Transformation of β-chalcogeno alkenylboranes into tetrasubstituted olefins

Article abstract of DOI:10.1016/j.tet.2003.11.023

In view of generating trisubstituted vinylic chalcogen derivatives, β-chalcogeno alkenylboranes generated through the chalcogen electrophile induced rearrangements of 1-alkynyltrialkyl borates have been subjected to Suzuki-Miyaura coupling and to boron to copper transmetalation followed by alkylation. Some of the trisubstituted vinyl sulfides obtained by this latter strategy have been converted efficiently into the title olefins through the NiCl₂(dmpe) catalyzed coupling with various Grignard reagents.

Full text of DOI:10.1016/j.tet.2003.11.023

Tetrahedron 60 (2004) 367–381
Transformation of b-chalcogeno alkenylboranes into
tetrasubstituted olefins
*
´ ´
Julien Gerard and Laszlo Hevesi
´ ´
Departement de Chimie, Facultes Universitaires Notre-Dame de la Paix; 61, rue de Bruxelles, B-5000 Namur, Belgium
Received 29 August 2003; revised 6 November 2003; accepted 6 November 2003
Abstract—In view of generating trisubstituted vinylic chalcogen derivatives, b-chalcogeno alkenylboranes generated through the chalcogen
electrophile induced rearrangements of 1-alkynyltrialkyl borates have been subjected to Suzuki–Miyaura coupling and to boron to copper
transmetalation followed by alkylation. Some of the trisubstituted vinyl sulfides obtained by this latter strategy have been converted
efficiently into the title olefins through the NiCl2(dmpe) catalyzed coupling with various Grignard reagents.
q 2003 Published by Elsevier Ltd.
1. Introduction
Some of these compounds are stable crystalline solids on
which X-ray structure determination have been carried out.
In all the cases examined, the boron and chalcogen moieties
have shown a cis relationship, attesting thereby the high
stereoselectivity of the rearrangement. Our goal will be to
preserve this stereochemistry throughout the two successive
steps leading to the target olefins: (i) electrophilic
substitution of the boron moiety by a carbon fragment and
(ii) replacement of the chalcogenyl group.
Recently we have reported on the efficient and highly
stereoselective rearrangement of 1-alkynyltrialkyl borates
triggered by chalcogen (S, Se, Te) electrophiles.1 We have
also shown that the b-chalcogeno alkenylboranes produced
via this rearrangement can be protodeborylated with
essentially complete retention of stereochemistry to produce
the corresponding vinyl sulfides, -selenides or -tellurides in
excellent yields. Finally, the latter have been converted into
trisubstituted olefins either by nickel catalyzed coupling
with Grignard reagents, or through Te/Li exchange (in the
case of alkylvinyl tellurides) followed by reaction of the so
obtained vinyllithiums with carbonyl compounds.
2. Results and discussion
Considering the much greater sensitivity of the C–B bond
as compared to the C–S(Se,Te) bonds, we decided to
transform first the b-chalcogeno alkenylboranes into fully
substituted vinyl chalcogenides 3 (Scheme 2). For this
purpose, we have investigated two different strategies: (i)
the Suzuki–Miyaura coupling and (ii) the boron to copper
exchange followed by alkylation.
We now wish to report a detailed account of our efforts
aimed at the conversion of the b-chalcogeno alkenylboranes
into the title olefins. As previously,1 these key intermediates
2 are formed in high yield on reaction of various
chalcogenyl halides with the in situ prepared lithium
1-alkynyltrialkyl borates 1 (Scheme 1).
Scheme 1.
Keywords: Rearrangement of 1-alkynyltrialkyl borates; Trisubstituted vinyl chalcogenides; Tetrasubstituted olefins; Alkenylboranes; Suzuki–Miyaura
coupling; Transmetalation; Nickel catalyzed coupling with Grignard reagents.
*
Corresponding author. Fax: þ32-81725451; e-mail address: laszlo.hevesi@fundp.ac.be
0040–4020/$ - see front matter q 2003 Published by Elsevier Ltd.
doi:10.1016/j.tet.2003.11.023

