3⬘,4⬘-dimethyl ether

3-Rhamnoside Clausena excavata aerial parts (Rutaceae) 208

Myricetin 3⬘,5⬘-dimethyl ether (syringetin)

3-(2⬙,3⬙-Diacetylglucoside) Warburgia stuhlmannii leaves (Canellaceae) 193

3,7,3⬘,4⬘,5⬘-Pentahydroxyflavone (5-deoxymyricetin)
3-Rutinoside Ateleia herbert-smithii leaves (Leguminosae) 209

3,4⬘-Dihydroxy-7,3⬘,5⬘-trimethoxyflavone
3-Galactosyl(1 4)xyloside Abrus precatorius seeds (Leguminosae) 210

556 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3

Table 5 (Cont’d)
Flavonol glycoside
5,7,2⬘-Trihydroxy-3,6,4⬘-trimethoxyflavone
7-Glucoside
5,2⬘,4⬘-Trihydroxy-3,7,5⬘-trimethoxyflavone
2⬘-Galactosyl(1 4)glucoside
3,5,2⬘-Trihydroxy-7,8,4⬘-trimethoxyflavone
5-Glucosyl(1 2)galactoside
5,7,2⬘,3⬘,4⬘-Pentahydroxy-3,6-dimethoxyflavone
7-Glucoside
Methylenedioxyflavonol glycosides
5-Hydroxy-3-methoxy-6,7-methylenedioxyflavone
4⬘-Glucuronide
Published on 07 July 2004 on http://pubs.rsc.org | doi:10.1039/B311404J
3-Hydroxy-5,4⬘-dimethoxy-6,7-methylenedioxyflavone
3-Xyloside (viviparum A)
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3,3⬘-Dihydroxy-5,4⬘-dimethoxy-6,7-methylenedioxyflavone
3-Xyloside (viviparum B)
a
Linkage not previously given.
Table 6 New branched trisaccharides of flavone glycosides a
Structure
O-α-Rhamnosyl(1 2)-O-[α-rhamnosyl(1 6)galactose] b
O-β-Glucosyl(1 2)-O-[α-rhamnosyl(1 6)glucose] b c
O-β-Apiosyl(1 2)-O-[β-glucosyl(1 4)glucose] d e
O-β-Glucuronosyl(1 3)-O-[β-glucuronosyl(1 2)glucuronic acid] d f
a
Except where otherwise indicated sugars are assumed to be in the pyranose form and to have the appropriate linkage i.e. β for glucose, α for
rhamnose etc. b Previously only found attached to flavonols. c Only present with an acetyl group at the 6-hydroxyl of the second glucose. d Newly
discovered during the period 2001–2003. e Only present with a malonyl group at the 6-hydroxyl of the first glucose. f Only present with a p-coumaroyl
or feruloyl group at the 2-hydroxyl of the second glucuronic acid moiety.
Nine other novel trisaccharides, seven linear and two
branched structures, which have been found combined with
flavonols during the review period, are listed in Table 7. The
most unusual structures are four linear trisaccharides with
xylose as the terminal sugar. Thus, xylosyl(1 3)rhamnosyl-
(1 6)galactose and xylosyl(1 6)glucosyl(1 2)rhamnose
were both found in combination with kaempferol at the
3-hydroxyl, the former from leaves of Astragalus caprinus
(Leguminosae) 126 and the latter from leaves of Helicia nilagirica
(Proteaceae).127 Xylose has not been recorded in a linear
trisaccharide in any of the previous reviews of flavone and
flavonol glycosides and 2-xylosylrutinose is the only previously
known branched xylose-containing trisaccharide. The other
two new structures are xylosyl(1 2)rhamnosyl(1 6)glucose
found at the 3-hydroxyl of quercetin in leaves of Camellia
saluensis (Theaceae) 167 and xylosyl(1 3)rhamnosyl(1 6)-
glucose isolated from leaves of Hamada scoparia (Chenopodi-
aceae) 192 at the 3-hydroxyl of isorhamnetin. The first ever
reported trirhamnose, rhamnosyl(1 3)rhamnosyl(1 3)-
rhamnose, acylated with p-coumaric acid on the first rhamnose,
has been found at the 7-hydroxyl of kaempferol with an acyl-
ated known branched trisaccharide, glucosyl(1 6)[rhamno-
syl(1 3)(2⬙-E-p-coumaroylglucose)] at the 3-position, in leaves
of Planchonia grandis (Lecythidaceae).156 Two other acylated
kaempferol 3-trioside-7-triosides containing known trisac-
charides were found in the same tissue. The previous maximum
number of sugars in any flavonol glycoside has been four,
so these findings are of some significance. The remaining two
linear trisaccharides, rhamnosyl(1 3)rhamnosyl(1 6)glucose
View Online
Source Reference
Tridax procumbens whole plant (Compositae) 211
Albizzia procera stems (Leguminosae) 212
Cassia occidentalis whole plant (Leguminosae) 213
Tridax procumbens aerial parts (Compositae) 88
Spinacia oleracea leaves (Chenopodiaceae) 214
Polygonum viviparum (Polygonaceae) 215
Polygonum viviparum (Polygonaceae) 215
Trivial name Reference
2-Rhamnosyl robinobioside 107
2-Glucosylrutinose 108
2G-Apiosylcellobiose 117
102, 118
from green tea (Camellia sinsensis) 128 and rhamnosyl(1 2)-
glucosyl(1 6)galactose from Cassia marginata (Legumin-
osae),129 both in combination with kaempferol at the 3-hydroxyl
and the latter also in combination with quercetin, represent new
linkages of previously known structures.
The only new branched trisaccharide is the 3-isomer of the
known 2G-glucosylgentiobiose. However, it is unusual in that it
has been reported at the 7-hydroxyl of kaempferol in leaves of
Brassica juncea (Cruciferae).130 There are no previous examples
of flavonol 7-triosides so this finding needs careful checking,
especially as the plant also contains two 3,7-diglycosides
containing three sugars, kaempferol 3-(2⵮-feruloylglucosyl)-
(1 2)glucoside-7-glucoside and kaempferol 3-glucosyl(1 2)-
glucoside-7-glucoside. The data given in the reference suggest a
slight sodium acetate shift in the UV spectrum of the 7-trioside
from 268 to 271 nm, whereas a 7-glycoside should give no shift.
Also, there is no indication of the colour of the compound in
UV light. A 3,7- disubstituted glycoside would appear dark
absorbing and change to bright yellow with NH3 vapour, while
a 7-glycoside would appear bright yellow before fuming with
NH3.
There are five recent reports of new branched tetra-
saccharides attached to flavonols (see Table 7), bringing the
total number of known structures to nine. Two of the new
molecules have xylose as the terminal sugar and both were
found attached to the 3-hydroxyl of quercetin, namely,
xylosyl(1 3)rhamnosyl(1 6)[apiosyl(1 2)galactose] from
leaves of Astragalus caprinus 126 and xylosyl(1 4)[xylosyl-
(1 6)glucosyl(1 2)rhamnose] from leaves of Helicia
N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 557

