Synthesis of Alkenes: Claisen Rearrangement of Allyl Vinyl Ethers, Part Iii Mechanistic Views The Organic Chemistry Notebook Series, A Didactical Approach, #11

REVISTA BOLIVIANA DE QUMICA (Rev.Bol.Quim.
)
Bolivian Journal of Chemistry
Received 08 23 2016
Accepted 09 12 2016
Bravo et Vila
Vol. 33, No.3, pp. 127-133, Jul./Ago. 2016

33(3) 127-133, Jul./Aug. 2016
Published 09 15 2016
.
SYNTHESIS OF ALKENES: CLAISEN REARRANGEMENT OF ALLYL

VINYL ETHERS, PART III; MECHANISTIC VIEWS; THE ORGANIC
CHEMISTRY NOTEBOOK SERIES, A DIDACTICAL APPROACH, N 11
Jos A. Bravo1,*, Jos L. Vila2
1Department
of Chemistry, Research Institute of Natural Products IIPN, Laboratory of Phytochemistry,

Universidad Mayor de San Andrs UMSA, P.O. Box 303, Calle Andrs Bello s/n, Ciudad Universitaria
Cota Cota, Phone 59122792238, La Paz, Bolivia, jabravo@umsa.bo
2Department
of Chemistry, Research Institute of Natural Products IIPN, Laboratory of Synthesis and Hemisynthesis of Natural Products, Universidad Mayor de San Andrs UMSA, P.O. Box 303, Calle Andrs Bello
s/n, Ciudad Universitaria Cota Cota, Phone 59122795878, La Paz, Bolivia, joselu62@hotmail.com
Keywords: Organic Chemistry, Alkenes, Allyl vinyl ethers, Claisen rearrangement, Mechanisms
of Reactions, W. Carruthers.
ABSTRACT
This is the eleventh theoretical assay in the series: The Organic Chemistry Notebook Series, a Didactical Approach.
The aim of this series of studies is to help students to have a graphical view of organic synthesis reactions of
diverse nature. We have taken a series of reactions compiled by W. Carruthers in Some modern methods of organic
synthesis, and we have proposed didactical and mechanistic views for them. This theme is included in the chapter
Formation of carbon-carbon double bonds in the mentioned text.
In chapter 11, we expose a complementing of Claisen rearrangements of ally-vinyl ethers started two papers
ago. Now its turn for the use of a variation of the Claisen rearrangement: the ester-enolate variation (also known as
the ketene acetal variation). In this sense, the synthesis of the natural product: methyl santolinate is briefly exposed in
a mechanistic manner. Also, the mechanism of the synthesis of -unsaturated amino acid derivative and ulterior
lactone hydrochloride from the Z-crotyl glicine ester is proposed on the basis of theoretical approaches. The
condensation between allylic alcohols and cyclic orthoesters to produce (via Claisen rearrangement) lactones with the
inverted allyl group as a substituent is mechanistically exposed. Vinyl lactones can be converted into cycloalkenes
(via Claisen rearrangement of cyclic enol ethers); weve analyzed the mechanism.
*Corresponding author: joseabravo@outlook.com
RESUMEN
Spanish title: Sntesis de alquenos mediante transposicin de Claisen de teres alil-vinlicos, parte III;
vistas mecanicsticas; de la serie: El cuaderno de notas de qumica orgnica, un enfoque didctico, N11.
Este es el dcimo ensayo terico en la serie: El cuaderno de qumica orgnica, un enfoque didctico.
El objetivo de esta serie de estudios es ayudar a los estudiantes a disponer de una visin grfica de reacciones
de sntesis orgnicas de diversa naturaleza. Hemos tomado una serie de reacciones compiladas por W. Carruthers en:
Some modern methods of organic synthesis, para las cuales hemos propuesto vistas mecanicsticas y didcticas.
Este tema esta incluido en el captulo Formation of carbon-carbon double bonds del mencionado texto.
En el captulo 11 exponemos un complemento de la transposicin de Claisen de teres alil-vinlicos comenzado
hace dos artculos. Ahora es turno del uso de una variacin de la Transposicin de Claisen: la variacin ester-enolato
(conocida tambin como variacin ceteno acetal). En este sentido, la sntesis del producto natural santolinato de
metilo es expuesta brevemente en una manera mecanicstica. Tambin el mecanismo de la sntesis de derivados de
amino acido -insaturados y produccin del ulterior clorhidrato de lactona a partir de ester de Z-crotyl glicina es
propuesto sobre la base de enfoques tericos. La condensacin entre alcoholes allicos y ortosteres cclicos para dar
lactonas con un grupo alilo invertido como sustituyente en , se expone mecanicsticamente. Vinil lactonas pueden
convertirse en cicloalquenos va transposicin de Claisen de enol teres; hemos propuesto el mecanismo.
Downloadable from: Revista Boliviana
127
de Qumica. Volumen 33 N3. Ao 2016
http://www.bolivianchemistryjournal.org, http://www.scribd.com/bolivianjournalofchemistry
REVISTA BOLIVIANA DE QUMICA (Rev.Bol.Quim.)

