Regio- and stereoselective synthesis of vinylallenes by 1,5-(S(N)'')- substitution of enyne acetates and oxiranes with organocuprates

Article abstract of DOI:10.1002/(SICI)1099-0690(199901)1999:1<267::AID-EJOC267>3.0.CO;2-V

Enyne acetates 2, 4, 6, and 8, as well as enyne oxiranes 10, with different substitution patterns react with organocuprates regioselectively under 1,5-(S(N)2'')-substitution to provide vinylallenes 11 and 12. With lithium dimethylcuprate, reduced vinylallenes originating from a [formal) transfer of a hydride ion to the substrate are formed in some cases. The products are usually obtained as mixtures of (E/Z)-isomers; however, pure (E)-vinylallenes are formed occasionally. The 1,5-substitutions can also be carried out with catalytic amounts of copper reagents. The reaction of chiral enyne acetate (S)-2a with tBu₂CuLi · LiCN proceeds enantioselectively, so that this transformation constitutes a new case of remote stereocontrol.

Full text of DOI:10.1002/(SICI)1099-0690(199901)1999:1<267::AID-EJOC267>3.0.CO;2-V

FULL PAPER
Regio- and Stereoselective Synthesis of Vinylallenes by 1,5-(SNЈЈ)-Substitution
of Enyne Acetates and Oxiranes with Organocuprates
Martin Purpura,[a] and Norbert Krause*[a,b]
Dedicated to Prof. Dr. Reinhard W. Hoffmann on the occasion of his 65th birthday
Keywords: Vinylallenes / Organocuprates / Substitution / Stereoselective synthesis / Copper catalysis
Enyne acetates 2, 4, 6, and 8, as well as enyne oxiranes 10,
with different substitution patterns react with organo-
cuprates regioselectively under 1,5-(SN2ЈЈ)-substitution to
provide vinylallenes 11 and 12. With lithium dimethyl-
cuprate, reduced vinylallenes originating from a (formal)
transfer of a hydride ion to the substrate are formed in some
cases. The products are usually obtained as mixtures of (E/Z)-
isomers; however, pure (E)-vinylallenes are formed occa-
sionally. The 1,5-substitutions can also be carried out with
catalytic amounts of copper reagents. The reaction of chiral
enyne acetate (S)-2a with tBu2CuLi
· LiCN proceeds
enantioselectively, so that this transformation constitutes a
new case of remote stereocontrol.
Introduction
Allenes are fascinating and useful molecules for several
reasons: the allenic moiety is found in many natural prod-
ucts, it can be utilized for the assembly of complex target
molecules of biological and/or pharmacological relevance,
and it constitutes an axis of chirality if substituted suit-
ably.[1] Among several known methods for the synthesis of
allenes,[1,2] the reaction of propargylic electrophiles A with
organocopper reagents is of particular importance because
it usually leads to the desired products B with high regio-
and stereoselectivity (i.e. as anti-SN2Ј substitution with pro-
pargylic rearrangement).[1,3] This opens a reliable stereose-
lective route to chiral allenes since the starting materials are
easily accessible in enantiomerically and/or diastereomer-
ically pure form.[4] Additional virtues of the method are its
applicability to substrates with many different leaving
groups X (among others, propargylic acetates, mesylates,
halides and epoxides have been converted into allenes suc-
cessfully) and the possibility to perform it catalytically, i.e.
with Grignard reagents and catalytic amounts of copper
salts.[1,3]
Scheme 1
alia, are valuable dienes in regio- and stereoselective Diels
ϪAlder reactions.[7] Additionally, it would be interesting to
study the stereochemical course of such transformations, i.e.
the possibility to control the configuration of the olefinic
double bond of the vinylallene, and to perform the reac-
tions enantio- or diastereoselectively (this would constitute
one of the few cases of remote stereocontrol in organo-
copper chemistry[6,8]). We therefore examined the reactions
of enyne electrophiles with organocopper reagents in
greater detail; our first results concerning the scope of 1,5-
substitutions of enyne acetates and oxiranes are presented
here.
In contrast to this well-established transformation, there
is almost no precedent for the corresponding reactions of
enynoic electrophiles C.[5,6] Of course, the introduction of
an additional double bond into the substrate causes an in-
crease of the number of possible regioisomeric products: the
nucleophile may attack at C-1, C-3, or C-5. The latter case,
i.e. a SN2ЈЈ or 1,5-substitution, would be the most interest-
ing, as this would lead directly to vinylallenes D which, inter
Results and Discussion
After preliminary studies had shown that the acetate
group is a suitable leaving group for 1,5-substitutions of
primary, secondary, and tertiary enyne electrophiles,[2b] we
synthesized several enyne acetates with different steric and
electronic properties. Thus, the secondary acetates 2aϪc
bearing different substituents at the triple bond were ob-
[a]
´
Kekule-Institut für Organische Chemie und Biochemie der
Universität Bonn,
Gerhard-Domagk-Straße 1, D-53121 Bonn, Germany
Fax: (internat.) ϩ49 (0)231/ 7553884
E-mail: nkrause@pop.uni-dortmund.de
New address: Organische Chemie II, Universität Dortmund,
D-44221 Dortmund, Germany
[b]
Eur. J. Org. Chem. 1999, 267Ϫ275
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1434Ϫ193X/99/0101Ϫ0267 $ 17.50ϩ.50/0
267

M. Purpura, N. Krause
FULL PAPER
tained from the aldehydes 1 by addition of MeLi or
With this set of different enyne electrophiles at hand, we
MeMgBr and esterification of the crude alcohols (for de- examined their behavior in substitution reactions in greater
tails see Experimental Section). Similarly, reduction of the detail. The results of the reaction of the enyne acetates 2,
ketones 3 followed by acylation gave acetates 4aϪc.
4, 6 and 8 with organocuprates are summarized in Table 1.
Scheme 6
Treatment of enyne acetate 2a with 2.0 equiv. of lithium
di-n-butylcuprate (nBu2CuLi · LiI) in diethyl ether at
Ϫ80°C resulted in complete consumption of the starting
material within 1 h. After aqueous workup and purification
of the crude product by column chromatography, the de-
sired 1,5-substitution product, vinylallene 11a, was isolated
with 90% yield as a 2:1 mixture of (E/Z) isomers (Table 1,
entry 1). The structural assignment of this hydrocarbon
bases on the typical allenic resonances in the 13C-NMR
spectrum at δ ϭ 203.5 (C-5), 100.6/100.5 (C-6), and 93.2/
88.6 (C-4), as well as on the appearance of the characteristic
peak at ν˜ ϭ 1948 cmϪ1 in the IR spectrum. Very similar
values were found for all other substitution products ob-
tained in this work. In this case, as in all other cases exam-
ined here, the isomers could not be separated by column
chromatography. Unfortunately, the resonances for the olef-
Scheme 2
Different substitution patterns were elaborated from ke-
tone 5 and the commercially available alcohol 7. Thus, re-
duction and esterification of 5 provided the cyclic acetate 6,
and oxidation of 7 to the aldehyde with activated manga-
nese dioxide, followed by addition of MeMgBr and acyla-
tion gave substrate 8.
1
inic and allenic protons in the H-NMR spectrum could
not be resolved; consequently an assignment of the configu-
ration of the olefinic double bond of 11a with the vicinal
3
coupling constant J2,3 (or with NOE experiments) was not
possible. However, the 13C-NMR resonances observed of
C-4 for (E)-11a (δ ϭ 93.2) and (Z)-11a (δ ϭ 88.6) are
characteristic for the geometrical isomers (see below) and
were used for the assignment in this case.
When THF was employed instead of diethyl ether as sol-
vent, the reaction of 2a and n-Bu2CuLi · LiI proceeded only
sluggishly even at elevated temperatures. Therefore, diethyl
ether was used as solvent for 1,5-substitutions throughout
this work, and the analogouos reaction of 2a with the cy-
ano-Gilman reagent tBu2CuLi · LiCN [10] under these con-
ditions furnished vinylallene 11b with 93% yield as a 1:3
mixture of (E/Z)-isomers (entry 2). Thus, the steric demand
of the cuprate affects the (E/Z)-selectivity, but not the re-
gioselectivity of the substitution. Again, the isomers could
Scheme 3
Another leaving group which has been used frequently in
SN2Ј substitutions is the oxirane moiety; in contrast to sim-
pler substrates which furnish unfunctionalized hydro-
carbons, oxiranes give substitution products with an ad-
ditional alcohol function which can be elaborated further.[3]
In order to examine substrates of this type also here, we
synthesized the enyne oxiranes 10a/b by treatment of the
corresponding carbonyl compounds 3a and 9 with the sul-
fur ylide formed from trimethylsulfonium bromide and
base.[9]
1
not be separated chromatographically; nevertheless, all H-
and 13C-NMR resonances could be assigned, allowing an
unambigous distinction of the isomers. Particularly indica-
3
tive are the coupling constants J2,3 ϭ 15.5 Hz for (E)-11b
3
and J2,3 ϭ 10.6 Hz for (Z)-11b. Also the differences of
chemical shifts of the (E)- and (Z)-isomer observed for 2-
H (δ ϭ 5.58 vs. 5.38), 4-H (δ ϭ 5.70 vs. 5.99), and C-4
(δ ϭ 93.6 vs. 89.1) are very useful for the assignment of
the configuration of the olefinic double bond since similar
patterns were found for many more vinylallenes prepared in
this work.