Table 7 New tri- and tetrasaccharides of flavonol glycosides a
Structure Reference
Linear trisaccharides
O-β-Xylosyl(1 2)-O-α-rhamnosyl(1 6)glucose 167
O-β-Xylosyl(1 3)-O-α-rhamnosyl(1 6)glucose 192
O-β-Xylosyl(1 6)-O-β-glucosyl(1 2)rhamnose 129
O-β-Xylosyl(1 3)-O-α-rhamnosyl(1 6)galactose 126
O-α-Rhamnosyl(1 3)-O-α-rhamnosyl(1 3)rhamnose b 156
O-α-Rhamnosyl(1 3)-O-α-rhamnosyl(1 6)glucose 128
O-α-Rhamnosyl(1 2)-O-β-glucosyl(1 6)galactose 129
Branched trisaccharides
O-α--Arabinopyranosyl(1 3)-O-[β- 189
galactosyl(1 6)galactose]
O-β-Glucosyl(1 3)-O-[β-glucosyl(1 6)glucose] 130
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Branched tetrasaccharides
O-β-Apiosyl(1 5)-O-β-apiosyl(1 2)-O-[α- 161
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rhamnosyl(1 6)glucose]
O-β-Xylosyl(1 3)-O-α-rhamnosyl(1 6)-O-[β- 126
apiosyl(1 2)galactose]
O-β-Xylosyl(1 4)-O-[β-xylosyl(1 6)-O-β- 127
glucosyl(1 2)rhamnose]
O-α-Rhamnosyl(1 2)-O-[β-xylosyl(1 3)-O-α- 135
rhamnosyl(1 6)galactose]
O-α-Rhamnosyl(1 2)-O-[β-glucosyl(1 3)-O-α- 155
rhamnosyl(1 6)galactose] c
a
Newly discovered during the period 2001–2003. b Attached at the 7-
hydroxyl of kaempferol with a p-coumaroyl group at the 4-hydroxyl of
the first rhamnose and with an additional trisaccharide attached to the
3-position of the aglycone. c Only present with a p-coumaroyl group at
the 4-hydroxyl of the first rhamnose.
nilagirica.127 Both tetrasaccharides co-occur with related new
trisaccharides (see above). Another tetrasaccharide, apiosyl-
(1 5)apiosyl(1 2)[rhamnosyl(1 6)glucoside], is unique in
that it contains two linked apiose moieties. It was isolated,
in combination with kaempferol 7-methyl ether (rhamnocitrin)
at the 3-position, from a whole plant extract of a mistletoe,
Viscum angulatum (Viscaceae).161 There is no previous record
of a diapiose either as a bioside or within a tri- or tetra-
saccharide. The remaining two conjugates were both
found attached to the 3-hydroxyl of kaempferol i.e.
rhamnosyl(1 2)[xylosyl(1 3)rhamnosyl(1 6)galactose] in
leaves of Astragalus caprinus 135 and the acylated rhamnosyl-
(1 2)[glucosyl(1 3)(4⬙-p-coumaroylrhamnosyl)(1 6)galac-
tose], together with the corresponding quercetin glycoside, in a
whole plant extract of Lysimachia capillipes (Primulaceae).155
Five new flavonol and two new flavone sulfates have been
recorded. Kaempferol and quercetin 3-sulfate-7-α-arabino-
pyranosides and quercetin 3-glucoside-3⬘-sulfate have been
isolated from leaves of the salt-tolerant plant, Atriplex hortensis
(Chenopodiaceae) 157 and quercetin 7,4⬘-disulfate from
Alchorrea laxiflora.187 The flavone sulfates, 8-hydroxyapigenin
(isoscutellarein) and isoscutellarein 4⬘-methyl ether 8-(2⬙,4⬙-
disulfatoglucuronide), are fruit constituents of Helicteres isora
(Sterculiaceae).111
It is interesting that more than half of all the new flavone and
flavonol glycosides reported between the years 2001–03 have
acylated structures (31 flavones and 87 flavonols). This
must reflect the greater availability of sophisticated MS and
NMR instrumentation. Two new acylating acids were found
in association with flavonol glycosides during this period,
α-methylsinapic acid and vinylpropionic acid. Thus,
kaempferol 4⬘-methyl ether 3-neohesperidoside has been
reported, with an α-methylsinapoyl group at the 4-hydroxyl of
the glucose and with an acetyl group at the 6-hydroxyl of the
rhamnose, from Aerva tomentosa (Amaranthaceae).163 In seeds
558 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3
View Online
of Psidium guaijava (Myrtaceae) 177 vinylpropionic acid has
been found directly attached to the 4⬘-hydroxyl of quercetin
3-(2⬙-galloylglucoside) without an intervening sugar molecule.
Of note is the second report of the lignan, µ-truxillic acid, in a
new biflavonol glycoside, monochaetin (81), in which two
molecules of quercetin 3-galactoside (hyperin) are attached
through the 6-hydroxyls of the two sugar moieties to the
carboxyl groups of 3,3⬘,4,4⬘-tetrahydroxy-µ-truxinic acid.
Monochaetin was isolated from a leaf extract of the Columbian
species, Monochaetum multiflorum (Melastomataceae).186 The
previous report of µ-truxillic acid was in the diflavone glycoside,
stachysetin (84), from Stachys aegyptica,218 in which two
molecules of apigenin 7-glucoside were found linked to
the carboxyl groups of p,p⬘-dihydroxytruxillic acid at the
6⬙-positions of the glucose molecules. Only two other diflav-
onoid esters of dicarboxylic acids have been reported
previously. These are sudachiin D from the green fruit peel of
Citrus sudachii,219 in which sudachitin (5,7,4⬘-trihydroxy-6,8,3⬘-
trimethoxyflavone) 4⬘-glucoside and sudachitin 7-glucoside are
connected by an ester linkage at their 6⬙-positions with 3-
hydroxy-3-methylglutaric acid, and a flavone from Agastache
rugosa (Labiatae),220 which has two molecules of acacetin
7-glucoside substituting a malonic acid residue. Two unusual
novel macrocyclic myricetin derivatives, nympholides A and B
(82,83), have been characterised recently from the water lily,
Nymphaea lotus,205 together with their probable previously
unknown precursor, myricetin 3⬘-(6⬙-p-coumaroylglucoside). In
both macrocyclic structures the p-coumaroyl double bond has
been replaced by a three proton saturated system and one of
the A-ring protons of the flavonol has disappeared so that
the p-coumaroyl moiety is attached through C3⵮ to C8 of the
myricetin as well as the 6⬙-position of the glucose. The stereo-
chemistry at position 3⵮- was determined as S in nympholide
A and as R in nympholide B.
Only three new glycosides were found to show biological
activity that related to their presence within the plant tissue.
Thus, two acylated flavonol glycosides, quercetin 3-α--arab-
inosyl(1 6)(2⬙-p-coumaroylglucoside) and quercetin 3-α--
arabinosyl(1 6)(2⬙-p-coumaroylgalactoside) were isolated as
the specific probing stimulants of a bean aphid, Megoura
crassicauda, from the leaf and stem of Vicia angustifolia.181 This
aphid feeds selectively on Vicia species such as the broad bean
(Vicia faba) and the narrowleaf vetch (Vicia angustifolium),
often causing serious damage to the plants. A new flavonol 3-
trioside, kaempferol 4⬘-methyl ether 3-glucosyl(1 2)[rhamno-
syl(1 6)glucoside], which has been shown to have significant
fungitoxic activity towards Fusarium oxysporum f. sp. dianthi
conidia germination, has been identified in uninfected plants of
the carnation, Dianthus caryophyllus cv. Novada.162 Its effective
in vitro concentration in the plant (3.9 µmol g⫺1 in the stem and
0.8 µmol g⫺1 in the roots) could explain the high resistance of
the cultivar Novada to this Fusarium species.
Amongst the new glycosides with a potential medicinal use is
a cytotoxic flavonol glycoside, myricetin 3-neohesperidoside,
 View Online

which has been isolated from leaves of Physalis angulata.202 5 Chalcones, dihydrochalcones and aurones
This glycoside showed remarkable cytotoxicity in vitro against New chalcones, dihydrochalcones and aurones reported during
murine leukemia cell line P-388, epidermoid carcinoma of the the 2001–2003 period are listed in Table 8.74,221–250 This table
nasopharynx KB-16 cells and lung adenocarcinoma A-549 with also includes a few structures reported at the end of 2000 and
ED50 values of 0.048, 0.50 and 0.55 µg ml⫺1, respectively. Two missed during the previous review. The list comprises 36 chalcones,
new acetylated flavonol glycosides from the flowers of Prunus 11 dihydrochalcones and two aurones. Nearly half of the new
mume 178 were found to inhibit aldose reductase, a key enzyme compounds contain isoprenyl or dimethylpyrano ring struc-
in the polyol pathway, which catalyzes the reduction of glucose tures, eleven are biflavonoids or oligoflavonoids and ten are
to sorbitol. The intercellular accumulation of sorbitol, which glycosides.
does not readily diffuse across cell membranes, has been
implicated in complications of diabetes such as cataract. Of the
two glycosides, isorhamnetin 3-(2G-acetylrutinoside) showed
the most potent inhibition of rat lens aldose reductase with an
IC50 of 9.8 µM compared with 18 µM for the corresponding
quercetin glycoside, 2⬙-acetylrutin. Three novel acetylated
kaempferol glycosides from the rhizomes of the fern Dryopteris
crassirhizma 146 were tested for their inhibitory effects on three
different activities of HIV Virus-1 reverse transcriptase. Two
of the compounds, kaempferol 3-(2⬙,3⬙-diacetylrhamnose)-7-
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rhamnoside and its 2⬙,4⬙-diacetyl isomer, inhibited DDDP

(DNA-dependent DNA polymerase) with IC50 values of 25 and
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28 µM, respectively but showed only moderate inhibition of