Received 08 23 2016
Accepted 09 12 2016
Bravo et Vila
Vol. 33, No.3, pp. 127-133, Jul./Ago. 2016

33(3) 127-133, Jul./Aug. 2016
.
INTRODUCTION
During master classes of organic chemistry, we noticed that students are confronted with a lack of knowledge with
regard to mechanisms. A mechanistic approach about any kind of reaction enhances the capacity of facing new
reactions with respect to an understanding of all processes involved in them, and also develops synthetic creativity.
As academics we feel concerned with the didactical importance of covering these needs in debutant students in
organic synthesis. This, the synthesis of alkenes by Claisen rearrangement of allyl vinyl ethers, part III; mechanistic
views; is the eleventh study in the series: The Organic Chemistry Notebook Series, a Didactical Approach [1-10].
REACTIONS AND THEIR MECHANISTIC PROPOSALS, DISCUSSION
The variation of the Claisen rearrangement: the ester enolate (known also as the ketene acetal variation) is useful in
stereocontrolled synthesis of natural products. Methyl santolinate 25, an irregular monterpene can be synthesized
from propionate ester 23, which gives mainly the Z-ketene acetal 24 and this gives 25. The reaction is carried on
lithium isopropylcyclohexylamide in THF and after on t-butyldimethylsilyl chloride [11]. The reaction path is: C.R.
(Claisen Rearrangement) at 650C followed by hydrolysis and esterification by using diazomethane to give santolinate
with high stereoselectivity [11,12]. See Figure 1 for the schematic reaction and its proposed mechanism.
Comments
The propionate ester (23) forms a six membered cycle in the chair form with lithium and nitrogen. The nitrogen
extracts a proton from the carbon of the ester. The formed carbanion establishes an alkene by dispatching the pi
electrons of the carbonyl over the oxygen atom which after establishes a covalence with Li+ (or at least neutralizes it
ionically). The tert-butyldimethylsilyl chloride interchanges its anion (Cl-) with RO-. Thus, with this alkoxy
protected (24), the Claisen rearrangement (C.R.) becomes effective to form the -alkene. There follows the
separation of the protecting group, the tert-butyldimethylsilyl group from the substrate, and generates a hydroxyl
group of an acid function. Final methylation converts the hydroxy group into a methoxy by the action due to
diazomethane to afford methyl santolinate (25).
Another synthetic pathway employing a C.R. uses the Z-crotyl glycine ester 26 which is converted in the unsaturated amino acid derivative 27a which at its turn converts into the lactone chloride 28. This is a natural
product isolated from Amanita phalloides (Green Death Cap Toadstool), after hydrolysis of - and -amanitin (toxic
cyclic peptides) [13,14]. When the transition state is assumed to be a chair-like conformer (29), the stereochemical
pathway of the rearrangement implies that the intermediate ketene acetal presents mostly the stereochemistry E (26)
instead of the Z-configuration [13,15]. This is the general case for esters of acids with a heterosubstituent on the carbon like -amino and -hydroxy acids [15,16]. See Figure 2 for the reaction scheme and Figure 3 for the
corresponding mechanistic proposal.
Comments
The ester 26 is submitted to the alkali action of LiN(iso-pr)2 to afford the anion N-. A charge transfer occurs from
nitrogen to oxygen. Every negative charge is neutralized at any moment by Li+. In this condition, the interaction of
the lithiated substrate and another equivalent of LiN(iso-pr)2 takes place under the form of the six membered cycle in
the chair form conformed by the adduct of 26-Li + LiN(iso-pr)2. The nitrogen of LiN(iso-pr)2 takes a hydrogen from
the substrate currently under the form of a chair six membered cycle, generating thus a carbanion in the substrate.
The tetravalent nitrogen positively charged [LiN+H(iso-pr)2] recovers neutrality and its tri-valence by excision of its
covalence to Li. The Li cation thus formed makes ionic pair with the negative charge now situated on the oxygen of
carbonyl after charge transfer from the carbanion; a new carbon-carbon double bond has formed. Lithium stabilizer
is replaced by silicon of trimethylsilyl chloride through a nucleophilic attack of the enol oxygen of substrate to
silicon of TMS chloride to expel Cl-. The same happens to the other Li+O- couple in the substrate. This substrate with
two protected enol groups (26) suffers the Claisen rearrangement to afford the -alkene. Acid hydrolysis withdraws
the protecting group trimethylsilyl at the carbonyl adjacent position. The second protecting group (OSiMe3) is
withdrawn by methanolysis after protonation. Follows a deprotonation of the methoxy group and protonation of the
nitrogen. This protic catalysis promotes the elimination of the methyl of the methoxy group and formation of a
carbonyl group. The carbocation Me+ establishes a bond with the anion OSiMe3 to give MeOSiMe3, weve reached
the intermediate 27a (Fig. 3).
128