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J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
Scheme 2.
2.1. Suzuki–Miyaura coupling of b-chalcogeno
alkenylboranes
atomic moieties leading to an internal alkyne and the
protodeborylation producing vinyl chalcogenides. These
reactions can occur separately or concomitantly. In order to
gain some insight into the details of these side reactions, we
have carried out a few additional experiments. Thus, (E)-1-
cyclohexyl-1-(dicyclohexylboryl)-2-(phenylseleno)-1-hep-
tene 2e has been subjected to a typical Suzuki–Miyaura
coupling reaction using iodobenzene as electrophile
(Scheme 3a). As can be seen, none of the desired vinyl
selenide was observed. Instead, n-pentylcyclohexylacetyl-
ene 5b and diphenylselenide 6e1 were formed in almost
quantitative yields (with respect to the amount of iodo-
benzene used). In this case, elimination of the boron and
selenium moieties, accompanied by the consumption of
iodobenzene by the insipient selenolate anion producing
The palladium catalyzed reaction between organoboron
compounds and alkynyl, alkenyl and aryl halides has
appeared to be a powerful and useful methodology for the
formation of carbon–carbon bonds.2 Since the reagents and
conditions of the so-called Suzuki–Miyaura coupling
should not alter the vinylchalcogen moiety, we have tested
it on four different b-chalcogeno alkenylboranes under
various conditions. The quite limited success of the method
is illustrated by the results shown in Table 1.
It turns out that the two major side reactions competing with
the desired coupling are the elimination of both hetero-
Table 1. Suzuki–Miyaura couplings of b-chalcogenovinyl boranes 2
Entry
Reagent
Base (equiv./PhI)
NaOH aq. (3.0)
Conditions
Yield (%)
3
4
5
6
33 (3a1)
—
2a
1
THF, rfx 3 h
62 (5a)
59 (6a1)
2
3
4
5
2a
2a
2a
2a
K3PO4 (3.0)
Na2HPO4 (3.0)
Na2CO3 (2.4)
Bu4NF (2.0)
DMF/THF rfx, 18 h
DMF/THF rfx, 16 h
DMF/THF rfx, 16 h
THF, rfx 13 h
33 (3a1)
0a (3a1)
0a (3a1)
37 (3a1)
—
—
—
58 (5a)
—
—
58 (6a1)
—
—
27 (4a)
35 (5a)
37 (6a1)
2b
2c
2d
6
Bu4NF (2.0)
THF, rfx 13 h
THF, rfx 16 h
70 (3b1)
0 (3c1)
Traces (4b)
9 (5b)
—
—
7b
NaOH aq. (3.0)
61 (4c)
—
8b
Bu4NF (2.0)
K3PO4 (2.0)
THF, rfx 20 h
37 (3d1)
34 (3d1)
—
—
—
—
c
c
9b
2d
DMF/THF rfx, 28 h
a
2a was recovered quantitatively.
These experiments were carried out in situ, without isolation of the alkenylborane.
The formation of these compounds has not been quantified.
b
c