Scheme 4
268
Eur. J. Org. Chem. 1999, 267Ϫ275

Regio- and Stereoselective Synthesis of Vinylallenes
FULL PAPER
Table 1: Reaction of enyne acetates 2, 4, 6, and 8 with organocuprates
Entry
Substrate Cuprate
Product R1
R2
R3
R4
R5
R6
Yield [%] (E)/(Z)
1
2a
2a
2b
2c
2c
4a
4a
4b
4b
4c
4c
6
nBu2CuLi · LiI
11a
11b
11c
11d
11e
11a
11f
11g
11h
11i
Me
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
H
Me
Me
Me
Me
Me
Me
Me
tBu
tBu
Ph
H
H
H
H
H
H
H
H
H
H
H
H
H
H
nBu
tBu
tBu
nBu
tBu
Me
tBu
Me
tBu
Me
tBu
Me
tBu
tBu
90
93
80
80
67:33
25:75
50:50
60:40
2
tBu2CuLi · LiCN
tBu2CuLi · LiCN
nBu2CuLi · LiCN
tBu2CuLi · LiCN
Me2CuLi · LiI
Me
H
3
Ph
H
4
Me3Si
Me3Si
nBu
nBu
nBu
nBu
nBu
nBu
nBu
nBu
H
H
5
H
96
40:60
[a]
[a]
6
H
7
tBu2CuLi · LiCN
Me2CuLi · LiI
H
78
92
95
66
94
83
85
83
33:67
>99:<1
60:40
>99:<1
40:60
Ϫ
8
H
9
tBu2CuLi · LiCN
Me2CuLi · LiI
H
10
11
12
13
14
H
tBu2CuLi · LiCN
Me2CuLi · LiI
11j
H
Ph
11k
11l
11m
(CH2)4
(CH2)4
H
6
tBu2CuLi · LiCN
tBu2CuLi · LiCN
Ϫ
>99:<1
8
Me
[a] Formation of a 1:1-mixture of 11a and the corresponding “reduced” vinylallene with R6 ϭ H (see text).
Next, we examined the possible influence of the substitu- in these cases, the reactions with the methyl and tert-butyl
ent at the triple bond of the enyne acetate on the course cuprates proceeded with the desired regioselectivity to give
of the substitution. The reaction of the phenyl-substituted the vinylallenes with good (11i) to excellent yields (11g, h,
acetate 2b with tBu2CuLi · LiCN, as well as the reactions j), and the substitution products formed from tBu2CuLi ·
of the silylated substrate 2c with both the n-butyl and tert- LiCN were isolated with (E)/(Z) ratios of about 1:1. How-
butyl cuprate, proceeded without difficulty to give the 1,5- ever, distinct differences from the previous results were ob-
substitution products 11cϪe with high chemical yields and served in the reactions of 4b/c with lithium dimethylcuprate
(E)/(Z) ratios around 1:1 (Table 1, entries 3Ϫ5). Thus, the (Me2CuLi · LiI): no reduction products with R6 ϭ H were
introduction of bulky or electron-releasing groups at this formed, and the vinylallenes 11g/i were isolated as (E)-iso-
position does not alter the course of the reaction with mers exclusively. The configuration of the olefinic double
3
organocuprates. The structural assignment was again made bond was assigned with the vicinal coupling constant JH,H
as outlined above with the typical coupling constants and (15.0/15.8 Hz), and also the characteristic chemical shifts in
chemical shifts (see Experimental Section). A surprising ob- the 1H- and 13C-NMR spectra (see above) were observed as
servation was then made when we tried to prepare the vinyl- expected. The reactions of the remaining enyne acetates 6
allene 11a by addition of lithium dimethylcuprate and 8 with the cuprates Me2CuLi · LiI or tBu2CuLi · LiCN
(Me2CuLi · LiI) to the n-butyl-substituted acetate 4a (entry (Table 1, entries 12Ϫ14) confirm the observations made
6): the desired product was formed, but only as a 1:1-mix- with the previous substrates: the regioselectivity does not
ture with the corresponding “reduced” vinylallene bearing depend on the structure of the reactants, and in all cases
a hydrogen atom instead of a methyl group at C-6 (i.e. R6 ϭ 1,5-substitution takes place exclusively to give the vinylal-
H). Both products were obtained as 2:1 mixtures of (E/Z)- lenes 11kϪm with good yields (83Ϫ85%). In the case of the
isomers with a combined yield of 80%. A similar product acyclic vinylallene 11m, only one isomer was formed which,
3
mixture was isolated when the cyano-Gilman reagent Me2- according to the vicinal coupling constant J2,3 ϭ 15.5 Hz,
CuLi · LiCN was used. There is some precedent for the has the (E)-configuration.
formation of (formal) reduction products in organocopper
So far, our study has shown that the 1,5-substitution of
chemistry[8b,11] (also in substitution reactions of propargylic enynoic acetates is a general method for the generation of
electrophiles[11c,11f]), and this has been attributed to elec- vinylallenes with different substitution patterns. Although
tron transfer processes, reactions of copper hydride species these products were often formed as mixtures of (E/Z)-iso-
or protonation of organometallic intermediates. Interest- mers, pure (E)-vinylallenes could be obtained in some cases.
ingly, with enyne acetates as substrates reduction only oc- We then extended our studies to the enyne oxiranes 10a/b
curred when methyl cuprates were employed as reagents. which were treated with lithium dimethylcuprate (Me2CuLi
Thus, the reaction of 4a with the tert-butyl cuprate tBu2- · LiI) or tBu2CuLi · LiCN under the usual conditions. It
CuLi · LiCN under the usual conditions (diethyl ether, turned out that both substrates react cleanly with the tert-
Ϫ80°C) proceeded cleanly to give the vinylallene 11f as a butyl cuprate to give the vinylallenes 12 with good yields
1:2-mixture of (E/Z)-isomers with 78% yield (Table 1, entry (61Ϫ72%); whereas 12a was obtained as (E)-isomer only,
7). Again, the characteristic 13C-NMR resonances of C-4 an (E)/(Z) ratio of 80:20 was determined for 12b. In the
at δ ϭ 96.3 and 91.7 served for the assignment of the geo- latter case, the (E)-configuration of the major isomer was
metrical isomers.
assigned with NOE experiments which confirmed the prox-
Until now, only enyne acetates with R4 ϭ Me had been imity of 1-H and 3-H, as well as of the methyl group at C-
used as substrates for 1,5-substitutions; we next extended 2 and 4-H (see Experimental Section). The unpredictable
our study to the acetates 4b/c with tert-butyl and phenyl behavior of lithium dimethylcuprate in these transforma-
groups, respectively, at this position (entries 8Ϫ11). Also tions was again unraveled when oxirane 10b was treated
Eur. J. Org. Chem. 1999, 267Ϫ275
269

M. Purpura, N. Krause
FULL PAPER
with this reagent: exclusive reduction to the vinylallene 13 entry 2), vinylallene 11b was formed as a 1:3 mixture of
took place, which was isolated with 54% yield as single iso- (E/Z)-isomers, and the GC analysis with octakis(2,6-di-O-
mer. The similarity of the NMR data with those of (E)-12b methyl-3-O-pentyl)-γ-cyclodextrin as chiral stationary
let us assume that this also possesses the (E)-configuration. phase revealed enantiomeric excesses of 20% ee for (E)-11b
and 74% ee for (Z)-11b. Thus, the 1,5-substitution of chiral
enyne acetates does indeed take place enantioselectively
with remote stereocontrol.
Scheme 7
Scheme 6
Conclusion
Finally, we wanted to establish whether the 1,5-substi-
tutions of enyne electrophiles can also be carried out with
In this work we have shown that 1,5-(SN2ЈЈ)-substitutions
of enyne acetates and oxiranes with organocuprates take
catalytic amounts of copper salts, and whether they take
place with complete regiocontrol to provide vinylallenes, re-
place enantioselectively with chirality transfer from the sub-
gardless of the steric and electronic properties of the reac-
tants. With lithium dimethylcuprate, however, reduced vi-
nylallenes originating from a (formal) transfer of a hydride
ion to the substrate are formed in some cases. The products
are usually obtained as mixtures of (E/Z)-isomers; however,
pure (E)-vinylallenes are formed occasionally. We were also
able to show that the 1,5-substitution of chiral enyne ace-
tates proceeds enantioselectively, so that this reaction con-
strate to the vinylallene. Complex product mixtures were
obtained when enyne acetate 2a was treated with nBuMgCl
or tBuMgCl in the presence of catalytic amounts of CuCl
according to procedures for SN2Ј-substitutions of propar-
gylic acetates[3], and the use of stoichiometric amounts of
magnesium cuprates R2CuMgCl (prepared from 2 equiv. of
Grignard reagents and 1 equiv. of copper salts) gave rise to
the formation of the SN2Ј-(1,3)-substitution product. These
findings clearly indicate that the presence of lithium cup-
stitutes a new type of remote stereocontrol. Further work
will be devoted to the optimization of a catalytic version of
rates is essential for the desired 1,5-substitutions. Accord-
these transformations, as well as to the investigation of the
ingly, we tested a different procedure which has been used
chirality transfer and the determination of the absolute con-
successfully in catalytic 1,6-addition reactions to acceptor-
figuration of the products.
substituted enynes,[2b] i.e. the simultaneous addition of sub-
strate and organolithium reagent to catalytic amounts of
the cuprate. Indeed, the reaction of 2a with 1 equiv. of
tBuLi and 10 mol% of tBu2CuLi · LiI in diethyl ether at
Experimental Section
General Information: NMR spectra were recorded with a Bruker
Ϫ50°C under these conditions proceeded cleanly to give vi-
nylallene 11b with 90% yield as 1:2 mixture of (E/Z) iso-
WM 400 spectrometer at 400 MHz (1H) and 100.6 MHz (13C) in
1
CDCl3 as solvent and internal standard (δ ϭ 7.27 for H, δ ϭ 77.05
mers. Thus, the 1,5-substitutions can also be performed ef-
for 13C). The signals of a major component of a product mixture
ficiently with reduced amounts of organolithium and cop-
are marked with an asterisk (*). Ϫ IR spectra were obtained with
per reagents; it is reasonable to assume that the cuprate
a Perkin-Elmer 1600 FT-IR spectrometer, mass spectra with A.E.I.
R2CuLi is also responsible for the product formation in the
MS-30 and MS-50 spectrometers (EI, 70 eV). GC-MS spectra were
catalytic procedure, and it is regenerated continuously by
reaction of the organocopper reagent RCu produced in the
1,5-substitution with the added RLi.
recorded with a Hewlett Packard HP 5850 Series II spectrometer.