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33(3) 127-133, Jul./Aug. 2016
Accepted 09 12 2016
Bravo et Vila
OSi(CH3)2C4H9
(1) LiN(iso-pr)(C6H11)
o
THF, -78 C
O
O
CH3O2
CH3
(1) 65 C
(2) CH3CO2H-H2O
(3) CH2N2
(2) t-C4H9(CH3)2SiCl
H
24
23
25
Mechanism for 25
OR'
(1) LiN(iso-pr)(C6H11)
o
THF, -78 C
23
OR'
O .. CH3
H
Li
CH3
H
OR'
OR'
-
O ..
H
+
Li
H
O
H
Li
CH3
OLi
CH3
OSiMe2-t-but
O R'
Li
H
CH3
24
OSiMe2-t-but OSiMe2-t-but
O
Me2BuSiO
OSiMe2-t-but
CH3
24
O
H
OSiMe2-t-but
CH3
O
H CH3COOH/H2O
H
Me2BuSiO
-H+
CH3
H
H
CH2
+
H 180o
CH3
OSiMe2-t-but
.. ..O-CH2-N=N:
CH3
O
H
..
OH
CH3
H
H
H 3C
O+H2
H+OSiMe2-t-but
CH3
H2O:
O
H
Me2BuSiO
Me2BuSiO
O
C.R.
OCH2+
CH3 + N2 + H
O
H
OCH3
CH3
O
H
25
Figure 1. Claisen rearrangement; synthesis of methyl santolinate (25) from propionate ester (23); reviewed by W. Carruthers
[11]. Mechanistic views by the authors
O
t-C 4H9OCONH
H 3C
OSi(CH3)3
O
(1) 2 equiv. LiN(iso-pr)2

o
THF, -75 C
t-C 4H9O
H
R1
N
CO2H
(b)
CH3
27
+
H
t-BocNH
CO2H
several steps
(a)
Cl-H3N+
O
H 3C
R2
t-BocNH
H
26'
O
(1) reflux
(2) CH3OH
26
(CH3)3SiO
OSiMe3
(2) 2(CH3)3SiCl
N
H 3C
CH3
OH
29
28
Figure 2. Claisen rearrangement; synthesis of lactone hydrochloride (28) from Z-crotyl glycine ester (26); reaction passes by
ketene acetal intermediate with the E-configuration (26); reviewed by W. Carruthers [13].
129

Received 08 23 2016
Accepted 09 12 2016
Bravo et Vila
Mechanism for 27a

O
t-C 4H9OCONH
H 3C
H
H
O
O
1 equiv. LiN(iso-pr)2
o
THF, -75 C
Li
O-Li+
i-pr +N
H
i-pr
OR'
H
2Me2SiCl
Me3SiO
OSiMe3
O
O H2O, H+
N
Me
Me3SiO
-H+
OSiMe3
H-
H 2+ O
Me3SiO
O
H
O +H+
O -H+
N
Me
O +H
H
NaOH
H 2N
Me
H
H 2C
2HCl
O
-
C Na
H 2C
OH
OH
N
Me
O
27a
+ MeOSiMe3
O
H
O H
O +H
N+ Me
O
H 2C
O
O
H H
O
O H H H
N
Me
O
H
+ -OSiMe3
O
H H
H 2C
H 2N
Me
CH3OH
N
Me
N
Me
Me3SiO
H 3C O
HO
O
N
Me
O +H
HO
H H
N
Me
H
H H
OSiMe3
H
O
Me3SiO
N
Me
CH3O
H
H 2C
N
Me
Me
OSiMe3
180o
N
O
HO
N
Me
OSiMe3 Me2SiO
N
Me
H2O H+OSiMe3
H
O
N
Me
HO
OSiMe2
OSiMe3
H
180o
CH3O+H
O
H
H
OSiMe3
OSiMe3
O
Me2SiO
OSiMe3
OSiMe3
Me
N
OSiMe2
OR'
OSiMe2
CH3
H
i-pr
Me3SiO
O Li
i-pr N
OSiMe2
-.. H
Li+
C.R.
Me2SiO
OSiMe2
26'
Li
OR'
OSiMe2
-..
Li+
O-Li+
H
i-pr N
i-pr
OSiMe2
R'
OR'
i-pr
Me2SiO
OR'
O
O-Li+
i-pr N
N
O- Li+
OR'
O- Li+
O
OR'
N - Li
26
O
Vol. 33, No.3, pp. 127-133, Jul./Ago. 2016