RDDP (RNA-dependent DNA polymerase) (IC50 values, 215
and 240 µM, respectively). The third glycoside, the 3⬙,4⬙-di-
acetyl isomer was inactive in both assays and all three showed
no inhibition of RNase activity at concentrations below
500 µM.
However, the most frequent biological tests carried out on
new flavonoid constituents are those to detect and evaluate
antioxidant activity. Flavonoids have been shown to act as
scavengers of various oxidising species such as superoxide
anion (O2 ⫺ⴢ), peroxyl and hydroxyl radicals and may also act
as quenchers of singlet oxygen. As flavonoids do not react
specifically with a single oxygen species, a number of different
evaluation methods are used, which can make comparison of
data from different studies difficult. One of the frequently used
methods, the DPPH (1,1-diphenyl-2-picrylhydrazyl) assay,
revealed significant antioxidant activity with an IC50 value of
8.4 µg ml⫺1 (compared with an IC50 = 1.9 µg ml⫺1 for -ascorbic
acid) for the new flavonol triglycoside, kaempferol 7-(3G-gluco-
sylgentiobioside) isolated from leaves of Brassica juncea.130 The
antiradical activity of galloylated flavonol glycosides from
leaves of Pemphis acidulata,137 a plant of the seashore, was also
measured by the DPPH method and the results compared with
those for the equivalent non-galloylated flavonol glycosides.
The galloyl derivatives, including the newly reported
kaempferol 3-(6⬙-galloylgalactoside), all showed very strong
radical scavenging activity with higher efficiency than the non-
galloylated glycosides, but not so efficient as the corresponding
aglycone. Again, amongst the galloyl flavonoids, quercetin
glycosides showed stronger activity than the kaempferol
derivatives, indicating the importance of a catechol grouping in
the B-ring in enhancing the antioxidant activity. Two further
acylated flavonol glycosides from the leaves of the maiden-
hair tree (Ginkgo biloba),150 the 3-(6⬙-p-coumaroylglucosyl)-
(1 2)rhamnosides of isorhamnetin and kaempferol, were
shown to exhibit strong free radical scavenging activity in
the DPPH assay and also inhibitory activity comparable with
the positive control against TPA-induced free radical formation
in an HL-60 cell culture system. The antioxidant activity
of some flavonol glycoside constituents of Carthamnus
tinctorius 175 was tested using hydroxyl radical-induced 2-deoxy-
ribose degradation and lipid peroxidation of rat liver. The
damage caused by the high and indiscriminate activity of free
hydroxyl (OHⴢ) radicals can be modulated by dietary anti-
oxidant flavonoids. Among the Carthamnus flavonoids tested
two acetylated glycosides, luteolin 7-(6⬙-acetylglucoside) and
the new glycoside quercetin 7-(6⬙-acetylglucoside), showed the
most potent antioxidative activities in both in vitro model
systems.175

N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 559
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Table 8 Chalcones, dihydrochalcones and aurones reported in the period 2001–2003

Compound a Source Reference

CHALCONES
2⬘-Hydroxy-2,4⬘,6⬘-trimethoxychalcone Andrographis lineata whole plant (Acanthaceae) 221
2⬘-Hydroxy-3,4,5-trimethoxychalcone (crotaoprostin) Crotalaria prostrata aerial parts (Leguminosae) 222
2⬘-Hydroxy-2,3,4⬘,6⬘-tetramethoxychalcone Caesalpinia pulcherrima aerial parts (Leguminosae) 223
2⬘-Hydroxy-3,4,3⬘,4⬘,6⬘-pentamethoxychalcone Citrus kinokuni peel (Rutaceae) 224
2,3,4,2⬘,4⬘,6⬘-Hexamethoxychalcone Andrographis neesiana whole plant (Acanthaceae) 225
3,4-Methylenedioxy-2⬘,4⬘-dimethoxychalcone Millettia erythrocalyx roots (Leguminosae) 226
5⬘-Bromo-2⬘-hydroxy-4,4⬘,6⬘-trimethoxychalcone Garcinia nervosa leaves (Guttiferae) 227
Epoxyobovatachalcone (85) Tephrosia carrollii (Leguminosae) 228
β,2⬘,6⬘-Trihydroxy-3⬘-prenyl-4⬘-methoxychalcone (86) Tephrosia major (Leguminosae) 229
Licoagrochalcones B, C, D (87–89) Glycyrrhiza glabra hairy root culture (Leguminosae) 230
6⬘-Hydroxy-2⬘,4-dimethoxylonchocarpin (90) Lonchocarpus xuul leaves, Lonchocarpus yucatanensis leaves 74
(Leguminosae)
Artoindonesianin J (91) Artocarpus bracteata root and tree bark (Moraceae) 231
3,4,2⬘,4⬘-Tetrahydroxy-5,3⬘-digeranylchalcone (92) Dorstenia prorepens twigs (Moraceae) 232
4,2⬘,5⬙-Trihydroxy-6⬙,6⬙-dimethyldi- Dorstenia zenkeri twigs (Moraceae) 232
hydropyrano[2⬙,3⬙:4⬘,3⬘]chalcone (93)
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Diels–Alder adduct 94 (dimeric)

4,2⬘,4⬘-Trihydroxy-3⬘-[2⬙-hydroxy-3⬙-methylbut-3⬙-enyl]chalcone Maclura tinctoria leaves (Moraceae) 233
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(95)
2⬘-Hydroxy-4,4⬘-dimethoxy-6⬙,6⬙-di- Neoraputia magnifica fruits (Rutaceae) 234
methylpyrano[2⬙,3⬙:6⬘,5⬘]chalcone (96)
2⬘-Hydroxy-3,4,4⬘-trimethoxy-6⬙,6⬙-di-
methylpyrano[2⬙,3⬙:6⬘,5⬘]chalcone (97)
Cedreprenone (98) Cedrelopsis grevei seeds (Ptaeroxylaceae) 235
Cedrediprenone (99)
2⬘,4⬘-Dihydroxy-3⬘-C-(2,6-dihydroxybenzyl)-6⬘-methoxychalcone Desmos chinensis (Annonaceae) 236
(100)

DIMERIC OR OLIGOMERIC CHALCONES

Rhuschalcones II–VI (102–106) Rhus pyroides root bark (Anacardiaceae) 237
Ochnachalcone (107) Ochna calodendron (Ochnaceae) 238
Azobechalcone (108) Lophira alata (Ochnaceae) 239

CHALCONE GLYCOSIDES
Chalconaringenin 2⬘,4⬘-diglucoside Asarum canadense leaves (Aristolochiaceae) 240
Chalconaringenin 2⬘-glucoside-4⬘-gentiobioside
2,2⬘,6⬘-Trihydroxy-4⬘-methoxychalcone 2⬘-glucoside Andrographis echioides (Acanthaceae) 241
(androechin)
4,2⬘,3⬘,4⬘-Tetrahydroxychalcone 4⬘-(2-p-coumaroylglucoside) Maclura tinctoria (Moraceae) 242
4,2⬘,3⬘,4⬘-Tetrahydroxychalcone 4⬘-(2-p-coumaroyl-6-
acetylglucoside)
4,2⬘,4⬘-Trihydroxychalcone 3⬘-prenyl-4⬘-glucoside (109)

DIHYDROCHALCONES
(⫺)-Hydroxypanduratin A (110) Boesenbergia pandurata rhizome (Zingiberaceae) 243
(±)-Nicolaioidesins A, B and C (111–113) Renealmia nicolaioides roots (Zingiberaceae) 244
2⬘-Hydroxy-4⬘-methoxy-2⬙-[2-hydroxy-5-methoxycarb- Piper longicaudatum (Piperaceae) 245
onylphenyl]-furano[4⬙,5⬙:5⬘,6⬘]dihydrochalcone
(longicaudatin) (114)

DIMERIC DIHYDROCHALCONES
Cycloaltilisin 6 (115) Artocarpus altilis bud covers (Moraceae) 246
Dihydrolophirone C (116) Ochna afzelii stem bark (Ochnaceae) 247
Isolophirone C (117)

DIHYDROCHALCONE GLYCOSIDES
4-Hydroxy-2⬘,4⬘,6⬘-trimethoxydihydrochalcone 4-glucoside Bidens bipinnata aerial parts (Compositae) 248
(bidenoside B)
α,4,2⬘,4⬘-Tetrahydroxydihydrochalcone α-O-β-glucoside Glycyrrhiza pallidiflora hairy root culture (Leguminosae) 249
(licoagroside F) (118)
Phloretin 3⬘,5⬘-di-C-glucoside (119) Fortunella spp. leaves and fruits (Rutaceae) 250

AURONES
Licoagroaurone (120) Glycyrrhiza glabra hairy root culture (Leguminosae) 230
(Z )-6,7,3⬘,4⬘-Tetrahydroxyaurone 6-(3,6-di-acetylglucoside) Bidens pipinnata aerial parts (Compositae) 248
(bidenoside A)
a
Prenyl = 3,3-dimethylallyl. In the glycosides, the linkages between flavonoid aglycones and sugars, and between sugars and other sugars or acyl
groups, are all -O-, unless specified as -C-. Sugars are all in the pyranose form. Sugar linkages are β for glucose. Where hydroxycinnamic acids are the
acyl groups, they are assumed to be in the E-form.