Ϫ GC analyses were carried out with a Dani 86.10 or a Carlo Erba
GC 8000 gaschromatograph with hydrogen as carrier gas and OV-
1701 or octakis(2,6-di-O-methyl-3-O-pentyl)-γ-cyclodextrin capil-
lary colums. Ϫ Elemental analyses were obtained with Perkin-
Elmer CHN 240 A and B analyzers. Due to their tendency to poly-
merization and oxidation, correct elemental analyses of the vinyl-
allenes prepared in this work could not be obtained; instead, they
were characterized by high-resolution mass spectra (HRMS), and
GC analysis showed them to be at least 90% pure. Ϫ The reactions
were carried out in thoroughly dried glassware under argon. Di-
ethyl ether was distilled from LiAlH4 prior to use. MeLi, nBuLi,
and tBuLi were titrated with diphenylacetic acid according to the
In order to explore whether the 1,5-substitution of chiral
enyne acetates takes place enantioselectively with efficient
chirality transfer from the center of chirality of the sub-
strate to the stereogenic axis of the vinylallene, the enanti-
omerically pure enyne acetate (R)-2a (> 96% ee by GC
analysis) was generated by kinetic deracemization of the ra-
cemic acetate in the presence of the lipase from Pseudo-
monas fluorescens. In a preliminary experiment, this was
treated with the cyano-Gilman reagent tBu2CuLi · LiCN;
as in the corresponding reaction of racemic 2a (Table 1, procedure of Kofron and Baclawski.[12]
270 Eur. J. Org. Chem. 1999, 267Ϫ275

Regio- and Stereoselective Synthesis of Vinylallenes
FULL PAPER
2-Acetoxy-3-hepten-5-yne (2a): The crude aldehyde 1a prepared
from 6.91 g (50.0 mmol) of ethyl 2-hexen-4-ynoate according to
ref.[7] was dissolved in 100 mL of diethyl ether and treated at
ethyl ether) and 12.2 g (0.12 mol) of acetic anhydride. Yield: 6.30
g (50%) of 2c as colorless oil after purification by column chroma-
1
tography (SiO2, cyclohexane/diethyl ether, 10:1). Ϫ H NMR: δ ϭ
Ϫ80°C with 17 mL (51.0 mmol) of MeMgBr (3.0  in diethyl 6.10 (dd, J ϭ 16.0/6.4 Hz, 1 H, 3-H), 5.69 (dd, J ϭ 16.0/1.2 Hz, 1
ether). Within 2 h the mixture was warmed with stirring to Ϫ40°C H, 4-H), 5.33 (qid, J ϭ 6.4/1.2 Hz, 1 H, 2-H), 2.02 (s, 3 H, OC-
and then hydrolyzed by addition of 30 mL of a saturated NH4Cl OCH3), 1.28 (d, J ϭ 6.4 Hz, 1 H, 1-H), 0.15 [s, 9 H, Si(CH3)3]. Ϫ
solution. After extraction with diethyl ether, the combined organic
layers were washed with water and dried with MgSO4. The solvent
was removed in vacuo, and the crude alcohol thus obtained was
dissolved in 150 mL of diethyl ether and treated with 10.2 g (0.10
mol) of acetic anhydride and a small amount of 4-(dimethylamino)-
13C NMR: δ ϭ 170.4 (x, CϭO), 143.4 (ϩ, C-3), 111.4 (ϩ, C-4),
101.8 (x, C-6), 96.2 (x, C-5), 70.1 (ϩ, C-2), 21.4 (ϩ, C-1), 20.3
(ϩ,OCOCH3), 0.1 [ϩ, Si(CH3)3]. Ϫ IR: ν˜ ϭ 2978 cmϪ1 (s, CϪH),
2252 (m, CϵC), 1735 (s, CϭO), 1240 (s, CϪOϪC). Ϫ MS: m/z
(%) ϭ 210 (21) [Mϩ], 195 (16) [M Ϫ CH3], 167 (59), 73 (100).
pyridine (DMAP). After stirring for 2 h at room temperature, 10 Ϫ C11H18O2Si (210.34): calcd. C 62.81, H 8.63; found C 62.95,
mL of methanol was added, and the mixture was stirred for an-
other 15 min before neutralization with a saturated NaHCO3 solu-
tion. Separation of the layers was followed by washing of the aque-
ous phase with diethyl ether. The combined organic layers were
dried with K2CO3; the crude product obtained removal of the sol-
vent in vacuo was purified by column chromatography (SiO2, cyclo-
hexane/diethyl ether, 10:1) to give 5.60 g (74%) of 2a as colorless
H 9.34.
2-Acetoxy-3-decen-5-yne (4a): 7.50 g (50.0 mmol) of ketone 3a (pre-
pared with 96% yield by olefination of 2-heptynal[13] with (di-
ethoxyphosphoryl)acetone[15] in the presence of K2CO3/H2O[16]) in
50 mL of diethyl ether was added dropwise at Ϫ60°C to a stirred
suspension of 1.90 g (50.0 mmol) of LiAlH4 in 100 mL of diethyl
ether. After stirring for 1 h at Ϫ60°C, 20 mL of a saturated NH4Cl
solution was added dropwise with vigorous stirring and the mixture
was filtered through Celite. The crude alcohol obtained after re-
moval of the solvent in vacuo was esterified according to the pro-
cedure given for 2a by treatment with 10.2 g (0.10 mol) of acetic
anhydride. Chromatographic purification (SiO2, cyclohexane/di-
ethyl ether, 10:1) gave 9.00 g (93%) of 4a as yellow oil. Ϫ 1H NMR:
δ ϭ 5.95 (dd, J ϭ 15.9/6.5 Hz, 1 H, 3-H), 5.65 (d, J ϭ 15.9 Hz, 1
H, 4-H), 5.32 (qi, J ϭ 6.5 Hz, 1 H, 2-H), 2.27 (t, J ϭ 5.1 Hz, 2 H,
7-H), 2.01 (s, 3 H, OCOCH3), 1.98Ϫ1.32 (m, 4 H, 8/9-H), 1.27 (d,
J ϭ 6.4 Hz, 1 H, 1-H), 0.89 (t, J ϭ 6.9 Hz, 3 H, 10-H). Ϫ 13C
NMR: δ ϭ 170.1 (x, CϭO), 140.2 (ϩ, C-3), 112.1 (ϩ, C-4), 92.1
(x, C-6), 77.9 (x, C-5), 70.2 (ϩ, C-2), 30.7 (Ϫ, C-8), 21.9 (Ϫ, C-7),
21.2 (ϩ, C-1), 19.9 (ϩ, OCOCH3), 19.0 (Ϫ, C-9), 13.6 (ϩ, C-10).
Ϫ IR: ν˜ ϭ 2932 cmϪ1 (s, CϪH), 2216 (m, CϵC), 1742 (s, CϭO),
1237 (s, CϪOϪC). Ϫ MS: m/z (%) ϭ 194 (20) [Mϩ], 179 (9) [M Ϫ
CH3], 151 (71) [M Ϫ COCH3], 95 (100). Ϫ C9H12O2 (194.27): calcd.
C 74.19, H 9.34; found C 74.15, H 9.61.
1
oil. Ϫ H NMR: δ ϭ 5.96 (dd, J ϭ 15.9/6.5 Hz, 1 H, 3-H), 5.67
(dq, J ϭ 15.9/2.2 Hz, 1 H, 4-H), 5.33 (qi, J ϭ 6.5 Hz, 1 H, 2-H),
2.02 (s, 3 H, OCOCH3), 1.92 (d, J ϭ 2.2 Hz, 3 H, 7-H), 1.28 (d,
J ϭ 6.5 Hz, 1 H, 1-H). Ϫ 13C NMR: δ ϭ 170.1 (x, CϭO), 140.4
(ϩ, C-3), 112.0 (ϩ, C-4), 96.1 (x, C-6), 77.2 (x, C-5), 70.2 (ϩ, C-
2), 21.3 (ϩ,C-1), 20.0 (ϩ,OCOCH3), 4.3 (ϩ, C-7). Ϫ IR: ν˜ ϭ 2921
cmϪ1 (s, CϪH), 2222 (m, CϵC), 1743 (s, CϭO), 1237 (s, CϪOϪC).
Ϫ MS: m/z (%) ϭ 152 (13) [Mϩ], 137 (25) [M Ϫ CH3], 109 (73) [M
Ϫ COCH3], 91 (100). Ϫ C9H12O2 (152.19): calcd. C 71.03, H 7.95;
found C 70.66, H 8.02.
2-Acetoxy-6-phenyl-3-hexen-5-yne (2b): Crude phenylpropynal was
prepared from 6.13 g (60.0 mmol) of phenylacetylene according to
ref.[13] and dissolved in 50 mL of THF. After addition of 1.36 g
(6.0 mmol) of anhydrous ZnBr2, a solution of 14.6 g (60.0 mmol)
of α,α-bis(trimethylsilyl)-tert-butylacetaldimine[14] in 25 mL of
THF was added dropwise with stirring. The mixture was stirred for
1 h at room temperature and then treated with 120 mL of diethyl
ether and a solution of 10.0 g (74.0 mmol) of ZnCl2 in 100 mL of
water. After stirring for another hour at room temperature, the
mixture was filtered through Celite, and the layers were separated.