33(3) 127-133, Jul./Aug. 2016
O +H
H
H 2C
Cl- H
H 3N +
O
O
Me
H
C H
+ NaCl
H 2C
OH
28
Figure 3. Claisen rearrangement; synthesis of lactone hydrochloride (28) from Z-crotyl glycine ester (26); reaction passes by
ketene acetal intermediate with the E-configuration (26); reviewed by W. Carruthers [13]. Mechanistic views by the authors
130

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Vol. 33, No.3, pp. 127-133, Jul./Ago. 2016

33(3) 127-133, Jul./Aug. 2016
.
The -unsaturated carboxylic acid 27a suffers lactonization by means of an intracyclic nucleophilic attack over the
alkenic double bond. The -lactone formed incorporates a terminal vinyl group by means of elimination of hydride
which attacks the carbonyl group becoming thus a temporary alkoxy group. The alkoxy group regenerates the
carbonyl and provokes the excision of the molecule by means of breaking the bond C-N. The -vinyllactone is now
protonated. A proton transfer betweenthe positively charged oxygen and the anionic nitrogen gives the substrate
electronic stability again. The hydroxyl addition over the vinyl terminal methylene occurs to afford a terminal
primary alcohol. The lactone cycle resists against ring rupture and the electronic excess settles now over the
quaternary carbon of the terminal vinyl group. This anion forms ionic pair with cation sodium. One of two
equivalents of HCl serves to withdraw cationic sodium which makes couples with one Cl- and installs a proton over
the carbanion . The other HCl equivalent protonates the nitrogen which makes ionic pair with Cl-. Weve reached the
product 28 (Fig. 3).
Its been established that the C.R. of vinyl ethers of acyclic allylic alcohols happens through T.S. of the chair
type [15]. There are other examples where the substrates own a double bond of vinyl ether or of allylic alcohol as
part of a cycle [15]. In such case, the T.S. is a well-defined boat conformer [15]. The T.S. in the chair form in these
cases implies much strain [15]. For example, lets see the reaction between allylic alcohols and cyclic orthoesters that
through Claisen rearrangement give lactones with the allyl group inverted as an -substituent [15]. The cyclic
orthoester 29 reacts with the cyclic allyl alcohol 30; the product is lactone 31. The yield was 80 % and the
stereoselectivity complete. The configuration of the chiral center at the cyclohexene is controlled by the
configuration in the allylic hydroxyl group which is a leaving group. Regarding the configuration of the chiral center
in the lactone, this is determined by the conformation of the chair type or the boat type of the transition state. Thus,
the stereochemistry of 31 indicates that the reaction was carried on through a transition state of the boat type [15,16].
See Figure 4.
catalytic CH3CH2CO2H
+
O
H 5C 2O
reflux
1,2-dimethylbenzene
H5C6CO2
OC2H5
OH
29
H5C6CO2
30
31
Mechanism for 31
H
CH3CH2CO2H
Ph
Ph
Ph
OH
O
30
O
H 5C 2O
H +O
H+OC2H5
O
O
+ EtOH C.R.
H
O
H+OC2H5
OC2H5
29
Ph
H O
O
boat-like T.S.
Ph
O
O
O
H
H
O
H5C6CO2
31
31
Figure 4. Claisen rearrangement; reaction of cyclic orthoester 29 with allylic alcohol 30 to form lactone 31 (-unsaturated
lactone); reviewed by W. Carruthers [15]. Mechanistic views by the authors
Comments
Although the orthoester tri-oxygenated carbon (29) manifests a lower electrophilicity than the carbonyl carbon of the
benzoyl substituent in 30, proved by the fact of the lower chemical shift value of the O3C from orthoester with
respect of carbonyl carbon (o3c 114.2 vs. c=o 166.8 of methyl benzoate [17,18 respectively]), the nucleophilic
attack occurs over the H+O3C from orthoester instead of the benzoyl carbonyl. The reason is attributable to the protic
catalysis from propionic acid, experimented firstly by one of the oxygen atoms of the O3C from orthoester instead of
the carbonyl oxygen. By statistic reasons the catalyst interacts firstly with one of the oxygen atoms of the O3C
instead of the carbonyls oxygen. In this three-oxygen group, the oxygen atoms are closer each other. In contrast, the
benzoate presents only two oxygen atoms. This fact makes of this carbon (H+O3C) a preferred nucleophile attack site
in the mixture instead of the carbonyl of benzoate (O=C-O with no H+ catalyst, 30). We mean by this that the
131