J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
369
Scheme 3.
diphenylselenide,3 completely predominated. However,
when 2e was refluxed in THF with aqueous sodium
hydroxide, no elimination occurred and the starting material
was recovered entirely (Scheme 3b). Similarly, refluxing 2e
under the same conditions but in the presence of the
palladium catalyst produced only trace amounts of the
internal alkyne 5b, leaving 92% of 2e unchanged
(Scheme 3c). These results indicate that coordination of
hydroxide ion onto the boron atom of the starting
b-chalcogeno alkenylboranes is not responsible for the
elimination. Therefore, this side reaction must occur at the
level of a b-chalcogeno alkenylpalladium intermediate.
Moreover, the latter species should contain the phenyl
group already attached to palladium, since withdrawing
iodobenzene from the reaction mixture brings about a
remarkable decrease of the alkyne’s yield. Scheme 4
shows the series of events which seems the most
probable.
yield of vinyl sulfide 3b1 and only to a small amount of
n-pentylcyclohexylacetylene 5b (Table 1, entry 6).
The nature of the ‘base’ required for the Suzuki–Miyaura
couplings does not seem to be decisive here since the
amounts of coupling product formed from 2a were almost
identical, regardless of whether NaOH, K3PO4 or Bu4NF
were used (Table 1, entries 1, 2, and 5). Surprisingly, in the
presence of sodium hydrogenphosphate or sodium carbon-
ate, no reaction took place at all (Table 1, entries 3 and 4).
As mentioned above, the second major side reaction
observed was protodeborylation of b-chalcogeno alkenyl-
boranes 2 producing the corresponding vinyl chalcogenides
4. According to earlier findings,4 secondary alkyl and
cycloalkyl substituted alkenylboranes are usually very
reluctant to this reaction, whereas primary alkyl derivatives
undergo protodeborylation efficiently. While this trend is
reasonably well confirmed by entries 6 and 7 of Table 1, we
cannot rationalize the presence of (E)-1-cyclohexyl-2-
(phenythio)-1-hexene 4a (27%) among the products in
entry 5. In view of the nearly quantitative yield in
n-pentylcyclohexylacetylene 5b in the experiment with 2e
(Scheme 3a), formation of only traces of 3-tetradecyne 5c
from 2c is also rather puzzling (Table 1, entry 7). In this
case, the main product appeared to be (E)-4-(phenylseleno)-
3-tetradecene 4c (61%) arising from protodeborylation. It is
interesting to note that this latter process does not appear to
take place exclusively by coordination of hydroxide ion
In the light of the above, it is much easier to understand the
results of Table 1. Indeed, entry 1 shows that the behaviour
of b-phenylthio alkenylborane 2a towards the Suzuki–
Miyaura coupling is fairly comparable to that of 2e; the
difference lies in the ratio of coupling to elimination, that is
roughly 1:2 for 2a instead of 0:100 for 2e. Clearly, the
phenylthio group (a weaker leaving group than the
phenylseleno group) allows the coupling reaction to
compete to some extent with syn-elimination. In agreement
with this view, b-butylthio alkenylborane 2b led to a good
Scheme 4.