The aqueous layer was washed with diethyl ether, and the combined
organic layers were washed with water and dried with MgSO4. Re-
moval of the solvent in vacuo gave crude aldehyde 1b which was
converted into acetate 2b according to the procedure given for 2a
by treatment with 38 mL (61 mmol) of MeLi (1.6  solution in
diethyl ether) and 12.2 g (0.12 mol) of acetic anhydride. Yield: 6.70
g (52%) of 2b as colorless oil after purification by column chroma-
3-Acetoxy-2,2-dimethyl-4-undecen-6-yne (4b): The reduction of 6.92
g (36.0 mmol) of ketone 3b (obtained with 87% yield from 2-hep-
tynal[13] and 1-(diethoxyphosphoryl)-3,3-dimethyl-2-butanone[15]
according to ref.[16]) with 1.37 g (36.0 mmol) of LiAlH4 and the
subsequent esterification with 7.40 g (72.0 mmol) of acetic anhy-
dride was carried out as described for 4a and provided 8.00 g (94%)
of 4b as yellow oil after chromatographic purification of the crude
1
product (SiO2, cyclohexane/diethyl ether, 10:1). Ϫ H NMR: δ ϭ
5.93 (dd, J ϭ 16.0/7.6 Hz, 1 H, 4-H), 5.63 (dm, J ϭ 16.0 Hz, 1 H,
5-H), 4.96 (dd, J ϭ 7.6/1.0 Hz, 1 H, 3-H), 2.27 (td, J ϭ 6.6/2.0 Hz,
2 H, 8-H), 2.03 (s, 3 H, OCOCH3), 1.52Ϫ1.33 (m, 4 H, 9/10-H),
0.88 [s, 9 H, C(CH3)3], 0.84 (t, J ϭ 7.3 Hz, 3 H, 11-H). Ϫ 13C
NMR: δ ϭ 170.2 (x, CϭO), 136.6 (ϩ, C-4), 114.1 (ϩ, C-5), 91.7
(x, C-7), 80.9 (ϩ, C-3), 78.2 (x, C-6), 34.5 (x, C-2), 30.7 (Ϫ, C-8),
25.7 [ϩ, C(CH3)3], 22.0 (ϩ, OCOCH3), 21.1 (Ϫ, C-9), 19.1 (Ϫ, C-
10), 13.6 (ϩ, C-11). Ϫ IR: ν˜ ϭ 2958 cmϪ1 (s, CϪH), 2144 (m,
CϵC), 1742 (s, CϭO), 1251 (s, CϪOϪC). Ϫ MS: m/z (%) ϭ 236
(8) [Mϩ], 179 (10), 152 (11), 137 (100). Ϫ C15H24O2 (236.35): calcd.
C 76.23, H 10.23; found C 76.10, H 10.37.
1
tography (SiO2, cyclohexane/diethyl ether, 10:1). Ϫ H NMR: δ ϭ
7.42Ϫ7.30 (m, 5 H, Phenyl-H), 6.17 (dd, J ϭ 16.0/6.4 Hz, 1 H, 3-
H), 5.92 (dd, J ϭ 16.0/1.2 Hz, 1 H, 4-H), 5.43 (qid, J ϭ 6.4/1.2
Hz, 1 H, 2-H), 2.07 (s, 3 H, OCOCH3), 1.36 (d, J ϭ 6.4 Hz, 1 H,
1-H). Ϫ 13C NMR: δ ϭ 170.2 (x, CϭO), 141.8 (ϩ, C-3), 131.6 (ϩ,
C-2Ј), 128.5/128.4 (ϩ, C-3Ј/4Ј), 123.1 (x, C-1Ј), 111.4 (ϩ, C-4), 90.8
(x, C-6), 86.9 (x, C-5), 70.1 (ϩ, C-2), 21.3 (ϩ,C-1), 20.0
(ϩ,OCOCH3). Ϫ IR: ν˜ ϭ 2958 cmϪ1 (s, CϪH), 2144 (m, CϵC),
1742 (s, CϭO), 1251 (s, CϪOϪC). Ϫ MS: m/z (%) ϭ 214 (24) [Mϩ],
199 (18) [M Ϫ CH3], 171 (100), 153 (50). Ϫ C14H14O2 (214.26):
calcd. C 78.48, H 6.59; found C 78.46 H 6.70.
1-Acetoxy-1-phenyl-2-nonen-4-yne (4c): The reduction of 7.00 g
(33.0 mmol) of ketone 3c (obtained with 79% yield from 2-hep-
tynal[13] and 2-(diethoxyphosphoryl)-1-phenylethanone[15] accord-
ing to ref.[16]) with 1.30 g (33.0 mmol) of LiAlH4 and the sub-
sequent esterification with 6.70 g (66.0 mmol) of acetic anhydride
was carried out as described for 4a and provided 8.20 g (97%) of
4c as orange oil after chromatographic purification of the crude
2-Acetoxy-6-trimethylsilyl-3-hexen-5-yne (2c): According to the
procedure given for 2b, crude 3-trimethylsilylpropynal prepared
from 5.89 g (60.0 mmol) of trimethylsilylacetylene was converted
into enyne acetate 2c by treatment with 1.36 g (6.0 mmol) of anhy-
drous ZnBr2, 14.6 g (60.0 mmol) of α,α-bis(trimethylsilyl)-tert-bu-
tylacetaldimine, 38 mL (61 mmol) of MeLi (1.6  solution in di-
Eur. J. Org. Chem. 1999, 267Ϫ275
271

M. Purpura, N. Krause
FULL PAPER
1
product (SiO2, cyclohexane/diethyl ether, 10:1). Ϫ H NMR: δ ϭ
7.24Ϫ7.17 (m, 5-H, Phenyl-H), 6.19 (dd, J ϭ 6.4/1.0 Hz, 1 H, 1-
H), 6.06 (dd, J ϭ 15.8/6.4 Hz, 1 H, 2-H), 5.63 (dm, J ϭ 15.8 Hz,
1 H, 3-H), 2.20 (td, J ϭ 6.9/2.2 Hz, 2 H, 6-H), 2.01 (s, 3 H, OC-
OCH3), 1.45Ϫ1.25 (m, 4 H, 7/8-H), 0.82 (t, J ϭ 7.2 Hz, 3 H, 9-H).
5.4/4.2 Hz, 1 H, 1-H), 2.62 (dd, J ϭ 5.4/2.7 Hz, 1 H, 1-H), 2.27
(td, J ϭ 6.9/2.0 Hz, 2 H, 7-H), 1.54Ϫ1.29 (m, 4 H, 8/9-H), 0.88 (t,
J ϭ 7.2 Hz, 3 H, 10-H). Ϫ 13C NMR: δ ϭ 138.5 (ϩ, C-3), 114.7
(ϩ, C-4), 96.8 (x, C-6), 78.0 (x, C-5), 51.8 (ϩ, C-2), 49.0 (Ϫ, C-1),
30.6 (Ϫ, C-8), 21.9 (Ϫ, C-9), 19.0 (Ϫ, C-7), 13.5 (ϩ, C-10). Ϫ IR:
Ϫ
13C NMR: δ ϭ 170.0 (x, CϭO), 138.8 (ϩ, C-2), 138.4 (x, Phen- ν˜ ϭ 2956 cmϪ1 (s, CϪH), 2214 (m, CϵC), 1633 (m, CϭC). Ϫ MS:
yl), 128.6, 128.3, 127.2 (3ϩ, Phenyl), 113.2 (ϩ, C-3), 92.8 (x, C-5),
80.0 (x, C-4), 75.4 (ϩ, C-1), 30.7 (Ϫ, C-6), 21.9 (Ϫ, C-7), 21.2 (ϩ,
OCOCH3), 19.1 (Ϫ, C-8), 13.6 (ϩ, C-9). Ϫ IR: ν˜ ϭ 2957 cmϪ1 (s,
CϪH), 2217 (m, CϵC), 1740 (s, CϭO), 1229 (s, CϪOϪC). Ϫ MS:
m/z (%) ϭ 256 (19) [Mϩ], 241 (5) [M Ϫ CH3], 214 (54), 105 (100). Ϫ
C17H20O2 (256.34): calcd. C 79.65, H 7.86; found C 79.27, H 8.24.
m/z (%) ϭ 150 (16) [Mϩ], 135 (5) [M Ϫ CH3], 108 (41), 79 (100).
Ϫ C10H14O (150.22): calcd. C 79.96, H 9.39; found C 80.19, H 9.37.
1-Methyl-1-(1-octen-3-yn-1-yl)oxirane (10b): According to the pro-
cedure given for 10a, treatment of 6.40 g (42.0 mmol) of 3a with
10.0 g (64.0 mmol) of trimethylsulfonium bromide, 16.9 g (0.26
mol) of K2CO3, and 0.20 g (11.0 mmol) of water furnished 5.60 g
(81%) of 10b as red oil after purification of the crude product by
column chromatography (SiO2, cyclohexane/diethyl ether, 10:1). Ϫ
1H NMR: δ ϭ 5.77 (d, J ϭ 16.0 Hz, 1 H, 3-H), 5.73 (dt, J ϭ 16.0/
2.0 Hz, 1 H, 4-H), 2.79 (d, J ϭ 5.2 Hz, 1 H, 1-H), 2.70 (dd, J ϭ
5.2/0.5 Hz, 1 H, 1-H), 2.28 (td, J ϭ 6.9/2.0 Hz, 2 H, 7-H),
1.60Ϫ1.24 (m, 4 H, 8/9-H), 1.41 (d, J ϭ 0.5 Hz, 3 H, 2-CH3), 0.89
(t, J ϭ 7.2 Hz, 3 H, 10-H). Ϫ 13C NMR: δ ϭ 142.0 (ϩ, C-3), 112.3
(ϩ, C-4), 92.4 (x, C-6), 78.1 (x, C-5), 56.1 (Ϫ, C-1), 55.4 (x, C-2),
30.7 (Ϫ, C-8), 21.9 (Ϫ, C-9), 19.3 (ϩ, 2-CH3), 19.0 (Ϫ, C-7), 13.6
(ϩ, C-10). Ϫ IR: ν˜ ϭ 2956 cmϪ1 (s, CϪH), 2214 (m, CϵC), 1682
(m, CϭC). Ϫ MS: m/z (%) ϭ 164 (11) [Mϩ], 149 (4) [M Ϫ CH3],
122 (62), 79 (100). Ϫ C11H16O (164.25): calcd. C 80.44, H 9.82;
found C 80.50, H 9.64.