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33(3) 127-133, Jul./Aug. 2016
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Bravo et Vila
electrophile is the H O3C of the orthoester (29) and the nucleophile, the hydroxyl oxygen of the allylic alcohol (30).
On the contrary, due to the protic catalysis, a nucleophilic attack of the nucleophile oxygen from any of the ethoxy
protonated groups of the orthoester (29) over the electrophile carbonyl carbon of the unprotonated benzoate of the
allylic alcohol, is not feasible. The nucleophilic attack over carbonyl or H+O3C from ester depends on polar and
steric factors. In spite of the fact that H+O3C from ester is tetrahedral and the carbonyl carbon is planar (steric
factor), the polar factor (generated by the H+ catalyst) drives the nucleophile (ROH) towards the H+O3C from ester.
The benzoate-orthoester adduct transfers the catalyst from the recently formed (so far protonated) ether bridge to one
of the ethoxy groups of the ester moiety of the adduct. This good leaving group leaves the adduct forming a
carbocation (not graphically described in Fig. 4). The presence of the carbocation charge promotes a proton
elimination from the vicinal CH2 group to form an alkene. Both moieties are now situated in a transition state in the
boat form. This mutual position makes the Claisen rearrangement possible to afford the final product 31.
In a series of reactions related to those exposed above, vinyl lactones 32 are converted into cycloalkenes
through Claisen rearrangements using cyclic enol ethers 33. Un such reactions, the stereochemistry of the products
implies a transition state employing a boat conformation [15,19]. See Figure 5.
H 3C
H 3C
H 3C
H
O
OSi(CH3)2C4H9-t
(1) LiN(iso-C3H7)2
CO2H
C 2H 5
(1) Toluene, 105C
(2) CH3OH
(71%)
C 2H 5
C 2H 5
cyclic enol ether
vinyl lactone
32
33
34
Mechanism for 34
t-but
Me
O-
..
vinyl lactone H
H O
H O Si
Me
H
boat-like T.S. H + ClN+
33
Li
N+
Li
Li
t-but
Me
O Si
H +
Me
O HMe
t-but
Me
HO Si
H 3C
H
Me
OMe
H
HOMe
CO2H
C 2H 5
H
O
H
C.R.
H
cyclic enol ether H
N+
Li
t-but
Me
Me
H O
H
N
32
Si Cl
t-but
Me
O Si
Me
H
34
Figure 5. Claisen rearrangement; transformation of vinyl lactone 32 via cyclic enol ether 33 to afford 34 (-unsaturated
carboxylic acid); reviewed by W. Carruthers [15]. Mechanistic views by the authors
Comments
In step one of the mechanism for 34, the strong base NLi(i-pr)2 extracts the acidic hydrogen in of carbonyl of the
substrate 32. Thus, the just formed carbanion derives into a C-C double bond by p-orbital overlapping, sending thus
the pi bond of carbonyl over the carbonyl oxygen. The oxygen atom (nucleophile) attacks silicon (electrophile)
and expels chloride (leaving group) which makes ionic pair with the quaternary ammonium: N+LiH(i-pr)2. The
oxydimethylterbutyl cyclic enol ether suffers the Claisen rearrangement employing a transition state in the boat type.
This operation affords the -unsaturated carboxylic acid silylated. Methanolysis gives rise to final product 34.
ACKNOWLEDGEMENT
132

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Vol. 33, No.3, pp. 127-133, Jul./Ago. 2016

33(3) 127-133, Jul./Aug. 2016
.
The authors express their gratitude to Prof. Eduardo Palenque from the Department of Physics, Universidad Mayor
de San Andrs, for his bibliographic support.
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Synthesis of Alkenes: Claisen Rearrangement of Allyl Vinyl Ethers, Part Iii Mechanistic Views The Organic Chemistry Notebook Series, A Didactical Approach, #11

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REVISTA BOLIVIANA DE QUMICA (Rev.Bol.Quim.

Vol. 33, No.3, pp. 127-133, Jul./Ago. 2016