560 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3
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Just six new simple chalcones, containing only hydroxy and
methoxy substituents, have been described in the last three
years, from species of Andrographis 221,225 (Acanthaceae), three
legumes (Crotalaria prostrata,222 Caesalpinia pulcherrima 223
and Millettia erythrocalyx 226) and Citrus kinokuni (Rutaceae) 224
(see Table 8). Additionally a halogenated simple chalcone,
5⬘-bromo-2⬘-hydroxy-4,4⬘,6⬘-trimethoxychalcone, has been
reported from Garcinia nervosa (Guttiferae).227 New prenylated
chalcones were discovered in species belonging to only four
different plant families: the Leguminosae (6 new structures),
Moraceae (4), Rutaceae (2) and Ptaeroxylaceae (2). The prenyl-
ated legume chalcones include epoxyobovatachalcone (85),
which was isolated from Tephrosia carrollii (formerly called
T. woodii).228 The known obovatachalcone (6⬘-hydroxy-2⬘-
methoxy-6⬙,6⬙-dimethylpyrano[2⬙,3⬙:4⬘,3⬘]chalcone) was also
obtained from the same plant extract. The 1H NMR data
obtained for this obovatachalcone could not be distinguished
from those reported for the compound öaxacacin, which was
isolated from the same species, but which was previously
identified as 2⬘-hydroxy-6⬘-methoxy-6⬙,6⬙-dimethylpyrano-
[2⬙,3⬙:4⬘,3⬘]chalcone. Single X-ray crystallographic analysis
confirmed that the structure of the compound is that of
obovatachalcone and not that proposed for öaxacacin.228
From another species of Tephrosia, T. major (Leguminosae), a
new β-hydroxychalcone was isolated (86).229 Previously only
seven prenylated β-hydroxychalcones have been described, so
they are rather rare natural products.229
Many different medicinal properties have been attributed to
the roots and stolons of Glycyrrhiza glabra (licorice, fam.
Leguminosae), and the activities seem to be mainly due to
saponins and flavonoids.230 More than 300 flavonoids have
already been reported from this species, and now hairy root
cultures are yielding even more novel structures, including three
prenylated chalcones, licoagrochalcones B, C and D (87–89).230
Another legume genus that is a good source of unusual
flavonoids is Lonchocarpus. Leaves, stem bark and roots of
L. xuul and L. yucatanensis yielded the new prenylated chal-
cone, 6⬘-hydroxy-2⬘,4-dimethoxylonchocarpin (90).74
The presence of isoprenylated flavonoids is also a feature
of the genus Artocarpus (Moraceae). The new isoprenylated
chalcone, artoindonesianin J (91), was isolated from the root
and tree bark of A. bracteata.231 The two prenyl groups in this
compound form dimethylpyrano rings with neighbouring
phenolic hydroxyl groups. The new digeranylated chalcone
92 was obtained from another species of the Moraceae,
Dorstenia prorepens, whereas from the related D. zenkeri the
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novel dimethyldihydropyranochalcone 93 and the Diels–Alder
adduct 94 were isolated.232 The dimeric compound 94 is
thought to be derived from a cycloaddition reaction between
two prenylated chalcones.232 A chalcone with a hydroxylated
prenyl group (95) was found in the leaves of Maclura tinctoria,
which belongs to the same family.233
Several new chalcones and flavanones have been isolated
from the fruits of Neoraputia magnifica var. magnifica (fam.
Rutaceae), including 2⬘-hydroxy-4,4⬘-dimethoxy-5⬘,6⬘-(2⬙,2⬙-
dimethylpyrano)chalcone (96) and its 3-methoxy derivative
(97).234 The seeds of Cedrelopsis grevei (fam. Ptaeroxylaceae)
have yielded the new prenylated chalcones, cedreprenone (98)
and cedrediprenone (99).235 Cedrediprenone was found to
inhibit luminol-enhanced chemiluminescence of reactive
oxygen metabolites generated by human polymorphonuclear
leucocytes activated with opsonized zymosan, and to scavenge
superoxide anions in a cell free system. This suggests anti-
inflammatory activity.235 The relationships of the family
Ptaeroxylaceae were uncertain until recently, but it is now
thought to be close to families in the order Rutales (e.g.
Rutaceae, Meliaceae and Cneoraceae). The occurrence of
isoprenylated chalcones of similar structure (and also of iso-
prenylated flavanones, see below) in both the Ptaeroxylaceae
and Rutaceae supports this opinion.
More than a dozen different C-benzylated dihydrochalcones
and flavanones have already been described from species of the
genus Uvaria (fam. Annonaceae).251 Now in a different genus of
the Annonaceae, Desmos, the first C-benzylated chalcone has
been detected. It was isolated from the Chinese medicinal plant
D. chinensis and identified as 2⬘,4⬘-dihydroxy-3⬘-C-(2,6-di-
hydroxybenzyl)-6⬘-methoxychalcone (100).236
Production of biflavonoids is a characteristic feature of
gymnosperms, but biflavonoid compounds have been reported
also from a number of angiosperm families. For example,
several biflavones and biflavanones are known to occur in Rhus
succedanea belonging to the family Anacardiaceae.251 Six new
bichalcones have been isolated from the root bark of another
Rhus species, R. pyroides, the known rhuschalcone I (101) and
the new rhuschalcones II, III, IV, V and VI (102–106).237 In
rhuschalcones I–III (101–103) the two chalcone units are
connected via an ether link between C-4 of one of the units and
C-5⬘ of the other. In rhuschalcone IV (104), they are connected
via an ether linkage between C-4⬘ and C-5⬘, whereas in
rhuschalcones V and VI (105,106) there are carbon–carbon
connections between C-3 and C-5⬘ of the two units. Rhuschal-
cone V (105) is a dimer of a chalcone and a dihydrochalcone.
All rhuschalcones were found to be active on colon cancer lines,
especially HT29 and HCT-116. Rhuschalcones V and VI (with
C–C bonds between the units) were the least active of the six
compounds, whereas rhuschalcone IV was the most active and
also showed activity on melanoma cell lines.237
Another angiosperm family rich in biflavonoids is the
Ochnaceae and several bichalcones have already been reported
from the genera Ochna and Lophira.251 Now a pentaflavonoid,
ochnachalcone (107), has been isolated from the stem bark of
Ochna calodendron (Ochnaceae), and its structure elucidated by
spectroscopic means including HSQC, HMBC and ROESY
experiments.238 It is built up from two bichalcones, which are
connected via the flavan-3-ol, afzelechin. A novel hexachalcone,
azobechalcone (108), was isolated from the methanol extract
of the stem bark of Lophira alata, another member of the
Ochnaceae.239 Detailed analysis of the COSY LR 1H NMR
spectra of 108 indicated that three biflavonoid substructures
were present, all of which were similar to bichalcones pre-
viously isolated from Ochnaceae species.
Table 8 presents six new chalcone glycosides: the 2⬘,4⬘-di-O-
glucoside and 2⬘-O-glucoside-4⬘-O-gentiobioside of chalco-
naringenin (4,2⬘,4⬘,6⬘-tetrahydroxychalcone) from Asarum
canadense (Aristolochiaceae),240 the 2⬘-O-glucoside of 2,2⬘,6⬘-
trihydroxy-4⬘-methoxychalcone (androechin) from Androgra-
N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 563
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phis echioides (Acanthaceae),241 the 4⬘-O-(2-O-p-coumaroyl-
glucoside) and 4⬘-O-(2-O-p-coumaroyl-6-O-acetylglucoside)
of 4,2⬘,3⬘,4⬘-tetrahydroxychalcone from Maclura tinctoria
(= Chlorophora tinctoria) (Moraceae) and 4,2⬘,4⬘-trihydroxy-3⬘-
prenylchalcone-4⬘-O-glucoside (109) from the same plant
species.242 The antioxidant activity of the chalcone glycosides
of M. tinctoria was measured, using the trolox equivalent anti-
oxidant capacity assay and the coupled oxidation of β-carotene
and linoleic acid (autoxidation assay). All the chalcone glyco-
sides were more active than the flavanone naringenin and
glycosides of naringenin and eriodictyol isolated from the same
plant, but the prenylated chalcone glycoside 109 was the most
active compound in both assays.242
Most of the new dihydrochalcones reported were obtained
from bioactive fractions by activity-guided fractionations. The
new prenylated cyclohexenyl dihydrochalcone, (⫺)-hydroxy-
panduratin A (110), was isolated from the chloroform extract
of the red rhizome of Boesenbergia pandurata (= B. rotunda)
(fam. Zingiberaceae).243 This compound and the known (⫺)-
Published on 07 July 2004 on http://pubs.rsc.org | doi:10.1039/B311404J
F. polyandra and F. hindsii.250 The genus Fortunella is closely
related to Citrus, but none of the Fortunella species were found
to produce flavanone glycosides such as narirutin, which are the
main flavonoid constituents in citrus fruits. In turn, a large
number of Citrus species were examined for the presence of the
new dihydrochalcone glycoside. It was shown to be absent from
27 Citrus species, but present in C. madurensis and C. halimii
and also in seven hybrids between species of Citrus and
Fortunella. These results suggest that accumulation of the
dihydrochalcone is a genetic trait of the genus Fortunella and
that inheritance of this chemical character among the
intergeneric hybrids is controlled by a dominant allele. There-
fore C. madurensis and C. halimii were thought to originate
from natural hybrids between the genera Fortunella and
Citrus.250
One new aurone aglycone and one glycoside have been
reported in the last three years. The aglycone is licoagroaurone
(120), from a hairy root culture of Glycyrrhiza glabra (Legum-
inosae).230 This prenylated compound was isolated as an orange