1-Acetoxy-2-(2-heptynyliden)cyclohexene (6): The reduction of 7.40
g (39.0 mmol) of ketone 5[17] with 1.50 g (39.0 mmol) of LiAlH4
and the subsequent esterification with 8.00 g (78.0 mmol) of acetic
anhydride was carried out as described for 4a and provided 7.00 g
(77%) of 6 as yellow oil after chromatographic purification of the
crude product (SiO2, cyclohexane/diethyl ether, 10:1). Ϫ 1H NMR:
δ ϭ 5.36 (s, 1 H, 1Ј-H), 5.17 (m, 1 H, 1-H), 2.32Ϫ2.16 (m, 3 H, 4Ј-
H), 2.01 (s, 3 H, OCOCH3), 2.10Ϫ1.28 (m, 12 H, 3/4/5/6/5Ј/6Ј-H ),
0.86 (t, J ϭ 7.0 Hz, 3 H, 7Ј-H). Ϫ 13C NMR: δ ϭ 169.8 (x, Cϭ
O), 149.0 (x, C-2), 103.1 (ϩ, C-1Ј), 94.4 (x, C-3Ј), 76.8 (x, C-2Ј),
74.0 (ϩ, C-1), 33.2 (Ϫ, C-6), 30.8 (ϩ, C-5Ј), 29.1 (Ϫ, C-3), 26.5
(Ϫ, C-4), 22.8 (Ϫ, C-5), 21.8 (Ϫ, C-6Ј), 21.0 (ϩ,OCOCH3), 19.1
(Ϫ, C-4Ј), 13.5 (ϩ, C-7Ј). Ϫ IR: ν˜ ϭ 2933 cmϪ1 (s, CϪH), 2212 (w,
CϵC), 1740 (s, CϭO), 1236 (s, CϪOϪC). Ϫ MS: m/z (%) ϭ 234
(19) [Mϩ], 219 (4) [M Ϫ CH3], 191 (36) [M Ϫ COCH3], 91 (100). Ϫ
C15H22O2 (234.33): calcd. C 76.88, H 9.46; found C 76.44, H 9.68.
General Procedure for the Preparation of Vinylallenes by 1,5-Substi-
tution of Enyne Acetates and Oxiranes with Organocuprates: To a
suspension of 1.5Ϫ2.0 equiv. of copper(I) iodide or copper(I) cyan-
ide in diethyl ether 3.0Ϫ4.0 equiv. of the organolithium compound
in diethyl ether (MeLi), hexane (nBuLi), or pentane (tBuLi) is ad-
ded dropwise at Ϫ20 to Ϫ30°C under argon. After 15 min stirring
at this temperature, the cuprate solution is cooled to Ϫ80°C, and
1.0 equiv. of the enyne in diethyl ether is added. The mixture is
stirred at Ϫ60 to Ϫ80°C, and the reaction is monitored by GC and
TLC. After complete consumption of the starting material (1Ϫ3
h), 5Ϫ10 mL of a saturated NH4Cl solution is added, the mixture
is warmed up to room temp. and filtered through Celite. The sol-
vent is removed in vacuo, and the crude vinylallene is purified by
column chromatography (SiO2, cyclohexane).
2-Acetoxy-4-methyl-3-hexen-5-yne (8): To a solution of 3.80 g (39.0
mmol) of 7 in 150 mL of diethyl ether was added 68.0 g (0.75 mol)
of activated MnO2 (Merck), and the mixture was stirred for 4 h at
room temperature. After filtration through Celite, most of the sol-
vent was removed by distillation. The conversion of the crude alde-
hyde thus obtained into acetate 8 was carried out according to the
procedure given for 2a by treatment with 13 mL (39 mmol) of
MeMgBr (3.0  solution in diethyl ether) and 8.00 g (78.0 mmol)
of acetic anhydride. Yield: 3.80 g (64%) of 8 as yellow oil after
purification by column chromatography (SiO2, cyclohexane/diethyl
ether, 10:1). Ϫ 1H NMR: δ ϭ 5.82 (dd, J ϭ 8.9/1.2 Hz, 1 H, 3-H),
5.56 (dq, J ϭ 8.9/6.5 Hz, 1 H, 2-H), 2.80 (s, 1 H, 6-H), 2.01 (s, 3
H, OCOCH3), 1.87 (d, J ϭ 1.2 Hz, 3 H, 4-CH3), 1.27 (d, J ϭ 6.5
Hz, 3 H, 1-H). Ϫ 13C NMR: δ ϭ 170.2 (x, CϭO), 137.6 (ϩ, C-3),
120.0 (x, C-4), 85.6 (ϩ, C-6), 75.7 (x, C-5), 67.0 (ϩ, C-2), 21.2 (ϩ,
C-1), 20.1 (ϩ,OCOCH3), 17.6 (ϩ, 4-CH3). Ϫ IR: ν˜ ϭ 3290 cmϪ1
(s, CϵC-H), 2097 (w, CϵC), 1730 (s, CϭO), 1240 (s, CϪOϪC). Ϫ
MS: m/z (%) ϭ 152 (7) [Mϩ], 137 (27) [M Ϫ CH3], 109 (86) [M Ϫ
COCH3], 91 (100). Ϫ C9H12O2 (152.19): calcd. C 71.03, H 7.95;
found C 70.90, H 8.21.
6-Methyl-2,4,5-decatriene (11a): From 152 mg (1.0 mmol) of 2a in
10 mL of diethyl ether, 381 mg (2.0 mmol) of CuI in 20 mL of
diethyl ether and 2.5 mL (4.0 mmol) of nBuLi (1.6  in hexane).
Yield: 135 mg (90%) of 11a (2:1 mixture of (E/Z)-isomers according
1
to GC analysis) as a colorless liquid. Ϫ H NMR: δ ϭ 6.10Ϫ5.35
(m, 3 H, 2/3/4-H), 2.05Ϫ1.91 (m, 2 H, 7-H), 1.76Ϫ1.68 (m, 6 H, 1-
H/6-CH3), 1.47Ϫ1.31 (m, 4 H, 8/9-H), 0.89 (t, J ϭ 6.9 Hz, 3 H,
10-H). Ϫ 13C NMR: δ ϭ 203.5 (x, C-5), 128.2*/126.1 (ϩ, C-2),
126.0*/124.1 (ϩ, C-3), 100.6*/ 100.5 (x, C-6), 93.2*/88.6 (ϩ, C-4),
33.8 (Ϫ, C-7), 29.7 (Ϫ, C-8), 22.4 (Ϫ, C-9), 19.2*/19.0 (ϩ, 6-CH3),
13.1 (ϩ, C-1), 14.0 (ϩ, C-10). Ϫ IR: ν˜ ϭ 2925 cmϪ1 (s, CϪH),
1948 (m, CϭCϭC), 1450 (m, CϭC). Ϫ MS: m/z (%) ϭ 150 (6)
[Mϩ], 135 (4) [M Ϫ CH3], 100 (48), 93 (100). Ϫ HRMS (C11H18):
calcd. 150.1408; found 150.1406.
(1-Octen-3-yn-1-yl)oxirane (10a):[9,18] A mixture of 11.7 g (75.0
mmol) of trimethylsulfonium bromide, 19.7 g (0.30 mol) of K2CO3,
and 0.23 g (12.0 mmol) of water in 70 mL of acetonitrile was stirred
for 5 min at 60°C. With vigorous stirring, a solution of 6.70 g (49.0
mmol) of 9 (prepared from 2-heptynal[13] according to ref.[14]) in
25 mL of acetnitrile was added dropwise, and stirring was con-
6,7,7-Trimethyl-2,4,5-octatriene (11b): From 152 mg (1.0 mmol) of
tinued for further 2 h at 60°C. After cooling to room temp., the 2a in 10 mL of diethyl ether, 135 mg (1.5 mmol) of CuCN in 20
mixture was filtered, and 50 mL of diethyl ether was added to the
filtrate which was filtered again. Washing of the filtrate with pen-
tane, removal of the solvent in vacuo and purification of the crude
mL of diethyl ether and 2.0 mL (3.0 mmol) of tBuLi (1.5  in
pentane). Yield: 140 mg (93%) of 11b (1:3 mixture of (E/Z)-isomers
according to GC analysis) as a colorless liquid. Ϫ (E)-11b: 1H
product by column chromatography (SiO2, cyclohexane/diethyl NMR: δ ϭ 5.82 (ddq, J ϭ 15.5/10.3/1.7 Hz, 1 H, 3-H), 5.70 (dq,
1
ether, 10:1) gave 5.90 g (80%) of 10a as red oil. Ϫ H NMR: δ ϭ J ϭ 10.3/2.9 Hz, 1 H, 4-H), 5.58 (dqd, J ϭ 15.5/6.6/0.5 Hz, 1 H,
5.85 (dt, J ϭ 16.0/2.0 Hz, 1 H, 4-H), 5.64 (dd, J ϭ 16.0/ 7.9 Hz, 1
2-H), 1.76Ϫ1.70 (m, 6 H, 1-H/6-CH3), 1.06 [s, 9 H, C(CH3)3]. Ϫ
H, 3-H), 3.29 (ddd, J ϭ 7.9/4.2/2.7 Hz, 1 H, 2-H), 2.94 (dd, J ϭ 13C NMR: δ ϭ 202.7 (x, C-5), 128.3 (ϩ, C-2), 125.5 (ϩ, C-3), 109.4
272
Eur. J. Org. Chem. 1999, 267Ϫ275

Regio- and Stereoselective Synthesis of Vinylallenes
FULL PAPER
(x, C-6), 93.6 (ϩ, C-4), 33.7 (x, C-7), 29.2 [ϩ, C(CH3)3], 18.1 (ϩ,
6-CH3), 13.1 (ϩ, C-1). Ϫ (Z)-11b: 1H NMR: δ ϭ 5.99 (dq, J ϭ
10.8/1.2 Hz, 1 H, 4-H), 5.81 (ddq, J ϭ 10.8/10.6/1.7 Hz, 1 H, 3-
H), 5.38 (dqd, J ϭ 10.6/7.1/1.2 Hz, 1 H, 2-H), 1.76Ϫ1.70 (m, 6 H,
1-H/6-CH3), 1.07 [s, 9 H, C(CH3)3]. Ϫ 13C NMR: δ ϭ 204.3 (x, C-
5), 126.3 (ϩ, C-2), 123.7 (ϩ, C-3), 109.2 (x, C-6), 89.1 (ϩ, C-4),
33.7 (x, C-7), 29.2 [ϩ, C(CH3)3], 18.1 (ϩ, 6-CH3), 15.0 (ϩ, C-1).
Ϫ IR: ν˜ ϭ 2962 cmϪ1 (s, CϪH), 1944 (m, CϭCϭC), 1450 (m, Cϭ
C). Ϫ MS: m/z (%) ϭ 150 (12) [Mϩ], 135 (5) [M Ϫ CH3], 84 (54),
57 (100). Ϫ HRMS (C11H18): calcd. 150.1408; found 150.1410.
in 40 mL of diethyl ether and 4.0 mL (6.0 mmol) of tBuLi (1.5 
in pentane). Yield: 300 mg (78%) of 11f (1:2 mixture of (E/Z)-
isomers according to GC analysis) as a colorless liquid. Ϫ 1H
NMR: δ ϭ 6.18Ϫ5.30 (m, 3 H, 2/3/4-H), 2.10Ϫ1.96 (m, 2 H, 7-H),
1.75 (d, J ϭ 6.9 Hz, 3 H, 1-H), 1.42Ϫ1.34 (m, 4 H, 8/9-H), 1.07 [s,
9 H, C(CH3)3], 0.92 (m, 3 H, 10-H). Ϫ 13C NMR: δ ϭ 203.8*/
202.3 (x, C-5), 128.5/126.6* (ϩ, C-2), 125.2/123.4* (ϩ, C-3), 114.8/
114.6* (x, C-6), 96.3/91.7* (ϩ, C-4), 33.9 [x, C(CH3)3], 30.5 (Ϫ, C-
7), 29.4 [ϩ, C(CH3)3], 27.5 (Ϫ, C-8), 26.9 (Ϫ, C-9), 18.1/13.1* (ϩ,
C-1), 14.1 (ϩ, C-10). Ϫ IR: ν˜ ϭ 2960 cmϪ1 (s, CϪH), 1936 (m,
CϭCϭC), 1463 (m, CϭC). Ϫ MS: m/z (%) ϭ 192 (1) [Mϩ], 177
(1) [M Ϫ CH3], 150 (16), 57 (100). Ϫ HRMS (C14H24): calcd.
192.1878; found 192.1884.
7,7-Dimethyl-6-phenyl-2,4,5-octatriene (11c): From 214 mg (1.0
mmol) of 2b in 8 mL of diethyl ether, 135 mg (1.5 mmol) of CuCN
in 20 mL of diethyl ether and 2.0 mL (3.0 mmol) of tBuLi (1.5 
in pentane). Yield: 170 mg (80%) of 11c (1:1 mixture of (E/Z)-
isomers according to GC analysis) as a colorless liquid. Ϫ (E)-11c:
1H NMR: δ ϭ 7.33Ϫ7.26 (m, 5 H, Phenyl-H), 6.24Ϫ5.41 (m, 3 H,
2/3/4-H), 1.75 (dd, J ϭ 6.9/1.7 Hz, 3 H, 1-H), 1.19 [s, 9 H,
C(CH3)3]. Ϫ 13C NMR: δ ϭ 204.2 (x, C-5), 137.8 (x, Phenyl), 129.5/
127.8/126.6/125.6/124.9 (5ϩ, C-2/3/Phenyl), 116.9 (x, C-6), 94.7 (ϩ,
C-4), 34.7 (x, C-7), 29.9 [ϩ, C(CH3)3], 13.3 (ϩ, C-1). Ϫ (Z)-11c:
1H NMR: δ ϭ 7.33Ϫ7.26 (m, 5 H, Phenyl-H), 6.24Ϫ5.41 (m, 3 H,
2/3/4-H), 1.78 (dd, J ϭ 6.4/1.5 Hz, 3 H, 1-H), 1.18 [s, 9 H,
C(CH3)3]. Ϫ 13C NMR: δ ϭ 205.6 (x, C-5), 137.8 (x, Phenyl), 129.5/
127.8/126.6/ 125.6/124.9 (5ϩ, C-2/3/Phenyl), 116.9 (x, C-6), 90.1
(ϩ, C-4), 34.7 (x, C-7), 29.9 [ϩ, C(CH3)3], 18.2 (ϩ, C-1). Ϫ IR:
ν˜ ϭ 2962 cmϪ1 (s, CϪH), 1939 (m, CϭCϭC), 1597 (m), 1450 (m,
CϭC). Ϫ MS: m/z (%) ϭ 212 (2) [Mϩ], 197 (2) [M Ϫ CH3], 84
(42), 57 (100). Ϫ HRMS (C16H20): calcd. 212.1565; found 212.1564.
(E)-2,2,7-Trimethyl-3,5,6-undecatriene (11g): From 473 mg (2.0
mmol) of 4b in 15 mL of diethyl ether, 762 mg (4.0 mmol) of CuI
in 30 mL of diethyl ether and 5.0 mL (8.0 mmol) of MeLi (1.6 
in diethyl ether). Yield: 354 mg (92%) of 11g as a colorless liquid.
1
Ϫ H NMR: δ ϭ 5.76 (dd, J ϭ 15.0/10.0 Hz, 1 H, 4-H), 5.69 (dq,
J ϭ 10.0/2.5 Hz, 1 H, 5-H), 5.61 (d, J ϭ 15.0 Hz, 1 H, 3-H), 1.97
(m, 2 H, 8-H), 1.70 (d, J ϭ 2.5 Hz, 3 H, 7-CH3), 1.42Ϫ1.30 (m, 4
H, 9/10-H), 1.04 (s, 9 H, C(CH3)3), 0.91 (t, J ϭ 7.1 Hz, 3 H, 11-
H). Ϫ 13C NMR: δ ϭ 203.8 (x, C-6), 142.5 (ϩ, C-3), 121.8 (ϩ, C-
4), 100.5 (x, C-7), 93.5 (ϩ, C-5), 33.9 (Ϫ, C-8), 33.2 (x, C-2), 29.6
[ϩ, C(CH3)3], 29.6 (Ϫ, C-9), 22.4 (Ϫ, C-10), 19.1 (ϩ, 7-CH3), 14.0
(ϩ, C-11). Ϫ IR: ν˜ ϭ 2956 cmϪ1 (s, CϪH), 1948 (m, CϭCϭC),
1461 (m, CϭC). Ϫ MS: m/z (%) ϭ 192 (4) [Mϩ], 177 (2) [M Ϫ
CH3], 150 (32), 107 (100). Ϫ HRMS (C14H24): calcd. 192.1878;
found 192.1881.
6-Trimethylsilyl-2,4,5-decatriene (11d): From 210 mg (1.0 mmol) of
2c in 8 mL of diethyl ether, 135 mg (1.5 mmol) of CuCN in 20 mL
of diethyl ether and 1.9 mL (3.0 mmol) of nBuLi (1.6  in hexane).
Yield: 167 mg (80%) of 11d (3:2 mixture of (E/Z)-isomers according
2,2-Dimethyl-7-(1,1-dimethylethyl)-3,5,6-undecatriene (11h): From
473 mg (2.0 mmol) of 4b in 10 mL of diethyl ether, 270 mg (3.0
mmol) of CuCN in 30 mL of diethyl ether and 4.0 mL (6.0 mmol)
of tBuLi (1.5  in pentane). Yield: 445 mg (95%) of 11h (3:2 mix-
ture of (E/Z)-isomers according to GC analysis) as a colorless
1
to GC analysis) as a colorless liquid. Ϫ H NMR: δ ϭ 5.86Ϫ5.24
(m, 3 H, 2/3/4-H), 1.99Ϫ1.92 (m, 2 H, 7-H), 1.74Ϫ1.69 (m, 3 H, 1-
H), 1.40Ϫ1.30 (m, 4 H, 8/9-H), 0.89 (m, 3 H, 10-H), 0.10/0.09* [s,
9 H, Si(CH3)3]. Ϫ 13C NMR: δ ϭ 208.1/207.1* (x, C-5), 127.5*//
125.7/124.4*/122.1 (ϩ, C-2/3), 97.9*/97.3 (x, C-6), 89.2*/84.7 (ϩ,
C-4), 31.8*/31.3 (Ϫ, C-7), 29.1/29.0 (Ϫ, C-8), 22.6/22.4* (Ϫ, C-9),
14.0 (ϩ, C-1), 13.9 (ϩ, C-10), 1.5 [ϩ, Si(CH3)3]. Ϫ IR: ν˜ ϭ 2958
cmϪ1 (s, CϪH), 1916 (m, CϭCϭC), 1250 (s). Ϫ MS: m/z (%) ϭ
208 (4) [Mϩ], 193 (2) [M Ϫ CH3], 137 (65), 56 (100). Ϫ HRMS
(C13H24Si): calcd. 208.1647; found 208.1639.
1
liquid. Ϫ (E)-11h: H NMR: δ ϭ 5.80 (dt, J ϭ 10.0/3.2 Hz, 1 H,
5-H), 5.72 (dd, J ϭ 15.0/10.0 Hz, 1 H, 4-H), 5.60 (d, J ϭ 15.0 Hz,
1 H, 3-H), 2.02Ϫ1.94 (m, 2 H, 8-H), 1.40Ϫ1.34 (m, 4 H, 9/10-H),
1.06 [s, 9 H, C(CH3)3], 1.04 [s, 9 H, C(CH3)3], 0.91 (m, 3 H, 11-H).
Ϫ
13C NMR: δ ϭ 202.5 (x, C-6), 141.9 (ϩ, C-3), 122.1 (ϩ, C-4),
114.8 (x, C-7), 96.6 (ϩ, C-5), 34.0 [x, C(CH3)3], 33.4 [x, C(CH3)3],
30.5 [ϩ, C(CH3)3], 29.8 (-, C-8), 29.3 [ϩ, C(CH3)3], 27.0 (-, C-9),
22.6 (-, C-10), 14.1 (ϩ, C-11). Ϫ (Z)-11h: 1H NMR: δ ϭ 6.29 (dm,
J ϭ 11.6 Hz, 1 H, 5-H), 5.62 (dd, J ϭ 11.8/11.6 Hz, 1 H, 4-H),
5.26 (d, J ϭ 11.8 Hz, 1 H, 3-H), 2.02Ϫ1.94 (m, 2 H, 8-H),
1.40Ϫ1Ϫ34 (m, 4 H, 9/10-H), 1.18 [s, 9 H, C(CH3)3], 1.05 [s, 9 H,
C(CH3)3], 0.91 (m, 3 H, 11-H). Ϫ 13C NMR: δ ϭ 203.8 (x, C-6),
139.2 (ϩ, C-3), 124.1 (ϩ, C-4), 114.3 (x, C-7), 93.2 (ϩ, C-5), 34.0
[x, C(CH3)3], 33.4 [x, C(CH3)3], 30.5 [ϩ,C(CH3)3], 29.8 (Ϫ, C-8),
29.7 [ϩ, C(CH3)3], 27.0 (Ϫ, C-9), 22.6 (Ϫ, C-10), 14.1 (ϩ, C-11).