panduratin A (the 4⬘-methyl ether of 110) from the same extract powder. Although the proton and carbon NMR spectra of
showed significant topical anti-inflammatory activity in the aurones are very similar to those of flavones, they can be clearly
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assay of TPA-induced ear oedema in rats.243 From the roots distinguished from the HMBC spectrum. Besides, the orange
of Renealmia nicolaioides, which also belongs to the Zingi- colour of the substance and the λmax (256, 267 and 396 nm) also
beraceae, three similar new prenylated cyclohexenyl dihydro- indicated it was an aurone.230 The new aurone glycoside is
chalcones were obtained, (±)-nicolaioidesins A, B, and C (111– (Z )-6,7,3⬘,4⬘-tetrahydroxyaurone 6-(3,6-di-acetylglucoside)
113), in addition to the known panduratin A, 2⬘-hydroxy-4⬘,6⬘- (bidenoside A) from Bidens bipinnata (Compositae).248 Many
dimethoxychalcone and 5-hydroxy-7-methoxyflavanone.244 species of Bidens contain chalcones and aurones in their
Only the latter two compounds showed activity in a bioassay to yellow or orange flower petals,251 but it is uncertain whether
determine the induction of quinone reductase activity with this aurone glycoside is also a flower pigment in B. pinnata,
cultured Hepa lclc7 mouse hepatoma cells.244 There seems to be as the authors only specified that it was isolated from aerial
difference of opinion as to whether the cyclohexenyl derivatives parts.
110–113 should be classified as chalcones or dihydrochalcones.
(⫺)-Panduratin A and (⫺)-hydroxypanduratin A have been
described as chalcones,243 presumably because they co-occur 6 Flavanones and dihydroflavonols
with chalcones and are probably biosynthesised from them.
However, there is only a single bond between the α- and β-carb- Table 9 presents 54 flavanones (= dihydroflavones) and
ons, so that the nicolaioidins have been described as dihydro- 16 dihydroflavonols (also called 3-hydroxyflavanones or
chalcones.244 flavanonols) newly reported in the last three
A crude extract of leaves and twigs of Piper longicaudatum years.45,55,63,70,74,79,92,94,168,221,223,224,252–287 A few compounds
(Piperaceae) showed antibacterial activity towards Staphylo- missed in the previous review are also included.
coccus aureus and methicillin-resistant S. aureus. The active
fraction yielded the new longicaudatin (114) and three known
dihydrochalcones, including asebogenin (4,2⬘,6⬘-trihydroxy-4⬘-
methoxydihydrochalcone).245 However, only asebogenin
showed inhibitory activity against the two bacterial strains
(IC50 of 10 and 4.5 µg ml⫺1, respectively).245
A new dimeric dihydrochalcone, cycloaltilisin 6 (115), has
been isolated from the bud covers of Artocarpus altilis.246 This
bidihydrochalcone has a C–C bond between the C-5 and
the C-6 of the two units, respectively, whereas each di-
hydrochalcone unit has a geranyl side group. The known
monomeric 2-geranyl-3,4,2⬘,4⬘-tetrahydroxychalcone (called
AC-5-1) was isolated from the same extract. Both compounds
were shown to be potent inhibitors of catepsin K (a cysteine
protease implicated in osteoporosis), with an IC50 of 98 µM for
cycloaltilisin 6 and 170 µM for AC-5-1.246
Another new dihydrochalcone dimer, dihydrolophirone C
(116), and a dimer between a dihydrochalcone and a chalcone,
isolophirone C (117), have recently been found in the stem bark
of Ochna afzelii (Ochnaceae).247
Three new dihydrochalcone glycosides have been reported
in the period under review. They include two O-glycosides,
bidenoside B from Bidens bipinnata 248 and α,4,2⬘,4⬘-tetra-
hydroxydihydrochalcone α-O-β-glucoside (licoagroside F) (118)
from hairy root cultures of Glycyrrhiza pallidiflora. The latter
compound is the first example of an α-O-glycosidic α-hydroxy-
dihydrochalcone.249 The third is a C-glycoside, phloretin 3⬘,5⬘-
di-C-glucoside (119), which was isolated from the fruits of
Fortunella margarita and was also found to be present in large
quantities in the leaves and fruits of F. crassifolia, F. japonica,

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Table 9 Flavanones and dihydroflavonols reported in the period 2001–2003

Compound a Source Reference

FLAVANONES
5,2⬘-Dihydroxy-7,8-dimethoxyflavanone (dihydroskullcapflavone I) Andrographis lineata whole plant (Acanthaceae) 221
5,7,2⬘,5⬘-Tetramethoxyflavanone Andrographis rothii whole plant (Acanthaceae) 45
(2S )-5,7,2⬘,3⬘,4⬘-Pentamethoxyflavanone Andrographis affinis whole plant (Acanthaceae) 55
(2S )-5,6,7,8,4⬘-Pentamethoxyflavanone Citrus kinokuni peel (Rutaceae) 224
(2S )-5,6,7,3⬘,4⬘-Pentamethoxyflavanone
5,7,3⬘-Trihydroxy-6,4⬘,5⬘-trimethoxyflavanone Greigia sphacelata aerial parts (Bromeliaceae) 252
5,3⬘-Dihydroxy-6,7,4⬘,5⬘-tetramethoxyflavanone
5,7-Dimethoxy-3⬘,4⬘-methylenedioxyflavanone Caesalpinia pulcherrima aerial parts (Leguminosae) 223
Bauhinia variegata root bark (Leguminosae) 253
5,4⬘-Dihydroxy-7-methoxy-8-C-methylflavanone Callistemon coccineus leaf wax (Myrtaceae) 94
2,5-Dihydroxy-6-C-methyl-7-methoxyflavanone Leptospermum polygalifolium ssp. polygalifolium foliage 254
2,5-Dihydroxy-7-methoxy-8-C-methylflavanone (Myrtaceae)
(2R)-5,7-Dihydroxy-6-prenyl-8-methoxyflavanone (microfolione) Cedrelopsis microfoliata stem bark (Ptaeroxylaceae) 255
(2S )-5,3⬘-Dihydroxy-4⬘-methoxy-6⬙,6⬙-dimethylpyrano[2⬙,3⬙:7,8]flavanone Feronia limonia stem bark (Rutaceae) 256
(121)
(2S )-5,7,2⬘,4⬘-Tetrahydroxy-8-prenyl-5⬘-(1⵮,1⵮-dimethylallyl)flavanone Dalea scandens var. paucifolia roots (Leguminosae) 63
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(122)
(2S )-5,7,4⬘-Trihydroxy-8-prenyl-2⬘-methoxy-5⬘-(1⵮,1⵮-di-
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methylallyl)flavanone (123)
5,4⬘-Dihydroxy-8-hydroxymethyl-6⬙,6⬙-dimethylpyrano[2⬙,3⬙:7,6]flavanone Derris reticulata stems (Leguminosae) 257
(124)
2⬙,3⬙-Dihydroxylupinifolin (125)
Burttinonedehydrate (126) Erythrina burttii stem bark (Leguminosae) 258
Euchrenone a16 (127) Euchresta formosana roots (Leguminosae) 259
3⬘,4⬘-Methylenedioxy-[2⬙,3⬙:7,8]furanoflavanone (128) Lonchocarpus latifolius roots (Leguminosae) 92
6-Methoxy-[2⬙,3⬙:7,8]furanoflavanone (129) Millettia erythrocalyx roots (Leguminosae) 226
5-Hydroxy-4⬘-methoxy-6⬙,6⬙-dimethylpyrano-[2⬙,3⬙:7,8]flavanone (130) Macaranga conifera leaves (Euphorbiaceae) 260
5,4⬘-Dihydroxy-[2⬙-(1-hydroxy-1-methylethyl)dihydrofurano](2⬙,3⬙:7,8)
flavanone (131)
Tanariflavanones A and B (132 and 133) Macaranga tanarius fallen leaves (Euphorbiaceae) 261
Ugonin E (134) Helminthostachys zeylanica rhizomes (Ophioglossaceae/ 79
Ptaeridophyta)
Cycloaltilisin 7 (135) Artocarpus altilis bud covers (Moraceae) 246
6-Prenyl-7-hydroxy-6⬙,6⬙-dimethylpyrano[2⬙,3⬙:4⬘,3⬘]flavanone (dinklagin A) Dorstenia dinklagei twigs (Moraceae) 70
(136)
Dorsmanin I (137); dorsmanin J (138); epi-dorsmanin F (139); epi- Dorstenia mannii aerial parts (Moraceae) 262
dorsmanin G (140)
Macrourone C (141) Morus macroura bark (Moraceae) 263
Sanggenols L and M (142 and 143) Morus mongolica root bark (Moraceae) 264
5-Hydroxy-6-C-(2-hydroxy-5-methoxybenzyl)-7,8-dimethoxyflavanone Uvaria macrophylla roots (Annonaceae) 265
(macrophyllol A) (144)
5-Hydroxy-6,7-dimethoxy-8-C-(2-hydroxy-5-methoxybenzyl)flavanone Uvaria macrophylla roots (Annonaceae) 266
(macrophyllin) (145)
2⬙,3⬙-Dihydroochnaflavone (146) Ochna integerrima leaves (Ochnaceae) 267
2⬙,3⬙-Dihydroochnaflavone 7⬙-methyl ether (147)