Ϫ IR: ν˜ ϭ 2957 cmϪ1 (s, CϪH), 1935 (m, CϭCϭC), 1462 (m, Cϭ
C). Ϫ MS: m/z (%) ϭ 234 (<1) [Mϩ], 192 (11), 149 (13), 57 (100).
Ϫ HRMS (C17H30): calcd. 234.2347; found 234.2342.
7,7-Dimethyl-6-trimethylsilyl-2,4,5-octatriene (11e): From 210 mg
(1.0 mmol) of 2c in 8 mL of diethyl ether, 135 mg (1.5 mmol) of
CuCN in 20 mL of diethyl ether and 2.0 mL (3.0 mmol) of tBuLi
(1.5  in pentane). Yield: 200 mg (96%) of 11e (2:3 mixture of (E/
Z)-isomers according to GC analysis) as a colorless liquid. Ϫ (E)-
11e: 1H NMR: δ ϭ 5.84Ϫ5.25 (m, 3 H, 2/3/4-H), 1.73 (dd, J ϭ 6.6/
1.7 Hz, 3 H, 1-H), 1.12 [s, 9 H, C(CH3)3], 0.16 [s, 9 H, Si(CH3)3].
Ϫ
13C NMR: δ ϭ 207.1 (x, C-5), 127.6 (ϩ, C-2), 123.8 (ϩ, C-3),
108.8 (x, C-6), 90.2 (ϩ, C-4), 35.3 (x, C-7), 31.4 [ϩ, C(CH3)3], 13.3
1
(ϩ, C-1), 1.2 [ϩ, Si(CH3)3]. Ϫ (Z)-11e: H NMR: δ ϭ 5.84Ϫ5.25
(E)-5-Methyl-1-phenyl-1,3,4-nonatriene (11i): From 513 mg (2.0
mmol) of 4c in 15 mL of diethyl ether, 762 mg (4.0 mmol) of CuI
in 30 mL of diethyl ether and 5.0 mL (8.0 mmol) of MeLi (1.6 M
in diethyl ether). Yield: 280 mg (66%) of 11i as a colorless liquid.
(m, 3 H, 2/3/4-H), 1.71 (dd, J ϭ 6.9/1.7 Hz, 3 H, 1-H), 1.11 [s, 9
H, C(CH3)3], 0.17 [s, 9 H, Si(CH3)3]. Ϫ 13C NMR: δ ϭ 208.3 (x,
C-5), 125.9 (ϩ, C-2), 122.1 (ϩ, C-3), 108.3 (x, C-6), 85.8 (ϩ, C-4),
35.3 (x, C-7), 31.4 [ϩ, C(CH3)3], 18.2 (ϩ, C-1), 1.2 [ϩ, Si(CH3)3].
Ϫ IR: ν˜ ϭ 2959 cmϪ1 (s, CϪH), 1922 (s, CϭCϭC), 1450 (m, Cϭ
C). Ϫ MS: m/z (%) ϭ 208 (3) [Mϩ], 193 (1) [M Ϫ CH3], 168 (2),
152 (5), 57 (100). Ϫ HRMS (C13H24Si): calcd. 208.1647; found
208.1651.
1
Ϫ H NMR: δ ϭ 7.41Ϫ7.18 (m, 5 H, Phenyl-H), 6.61 (ddd, J ϭ
15.8/10.1/1.0 Hz, 1 H, 2-H), 6.48 (d, J ϭ 15.8 Hz, 1 H, 1-H), 5.92
(m, 1 H, 3-H), 2.03 (m, 2 H, 6-H), 1.77 (d, J ϭ 2.7 Hz, 3 H, 5-
CH3), 1.78Ϫ1.32 (m, 4 H, 7/8-H), 0.93 (t, J ϭ 7.1 Hz, 3 H, 9-H).
Ϫ
13C NMR: δ ϭ 205.8 (x, C-4), 137.6 (x, Phenyl), 129.2/128.6/
6-(1,1-Dimethylethyl)-2,4,5-decatriene (11f): From 388 mg (2.0
mmol) of 4a in 20 mL of diethyl ether, 270 mg (3.0 mmol) of CuCN
127.1/126.6/ 126.1 (5ϩ, C-1/2/Phenyl), 101.3 (x, C-5), 94.0 (ϩ, C-
3), 33.8 (Ϫ, C-6), 29.8 (Ϫ, C-7), 22.4 (Ϫ, C-8), 19.1 (ϩ, 5-CH3),
Eur. J. Org. Chem. 1999, 267Ϫ275
273

M. Purpura, N. Krause
FULL PAPER
14.0 (ϩ, C-9). Ϫ IR: ν˜ ϭ 2956 cmϪ1 (s, CϪH), 1944 (m, CϭCϭ
4), 33.8 (x, C-7), 30.2 [ϩ, C(CH3)3], 18.3 (ϩ, 4-CH3), 15.9 (ϩ, C-
C), 1594 (m), 1497 (m), 1447 (m, CϭC). Ϫ MS: m/z (%) ϭ 212 1). Ϫ IR: ν˜ ϭ 2958 cmϪ1 (s, CϪH), 1945 (w, CϭCϭC), 1463 (m,
(18) [Mϩ], 192 (6), 170 (78), 155 (100). Ϫ HRMS (C16H20): calcd.
212.1565; found 212.1565.
CϭC). Ϫ MS: m/z (%) ϭ 150 (11) [Mϩ], 135 (10) [M Ϫ CH3], 84
(48), 57 (100). Ϫ HRMS (C11H18): calcd. 150.1409; found 150.1418.
(E)-6-(1,1-Dimethylethyl)-2,4,5-decatrien-1-ol (12a): From 300 mg
(2.0 mmol) of 10a in 10 mL of diethyl ether, 270 mg (3.0 mmol) of
CuCN in 20 mL of diethyl ether and 4.0 mL (6.0 mmol) of tBuLi
(1.5  in pentane). Yield: 300 mg (72%) of 12a as a colorless liquid.
5-(1,1-Dimethylethyl)-1-phenyl-1,3,4-nonatriene (11j): From 513 mg
(2.0 mmol) of 4c in 10 mL of diethyl ether, 270 mg (3.0 mmol) of
CuCN in 30 mL of diethyl ether and 4.0 mL (6.0 mmol) of tBuLi
(1.5  in pentane). Yield: 480 mg (94%) of 11j (2:3 mixture of (E/
1
1
Ϫ H NMR: δ ϭ 6.00 (ddt, J ϭ 15.3/10.3/1.2 Hz, 1 H, 3-H), 5.80
Z)-isomers according to GC analysis) as a colorless liquid. Ϫ H
(dt, J ϭ 10.3/3.2 Hz, 1 H, 4-H), 5.70 (dt, J ϭ 15.3/5.9 Hz, 1 H, 2-
H), 4.10 (dd, J ϭ 5.9/1.2 Hz, 2 H, 1-H), 2.30 (s, 1 H, OH),
2.00Ϫ1.90 (m, 2 H, 7-H), 1.34Ϫ1.28 (m, 4 H, 8/9-H), 1.01 [s, 9 H,
C(CH3)3], 0.86 (t, J ϭ 7.2 Hz, 3 H, 10-H). Ϫ 13C NMR: δ ϭ 203.9
(x, C-5), 129.4 (ϩ, C-2), 128.4 (ϩ, C-3), 115.3 (x, C-6), 95.6 (ϩ, C-
4), 70.2 (Ϫ, C-1), 33.9 [x, C(CH3)3], 30.4 (Ϫ, C-7), 29.3 [ϩ,
C(CH3)3], 26.8 (Ϫ, C-8), 22.5 (Ϫ, C-9), 13.6 (ϩ, C-10). Ϫ IR: ν˜ ϭ
3600Ϫ3200 cmϪ1 (s, OH), 2960 (s, CϪH), 1937 (m, CϭCϭC). Ϫ
MS: m/z (%) ϭ 208 (1) [Mϩ], 166 (27), 105 (39), 57 (100). Ϫ HRMS
(C14H24O): calcd. 208.1827; found 208.1822.
NMR: (E)-11j: δ ϭ 7.44Ϫ7.19 (m, 5 H, Phenyl-H), 6.62 (dd, J ϭ
15.8/10.1 Hz, 1 H, 2-H), 6.50 (d, J ϭ 15.8 Hz, 1 H, 1-H), 6.06 (dt,
J ϭ 10.1/3.2 Hz, 1 H, 3-H), 2.10Ϫ1.97 (m, 2 H, 6-H), 1.45Ϫ1.38
(m, 4 H, 7/8-H), 1.12 [s, 9 H, C(CH3)3], 0.94 (m, 3 H, 9-H). Ϫ (Z)-
11j: δ ϭ 7.44Ϫ7.19 (m, 5 H, Phenyl-H), 6.47 (dm, J ϭ 11.1 Hz, 1
H, 3-H), 6.34 (d, J ϭ 11.3 Hz, 1 H, 1-H), 6.12 (dd, J ϭ 11.3/11.1
Hz, 1 H, 2-H), 2.10Ϫ1.97 (m, 2 H, 6-H), 1.45Ϫ1.38 (m, 4 H, 7/8-
H), 1.11 [s, 9 H, C(CH3)3], 0.94 (m, 3 H, 9-H). Ϫ 13C NMR: δ ϭ
205.8*/204.7 (x, C-4), 137.7 (x, Phenyl), 128.9/128.7/128.6/128.3/
127.9/127.3/127.1/ 127.0/126.7/126.0 (10ϩ, C-1/2/Phenyl), 115.6/
115.2 (x, C-5), 97.1/93.2* (ϩ, C-3), 34.1 (x, C(CH3)3), 30.5 (-, C-
6), 29.4 [ϩ, C(CH3)3], 27.0 (Ϫ, C-7), 22.7 (Ϫ, C-8), 14.2 (ϩ, C-9).