FLAVANONE GLYCOSIDES
Pinocembrin 7-glucoside (pinocembroside) Glycyrrhiza glabra aerial parts (Leguminosae) 268
Penthorum chinense (Saxifragaceae) 269
Pinocembrin 7-apiosyl(1 5)apiosyl(1 2)glucoside Viscum angulatum whole plant (Viscaceae) 270
Naringenin 4⬘-methyl ether 7-fucopyranosyl(1 6)glucoside (longitin) Mentha longifolia aerial parts (Labiatae) 271
Naringenin 4⬘-methyl ether 7-α--arabinofuranosyl(1 6)glucoside Punica granatum stem bark (Punicaceae) 272
Eriodictyol 7-α--arabinofuranosyl(1 6)glucoside
(2S )-Eriodictyol 7-(6-p-coumaroylglucoside) Phyllanthus emblica leaves and branches 273
(2S )-Eriodictyol 7-(6-galloylglucoside) (Euphorbiaceae)
Eriodictyol 3⬘-(6-p-coumaroylglucoside) Malus × domestica leaves treated with prohexadione-Ca 274
(Rosaceae)
(2R)-5,7,4⬘-Trihydroxy-3⬘,5⬘-dimethoxyflavanone 5-glucoside Thevetia peruviana leaves (Apocynaceae) 168
(peruvianoside I)
(2S )-5,7,4⬘-Trihydroxy-3⬘,5⬘-dimethoxyflavanone 5-glucoside
(peruvianoside II)
Matteucinol 7-β--apiofuranosyl(1 6)glucoside Rhododendron simsii leaves (Ericaceae) 275
Matteucinol 7-α--arabinopyranosyl(1 6)glucoside (miconioside A) Miconia traillii twigs and leaves (Melastomataceae) 276
Farrerol 7-β--apiofuranosyl(1 6)glucoside (miconioside B)
Matteucinol 7-(4⬙,6⬙-(S )-hexahydroxydiphenylglucoside) (148) Miconia myriantha twigs and leaves (Melastomataceae) 277
Matteucinol 7-(4⬙,6⬙-digalloylglucoside)

DIHYDROFLAVONOLS
(2R,3R)-3,5,8-Trihydroxy-7-methoxyflavanone Muntingia calabura leaves (Elaeocarpaceae) 278
3,5,2⬘-Trihydroxy-7,8-dimethoxyflavanone 3-acetate (2,3-trans- and cis- Notholaena sulfurea frond (lower surface) 279
isomers) (Pteridophyta)
2,3,5,7,4⬘-Pentahydroxy-6-C-methylflavanone Leptospermum polygalifolium ssp. polygalifolium foliage 254
2,3,5,7,4⬘-Pentahydroxy-8-C-methylflavanone (Myrtaceae)
3,5,7,4⬘-Tetrahydroxy-6,8-di-C-prenylflavanone (6,8-diprenylaromadendrin) Monotes africanus leaves (Dipterocarpaceae) 280

N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 565
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Table 9 Flavanones and dihydroflavonols reported in the period 2001–2003

Compound a Source Reference

3-Methoxy-[2⬙,3⬙:7,8]-furanoflavanone (149) Lonchocarpus latifolius roots (Leguminosae) 92

Jayacanol (150) Lonchocarpus oaxacensis roots (Leguminosae) 281
rel-5-Hydroxy-7,4⬘-dimethoxy-2⬙S-(2,4,5-trimethoxy-E-styryl)tetrahydro- Alpinia flabellata leaves (Zingiberaceae) 282
furo[4⬙R,5⬙R:2,3]flavanonol (151)
rel-5-Hydroxy-7,4⬘-dimethoxy-3⬙S-(2,4,5-trimethoxy-E-styryl)tetrahydro-
furo[4⬙R,5⬙R:2,3]flavanonol (152)
Muscanone (153) Commiphora wightii trunk (Burseraceae) 283
Cathayanons A and B (154) and (155) Morus cathayana root bark (Moraceae) 284

DIHYDROFLAVONOL GLYCOSIDES
2R,3R-Aromadendrin 7-(6-[4-hydroxy-2-methylenebutanoyl]glucoside) Afzelia bella stem bark (Leguminosae) 285
(156)
Taxifolin 3-(3-cinnamoylrhamnoside) Andira inermis leaves (Leguminosae) 286
3,5,7,3⬘,5⬘-Pentahydroxyflavanone 3-rhamnoside (neosmitilbin) Smilax glabra rhizome (Smilacaceae) 287
6-Prenyltaxifolin 7-glucoside Ochna integerrima leaves (Ochnaceae) 267
a
Prenyl = 3,3-dimethylallyl. In the glycosides, the linkages between flavonoid aglycones and sugars, and between sugars and other sugars or acyl
groups, are all -O-. Sugars are all in the pyranose form, unless specified differently. Sugar linkages are β for glucose and α for rhamnose, and specified
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for the remaining sugars. Where hydroxycinnamic acids are the acyl groups, they are assumed to be in the E-form.
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566 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3
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N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3
567
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More than a quarter of the new flavanones are glycosides; the

remainder consists mainly of polymethoxylated or isoprenyl-
ated aglycones. The new methoxylated flavanones were isolated
from Citrus kinokuni (Rutaceae) 224 and several species of
Andrographis (Acanthaceae).45,55,221 All the new Andrographis
flavanones were oxygenated in the 2⬘-position. Uncommon
oxygenation patterns are also a feature of the new flavanones
from Greigia sphacelata (Bromeliaceae), which have three
adjacent oxy groups in both the A and B rings.252 The new 5,7-
dimethoxy-3⬘,4⬘-methylenedioxyflavanone has been found in
two species of Leguminosae, Caesalpinia pulcherrima 223 and
Bauhinia variegata,253 whereas three new C-methylflavanones
have been isolated from two species of Myrtaceae, Callistemon
coccineus 94 and Leptospermum polygalifolium ssp. poly-
galifolium 254 (Table 9). The flavanones from the latter species
show an additional interesting feature as they are hydroxylated
in the 2-position, which is very unusual for flavonoids.
The same four plant families from which new isoprenylated
chalcones have been reported, the Leguminosae, Moraceae,
Rutaceae and Ptaeroxylaceae (Table 8), also have been good
sources of new isoprenylated flavanones, especially the Legu-
minosae and Moraceae with eight new compounds in each. In
addition, four new isoprenylated flavanones have been found in
species of Euphorbiaceae.
The stem bark of Cedrelopsis microfoliata (Ptaeroxylaceae)
has yielded the new 5,7-dihydroxy-6-prenyl-8-methoxyfla-
vanone (microfolione), which was found to show agonistic
activity on both alpha- and beta-estrogenic receptors, but was
much less active than genistein used as a positive control.255 The
dimethylpyranoflavanone 121 from the stem bark of Feronia
limonia from the related family Rutaceae was active against
both gram-positive and gram-negative bacteria, but did not
show antifungal activity.256 Significant activity against both
methicillin-susceptible and -resistant Staphylococcus aureus has
been shown by two new isoprenylated flavanones, 122 and 123,
from the roots of the legume Dalea scandens var. paucifolia,63
whereas cytotoxicity has been shown by two more new
isoprenylated legume flavanones, 124 and 125, from Derris
reticulata.257 No activity tests were carried out on the new
isoprenylated flavanones of four other legume species, burt-
tinonedehydrate (126) from Erythrina burttii,258 euchrenone a16
(127) from Euchresta formosana,259 3⬘,4⬘-methylenedioxy-
[2⬙,3⬙:7,8]furanoflavanone (128) from Lonchocarpus latifolius 92
and 6-methoxy-[2⬙,3⬙:7,8]furanoflavanone (129) from Millettia
erythrocalyx.226

568 N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3

Four new isoprenylated flavanones bearing pyrano or furano
rings have been isolated from two species of Macaranga
(Euphorbiaceae). Flavanones 130 and 131 from Macaranga
conifera leaves were tested for their potential cancer chemo-
preventive properties by measuring their inhibitory activities
against cyclooxygenases 1 and 2, but these compounds were not
active, in contrast to the known flavanone lonchocarpol A
(5,7,4⬘-trihydroxy-6,8-diprenylflavanone) present in the same
species.260 The constituents of M. tanarius, tanariflavanones A
(132) and B (133), were isolated from fallen leaves and showed
inhibition of radicle growth of lettuce seedlings at 200 ppm
(allelopathic activity).261
The only isoprenylated new flavanone recently obtained
from a fern species, ugonin E (134) from Helminthostachys
zeylanica rhizomes, is substituted in the 8-position with a
1,1-dimethylallyl group rather than with the more common
3,3-dimethylallyl (prenyl) group.79
Eight new isoprenylated flavanones were isolated from four
species of Moraceae, comprising cycloaltilisin 7 (135) from
Published on 07 July 2004 on http://pubs.rsc.org | doi:10.1039/B311404J
Artocarpus altilis,246 dinklagin A (136) from Dorstenia
dinklagei,70 dorsmanins I (137) and J (138), and epi-dorsmanins
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F (139) and G (140) from D. mannii,262 macrourone C (141)
from Morus macroura 263 and sanggenols L (142) and M (143)
from Morus mongolica.264 All three new flavanones from Morus
species are 2⬘,4⬘-dihydroxylated in the B-ring. Sanggenol L
(142) was obtained as a diastereomeric mixture. Sanggenol M
(143) is a Diels–Alder type adduct and can be regarded as
a cycloaddition product of a dehydrogeranylflavanone and a
prenylchalcone.264 This flavanone was found to be cytotoxic
against the human oral squamous cell carcinome cell line
HCS-2 and salivary gland tumour cell line HSG, whereas
normal human gingival fibroblasts were highly resistant to this
flavonoid, suggesting that sanggenol M displays a specific
cytotoxic activity against cancer cell lines rather than normal
cells.264 Cycloaltilisin 7 (135) from Artocarpus altilis showed
activity in a cathepsin K inhibition assay, but much less so than
the dimeric dihydrochalcone, cycloaltilisin 6 (115) isolated from
the same plant species 246 (see above).
As mentioned in the chalcone section, C-benzylated
flavonoids are characteristic of the Annonaceae and especially
the genus Uvaria. Two new benzylated flavanones, the isomers
macrophyllol A (144) 265 and macrophyllin (145),266 have now
been reported from Uvaria macrophylla. Also as mentioned
before, the family Ochnaceae is rich in biflavonoids. Two new
biflavonoids, 2⬙,3⬙-dihydroochnaflavone (146) and 2⬙,3⬙-di-
hydroochnaflavone 7⬙-methyl ether (147), have recently been
isolated from Ochna integerrima. The compounds consist of a
flavone unit (luteolin) and a flavanone unit (naringenin and
naringenin 7-methyl ether, respectively) connected via an
ether linkage between the 3⬘-hydroxyl of the flavone and the
4⬘-hydroxyl of the flavanone.267
Most of the new flavanone glycosides are either biosides or
acylated monosides of the common flavanones, naringenin and
eriodictyol,271–273 or the C-methylated flavanones, matteucinol
(5,7-dihydroxy-4⬘-methoxy-6,8-di-C-methylflavanone) and far-
rerol (5,7,4⬘-trihydroxy-6,8-di-C-methylflavanone).275–277 Addi-
tionally, a monoside and a trioside of pinocembrin (5,7-di-
hydroxyflavanone) have been reported. Pinocembrin is a
characteristic constituent of some gymnosperm families, e.g.
the Pinaceae, but also occurs in many angiosperms, so it is
surprising that the 7-glucoside of pinocembrin has not been
previously recorded. However, in 2001 it was reported at the
same time from two different plant species, Glycyrrhiza glabra
(Leguminosae) 268 and Penthorum chinense (Saxifragaceae).269
The trioside, pinocembrin 7-apiosyl(1 5)apiosyl(1 2)-
glucoside, was isolated from Viscum angulatum.270
The (2R)- and (2S )-stereoisomers of the flavanone glycoside,
5,7,4⬘-trihydroxy-3⬘,5⬘-dimethoxyflavanone 5-glucoside, peru-
vianosides I and II, respectively, were found in Thevetia peruvi-
ana leaves (Apocynaceae).168 This pair of flavanone glycosides
View Online
has the same A- and B-ring substitution patterns as the flavone
glycoside, tricin 5-glucoside, which is a common constituent of
grasses and palms. Peruvianosides I and II and a number of
flavonol glycosides from the same plant source were tested for
their inhibitory effects against HIV-1 reverse transcriptase and
IHV-integrase, but the flavanone glycosides, in contrast to the
flavonol glycosides, did not show any activity in the assays.168
When young leaves of apple (Malus × domestica, Rosaceae)
were treated with the dioxygenase inhibitor prohexadione-Ca,
which is known to reduce the incidence and severity of fire
blight and other fungal diseases, a number of induced flavon-
oids were produced which were not detected in untreated leaves.
One of the compounds induced is reported as the new
flavanone glycoside, eriodictyol 3⬘-(6-p-coumaroylglucoside).274
However, the structure drawn in the paper is that of eriodictyol
4⬘-(6-p-coumaroylglucoside).
The new C-methylated flavanone glycoside, matteucinol 7-
apiofuranosyl(1 6)glucoside, was isolated from the leaves of
Rhododendron simsii (Ericaceae). The compound showed anti-
oxidant activity in three different tests.275 All the remaining new
glycosides of the C-methylated flavanones were reported from
two species of Miconia (Melastomataceae). Twigs and leaves of
M. traillii yielded the new matteucinol 7-α--arabinopyr-
anosyl(1 6)glucoside (miconioside A) and farrerol 7-β--
apiofuranosyl(1 6)glucoside (miconioside B).276 An interest-
ing new glycoside from the twigs and leaves of M. myriantha
is matteucinol 7-(4⬙,6⬙-(S )-hexahydroxydiphenyl-glucoside)
(148),277 which contains ellagic acid as an acyl group. Ellagic
acid is a dimer of gallic acid, so it contains two carboxyl groups.
However, in the free state each carboxyl group of the acid forms
an internal ester linkage with the 3-hydroxyl group of the other
monomer. In the acylated matteucinol glycoside the internal
ester formation of ellagic acid has not taken place, but instead
one of the carboxyl groups of the dimer is esterified with the
4-hydroxyl of the glucose, whereas the other carboxyl is esteri-
fied with the 6-hydroxyl of the glucose, so that a ring structure
is formed. A matteucinol glucoside, which has gallic acid
monomers attached to the 4- and 6-hydroxyls of the glucose, is
also present in M. myriantha.277 Flavanone glycoside 148 and
free ellagic acid, which was isolated from the same plant,
showed inhibitory activity against Candida albicans secreted
aspartic proteases, with IC50 of 8.4 and 10.5 µM, respectively.277
Activity-guided fractionation of an ethyl acetate extract of
the leaves of Muntingia calbura (Elaeocarpaceae) yielded a new
dihydroflavonol with an unsubstituted B-ring, (2R,3R)-3,5,8-
trihydroxy-7-methoxyflavanone. This compound was active
using a quinone reductase induction assay with cultured Hepa
lclc7 (mouse hepatoma) cells.278 Both the 2,3-trans and 2,3-cis
diastereoisomers of 3,5,2⬘-trihydroxy-7,8-dimethoxyflavanone
3-acetate have been isolated from the yellow farinose coating
of the lower surface of the fronds of the fern, Notholaena sulfu-
rica.279 Forms of N. sulfurica having a white farinose coating on
the leaves instead of a yellow farina, produce a different range
of flavonoids.279
Leptospermum polygalifolium ssp. polygalifolium (Myrtaceae)
yielded the new 2-hydroxylated dihydroflavonols, 2,3,5-tri-
hydroxy-6-methyl-7-methoxyflavanone and 2,3,5-trihydroxy-7-
methoxy-8-methylflavanone (mixture of cis- and trans-isomers)
in addition to the corresponding 2-hydroxylated flavanones,
which have been discussed above.254
Six isoprenylated flavonoids have been isolated from a non-
polar extract of Monotes africanus (Dipterocarpaceae), includ-
ing the new dihydroflavonol, 3,5,7,4⬘-tetrahydroxy-6,8-di-C-
prenylflavanone (6,8-diprenylaromadendrin), and tested for
HIV-inhibitory activity in the XTT-based, whole-cell screen.
Three flavonoids, all containing a 5,7-dihydroxy-6,8-diprenyl
system in the A-ring, were active, the new dihydroflavonol, and
the known flavonol, 6,8-diprenylkaempferol, and flavanone,
6,8-diprenylnaringenin (lonchocarpol A or senegalensin).280
The roots of Lonchocarpus latifolius (Leguminosae) yielded
N a t . P r o d . R e p . , 2 0 0 4 , 2 1, 5 3 9 – 5 7 3 569
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the new dihydroflavonol, 3-methoxy-[2⬙,3⬙:7,8]-furanoflavanone
(149) 92 and the roots of L. oaxacensis the known mundilinol
and its 2⬘-hydroxylated derivative, jayacanol (150), which is
newly reported.281 The two corresponding flavanones, the
known mundulin and minimiflorin, were also isolated from this
tree. The antifungal activity of the two dihydroflavonols and
two flavanones from L. oaxacensis was tested against the wood
rotting fungus Postia placenta, but only the new jayacanol was
active.281
Two new flavonol–phenylbutadiene adducts, rel-5-hydroxy-
7,4⬘-dimethoxy-2⬙S-(2,4,5-trimethoxy-E-styryl)tetrahydrofuro-
[4⬙R,5⬙R:2,3]flavanonol (151) and rel-5-hydroxy-7,4⬘-dimeth-
oxy-3⬙S-(2,4,5-trimethoxy-E-styryl)tetrahydrofuro[4⬙R,5⬙R:2,3]-
flavanonol (152) were isolated from the leaves of the rare
Japanese species, Alpinia flabellata (Zingiberaceae).282
An unusually substituted dihydroflavonol, aromadendrin
3-O-(1⬙,8⬙,14⬙-trimethylhexadecanoate) (muscanone, 153) has
been isolated together with the flavanone naringenin from an
ethanolic extract of the dried trunk of Commiphora wightii
Published on 07 July 2004 on http://pubs.rsc.org | doi:10.1039/B311404J
Bailon, S. de Pascual-Teresa, L. Angenot and M. Tits, Phytochem.
Anal., 2002, 13, 114.
3 Y. Fukui, T. Kusumi, K. Masuda, T. Iwashita and K. Nomoto,
Tetrahedron Lett., 2002, 43, 2637.
4 T. Fossen and Ø. M. Andersen, Phytochemistry, 2003, 62,
1217.
5 Y. Lu, L. Y. Foo and Y. Sun, Tetrahedron Lett., 2002, 43, 7341.
6 E. E. Swinny, Z. Naturforsch., C, 2001, 56, 177.
7 N. Saito, F. Tatsuzawa, K. Miyoshi, A. Shigihara and T. Honda,
Tetrahedron Lett., 2003, 44, 6821.
8 F. Tatsuzawa, N. Saito, N. Murata, K. Shinoda, A. Shigihara and
T. Honda, Phytochemistry, 2003, 62, 1239.
9 F. Tatsuzawa, N. Murata, K. Shinoda, N. Saito, A. Shigihara and
T. Honda, Heterocycles, 2001, 55, 1195.
10 F. Tatsuzawa, N. Saito, N. Murata, K. Shinoda, A. Shigihara and
T. Honda, Heterocycles, 2002, 57, 1787.
11 T. Otsuki, H. Matsufuji, M. Takeda, M. Toyoda and Y. Goda,
Phytochemistry, 2002, 60, 79.
12 K. Toki, N. Saito, A. Shigihara and T. Honda, Phytochemistry, 2001,
56, 711.
13 K. Toki, N. Saito, A. Shigihara and T. Honda, Heterocycles, 2003,
60, 345.