Ϫ IR: ν˜ ϭ 2958 cmϪ1 (s, CϪH), 1934 (m, CϭCϭC), 1598 (m),
1491 (m), 1447 (m, CϭC). Ϫ MS: m/z (%) ϭ 254 (9) [Mϩ], 239 (2)
[M Ϫ CH3], 197 (78), 57 (100). Ϫ HRMS (C19H26): calcd. 254.2034;
found 254.2033.
6-(1,1-Dimethylethyl)-2-methyl-2,4,5-decatrien-1-ol (12b): From 164
mg (1.0 mmol) of 10b in 5 mL of diethyl ether, 135 mg (1.5 mmol)
of CuCN in 15 mL of diethyl ether and 2.0 mL (3.0 mmol) of
tBuLi (1.5  in pentane). Yield: 135 mg (61%) of 12b (4:1 mixture
of (E/Z)-isomers according to GC analysis) as a colorless liquid. Ϫ
1
(E)-12b: H NMR: δ ϭ 5.99 (dt, J ϭ 10.8/3.2 Hz, 1 H, 4-H), 5.80
(dt, J ϭ 10.8/1.2 Hz, 1 H, 3-H), 4.02 (s, 2 H, 1-H), 2.09 (s, 1 H,
OH), 2.00Ϫ1.90 (m, 2 H, 7-H), 1.74 (d, J ϭ 1.2 Hz, 3 H, 2-CH3),
1.40Ϫ1.30 (m, 4 H, 8/9-H), 1.02 [s, 9 H, C(CH3)3], 0.87 (t, J ϭ 7.2
Hz, 3 H, 10-H). Ϫ 13C NMR: δ ϭ 204.2 (x, C-5), 134.2 (x, C-2),
122.4 (ϩ, C-3), 114.8 (x, C-6), 92.7 (ϩ, C-4), 68.7 (Ϫ, C-1), 33.9
[x, C(CH3)3], 30.5 (Ϫ, C-7), 29.4 [ϩ, C(CH3)3], 27.2 (ϩ, 2-CH3),
1-(1-Cyclohexen-1-yl)-3-methyl-1,2-heptadiene (11k): From 234 mg
(1.0 mmol) of 6 in 10 mL of diethyl ether, 381 mg (2.0 mmol) of
CuI in 20 mL of diethyl ether and 2.5 mL (4.0 mmol) of MeLi (1.6
 in diethyl ether). Yield: 158 mg (83%) of 11k as a colorless liquid.
1
Ϫ H NMR: δ ϭ 5.72 (q, J ϭ 2.8 Hz, 1 H, 1-H), 5.60 (t, J ϭ 3.7
Hz, 1 H, 2Ј-H), 2.10Ϫ1.92 (m, 6 H, 3Ј/6Ј/4-H), 1.70 (d, J ϭ 2.8 Hz,
3 H, 3-CH3), 1.68Ϫ1.55 (m, 4 H, 4Ј/5Ј-H), 1.45Ϫ1.25 (m, 4 H, 5/
6-H), 0.89 (t, J ϭ 7.1 Hz, 3 H, 7-H). Ϫ 13C NMR: δ ϭ 201.5 (x,
C-2), 133.5 (x, C-1Ј), 124.7 (ϩ, C-2Ј), 102.5 (x, C-3), 96.9 (ϩ, C-
1), 34.1 (Ϫ, C-4), 29.9 (Ϫ, C-5), 25.8 (Ϫ, C-3Ј/6Ј), 22.7 (Ϫ, C-4Ј/
5Ј), 22.6 (-, C-6), 19.4 (ϩ, 3-CH3), 14.0 (ϩ, C-7). Ϫ IR: ν˜ ϭ 2924
cmϪ1 (s, CϪH), 1945 (w, CϭCϭC), 1446 (m, CϭC). Ϫ MS: m/z
(%) ϭ 190 (19) [Mϩ], 175 (3) [M Ϫ CH3], 148 (75), 105 (100). Ϫ
HRMS (C14H22): calcd. 190.1722; found 190.1726.
1
26.9 (Ϫ, C-8), 22.6 (Ϫ, C-9), 13.6 (ϩ, C-10). Ϫ H{1H}-NOE dif-
ference spectra (irradiation at Ǟ intensity enhancement at): δ ϭ
1.74 (2-CH3) Ǟ δ ϭ 5.99 (4-H), 4.02 (1-H); δ ϭ 4.02 (1-H) Ǟ δ ϭ
5.80 (3-H), 1.74 (2-CH3); δ ϭ 5.80 (3-H) Ǟ δ ϭ 4.02 (1-H); δ ϭ
5.99 (4-H) Ǟ δ ϭ 1.74 (2Ј-H). Ϫ IR: ν˜ ϭ 3600Ϫ3200 cmϪ1 (s,
OH), 2960 (s, CϪH), 1934 (m, CϭCϭC). Ϫ MS: m/z (%) ϭ 222
(1) [Mϩ], 191 (12), 180 (40), 57 (100). Ϫ HRMS (C15H26O): calcd.
222.1983; found 222.1967.
(E)-2-Methyl-2,4,5-decatrien-1-ol (13): From 164 mg (1.0 mmol) of
10b in 10 mL of diethyl ether, 381 mg (2.0 mmol) of CuI in 20 mL
of diethyl ether and 2.5 mL (4.0 mmol) of MeLi (1.6  in diethyl
1-(1-Cyclohexen-1-yl)-3-(1,1-dimethylethyl)-1,2-heptadiene
(11l):
From 234 mg (1.0 mmol) of 6 in 10 mL of diethyl ether, 135 mg
(1.5 mmol) of CuCN in 20 mL of diethyl ether and 2.0 mL (3.0
mmol) of tBuLi (1.5  in pentane). Yield: 197 mg (85%) of 11l as
a colorless liquid. Ϫ 1H NMR: δ ϭ 5.85 (t, J ϭ 3.3 Hz, 1 H, 1-H),
5.60 (t, J ϭ 3.8 Hz, 1 H, 2Ј-H), 2.12Ϫ1.90 (m, 6 H, 3Ј/6Ј/4-H),
1.71Ϫ1.55 (m, 4 H, 4Ј/5Ј-H), 1.43Ϫ1.26 (m, 4 H, 5/6-H), 1.05 [s, 9
H, C(CH3)3], 0.90 (t, J ϭ 7.1 Hz, 3 H, 7-H). Ϫ 13C NMR: δ ϭ
200.1 (x, C-2), 133.7 (x, C-1Ј), 124.1 (ϩ, C-2Ј), 116.6 (x, C-3), 99.9
(ϩ, C-1), 34.0 [x, C(CH3)3], 30.8 (Ϫ, C-4), 29.5 [ϩ, C(CH3)3], 27.2
(Ϫ, C-5), 25.8 (Ϫ, C-3Ј/6Ј), 22.8 (Ϫ, C-6), 22.7 (Ϫ, C-4Ј/5Ј), 14.1
(ϩ, C-7). Ϫ IR: ν˜ ϭ 2959 cmϪ1 (s, CϪH), 1936 (w, CϭCϭC), 1459
(m, CϭC). Ϫ MS: m/z (%) ϭ 232 (3) [Mϩ], 217 (4) [M Ϫ CH3],
190 (20), 175 (36), 57 (100). Ϫ HRMS (C17H28): calcd. 232.2190;
found 232.2192.
1
ether). Yield: 90 mg (54%) of 13 as a colorless liquid. Ϫ H NMR:
δ ϭ 6.00Ϫ5.93 (m, 1 H, 4-H), 5.86 (d, J ϭ 10.8 Hz, 1 H, 3-H),
5.29 (q, J ϭ 6.7 Hz, 1 H, 6-H), 4.04 (s, 2 H, 1-H), 2.13 (s, 1 H,
OH), 2.05Ϫ1.98 (m, 2 H, 7-H), 1.75 (s, 3 H, 2-CH3), 1.47Ϫ1.28
(m, 4 H, 8/9-H), 0.88 (t, J ϭ 7.1 Hz, 3 H, 10-H). Ϫ 13C NMR: δ ϭ
208.0 (x, C-5), 135.6 (x, C-2), 121.0 (ϩ, C-3), 92.1/89.1 (2ϩ, C-4/
6), 68.7 (Ϫ, C-1), 31.2 (Ϫ, C-7), 28.5 (Ϫ, C-8), 26.9 (Ϫ, C-9), 22.1
(ϩ, 2-CH3), 13.6 (ϩ, C-10). Ϫ IR: ν˜ ϭ 3600Ϫ3200 cmϪ1 (s, OH),
2957 (s, CϪH), 1942 (m, CϭCϭC). Ϫ MS: m/z (%) ϭ 166 (11)
[Mϩ], 149 (15), 124 (74), 91 (94), 79 (100). Ϫ HRMS (C11H18O):
calcd. 166.1358; found 166.1358.
(E)-4,7,7-Trimethyl-2,4,5-octatriene (11m): From 304 mg (2.0
mmol) of 8 in 15 mL of diethyl ether, 270 mg (3.0 mmol) of CuCN
in 30 mL of diethyl ether and 4.0 mL (6.0 mmol) of tBuLi (1.5 
in pentane). Yield: 249 mg (83%) of 11m as a colorless liquid. Ϫ
1H NMR: δ ϭ 6.00 (dm, J ϭ 15.5 Hz, 1 H, 3-H), 5.52 (dqd, J ϭ
15.5/6.7/1.2 Hz, 1 H, 2-H), 5.17 (m, 1 H, 6-H), 1.80Ϫ1.76 (m, 6 H,
1-H, 4-CH3), 1.03 [s, 9 H, C(CH3)3]. Ϫ 13C NMR: δ ϭ 203.2 (x,
C-5), 130.3 (ϩ, C-2), 123.2 (ϩ, C-3), 102.3 (ϩ, C-6), 101.6 (x, C-
Acknowledgments
We thank the Deutsche Forschungsgemeinschaft and the Fonds der
Chemischen Industrie for financial support of this work.
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