(Burseraceae) 283 and was found to be active against the yeast 14 N. Saito, K. Toki, H. Moriyama, A. Shigihara and T. Honda,
Candida albicans. 283 Phytochemistry, 2002, 60, 365.
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15 B. Reiersen, B. T. Kiremire, R. Byamukama and Ø. M. Andersen,

Numerous isoprenylated flavonoids have already been
reported from species of Morus (the mulberry tree), including a 16
number of Diels–Alder type adducts such as sanggenol M (143, 17
see above). Two more such adducts, cathayanons A (154) and B
(155), regarded as cycloaddition products of isoprenylated 18
dihydroflavonols and chalcones, have recently been isolated
19
from the root bark of Morus cathayana. The structures, elucid-
ated on the basis of spectroscopic evidence, were confirmed 20
by X-ray crystallography. The absolute configurations of
cathayanons A and B were determined as 2S,3R,14S,19S,20R 21
and 2S,3R,14R,19S,20R, respectively. Both compounds
exhibited potent activities on the inhibition of HL-60 cell 22
adhesion to BAEC at concentrations of 10⫺5 mol L⫺1, with 23
inhibitory rates of 44.72 and 39.02%, respectively.284
Only four dihydroflavonol glycosides have been reported in 24
the last three years, including two acylated ones from members
of the Leguminosae, aromadendrin 7-(6-[4-hydroxy-2-methyl- 25
enebutanoyl]glucoside) (156) from the stem bark of Afzelia 26
bella 285 and taxifolin 3-(3-cinnamoylrhamnoside) from the 27
leaves of Andira inermis.286 A new dihydroflavonol glycoside
with an unusual B-ring substitution, 3,5,7,3⬘,5⬘-pentahydroxy- 28
flavanone 3-rhamnoside (neosmitilbin), has been reported from
Smilax glabra rhizomes (Smilacaceae) 287 and an isoprenylated 29
flavanonol glycoside, 6-prenyltaxifolin 7-glucoside, from Ochna
30
integerrima leaves.267
Many biological and medicinal activities of the newly 31
reported flavanones and chalcones have already been men-
tioned above. However, a number of structure–activity studies 32
has also been carried out on known compounds. For example, 33
16 flavonoids and their derivatives isolated from species of 34
Desmos (Annonaceae) were evaluated for inhibition of HIV 35
replication in H9 lymphocyte cells. 2⬘,6⬘,β-Trihydroxy-3⬘-C-
methyl-5⬘-C-formylchalcone was the most active compound, 36
with an EC50 value of 0.022 µg ml⫺1 and a therapeutic index of 37
489. The second most active constituent was the flavanone
lawinal (5,7-dihydroxy-6-C-formyl-8-C-methylflavanone) with 38
an EC50 value of 2.30 µg ml⫺1.288 39
The well-known flavanone, (2S )-pinocembrin, has been
isolated as an active principle of inducibly produced antifungal 40
compounds from the bark of Pinus strobus infected with the
pinewood nematode, Bursaphelenchus xylophilus. This com- 41
pound can therefore be considered as a phytoalexin of 42
P. strobus.289 43
44
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