370
J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
onto 2e to form a vinylic borate complex followed by
reaction with water. Indeed, refluxing 2e for 16 h with
aqueous sodium hydroxide in THF gave only a 35% yield of
vinyl selenide 4c. This suggests that protodeborylation may
also be subject to palladium catalysis,5 in an analogous way
to the syn-elimination outlined in Scheme 4. Finally, the
experiments carried out on 2d (Table 1, entries 8 and 9)
confirm the difficulty to get good yields of coupling product
when the boron atom is substituted with primary alkyl
groups.
vinylsulfides with almost complete control of the
stereochemistry.
2.2. Boron to copper transmetalation followed by
alkylation
This is a well documented method for carrying out
carbodeborylation of various boron derivatives, particularly
alkenylboranes leading to olefinic products.9 Starting from
our b-chalcogeno alkenylboranes 2, we should synthesize
fully substituted vinyl chalcogenides which in turn should
lead to a variety of olefins with high degrees of regio- and
stereoselectivities.
Over the years, several alternative protocols appeared in the
literature aiming to improve the performance of the less
efficient Suzuki–Miyaura couplings. We tried two of these:
the first one, introduced by Soderquist and co-workers,6
consists in transforming the starting alkenylborane into
vinylborinate by anhydrous Me3NO mediated oxidation
before applying the coupling conditions; the second
alternative involves boron to copper transmetalation
prior to coupling.7 In our case, neither procedure allowed
us to improve the yield of vinyl sulphide 3d1, starting from
2d.
Two types of experimental procedures have been explored.
In the first one, both the activation of b-chalcogeno
alkenylboranes 2 and the transmetalation have been carried
out at low temperature (278 8C) and in the absence of
additives. The results of this procedure using various
substrates and electrophiles are displayed in Table 2.
Clearly, several situations can be distinguished. Whatever
the electrophile used, methyl iodide or allyl bromide,
carbodeborylations of b-phenylseleno- and b-phenyltelluro
alkenylboranes failed almost completely (Table 2, entries
16–19). As in the coupling experiments, syn elimination
leading to the appropriate internal alkyne and to phenyl-
methyl (or allyl) chalcogenides was largely predominat-
ing.10 Somewhat unexpectedly, B–Cu transmetalation
followed by allylation of 2k gave the product 3k4 in
excellent yield (Table 2, entry 15). Conjunction of
factors such as a sterically less congested vinylcopper
intermediate, the weakest leaving group, and the more
reactive electrophile may be responsible for this
observation.
Additionally, we also carried out Suzuki–Miyaura coupling
experiments on b-butylthio alkenylborane 2b (the best
performing one in Table 1) using benzyl bromide and
1-bromo-1-heptyne as electrophiles. The first one
(Scheme 5a) gave deceptively bad results; the syn-
elimination side reaction largely predominated, in spite of
the n-butylthio substituant on the starting compound, and
only trace amounts of the desired vinyl sulphide 3b2 were
formed. In contrast, coupling of 2b with 1-bromo-1-heptyne
produced the butylthioenyne 3b3 in excellent yield
(Scheme 5b). The high propensity of 1-halogeno-1-alkynes
for Suzuki–Miyaura coupling had been noted earlier.8
In all the remaining experiments of Table 2, b-phenylthio-
or b-butylthio alkenylboranes have been used as substrates
in the presence of various electrophiles. Although syn
elimination did occur on b-phenylthio derivatives in a few
poorly performing reactions, this side reaction was no
longer a serious competitor in most of the cases. Thus, high
yields of vinyl sulphide could be obtained with methyl
iodide (Table 2, entries 7 and 12), allyl bromide (Table 2,
entries 1, 2, and 13) and 1-iodo-1-heptyne (Table 2, entries 3
and 14) as electrophiles. Surprisingly, ethylation and
benzylation gave poor results (Table 2, entries 4, 8, and
9); once again, significant syn elimination and proto-
deborylation were observed, as illustrated by the formation
In all cases, the Z/E ratio of isolated vinyl sulphides
(determined by GC) was greater than 98:2. While the
absolute stereochemistry of all compounds was not
rigorously established, a reasonable assumption is made
that the coupling reaction proceeds as usual, with retention
of configuration.2 Finally, in spite of this satisfactory
stereochemical outcome and due to the two side reactions
occuring competitively with the desired cross-coupling, the
whole methodology turns out to be mainly unsuitable for the
electrophilic substitution of our intermediates. Neverthe-
less, in some specific cases, this procedure allows an
efficient and straightforward synthesis of trisubstituted
Scheme 5.

J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
Table 2. Carbodeborylation of b-chalcogenovinyl boranes 2
371
Entry
Reagent
R4X (equiv.)
Yield (%)
3
4
5
6
2f
1
CH2vCH–CH2Br
CH2vCH–CH2Br
81 (3f4)
—
—
—
—
2a
74 (3g4)
—
—
2g
3
4
5
6
2g
2g
2g
2g
n-Pent-CuC–Ib
PhCH2Br
MeCOCl
63 (3g3)
13 (3g2)
29 (3g5)
32 (3g6)
—
c
—
c
—
c
c
c
c
c
c
c
PhCOCl
c
2h
2i
7
MeI
72 (3h7)
—
—
8
9
2h
2h
EtI
PhCH2Br
3 (3h8)
11 (3h2)
11 (4h)
41 (5h)
5 (6h8)
c
c
c
10d
11d,f
12
MeI
MeI
MeI
0e (3i7)
6g (3i7)
68 (3d7)
—
—
—
—
—
—
—
2i
—
c
2d
2j
13
14
15
CH2vCH–CH2Br
n-Pent-CuC–Ib
CH2vCH–CH2Br
74 (3j4)
59 (3j3)
71 (3k4)
—
—
—
—
—
—
—
—
—
2j
2k
2l
16
MeI
0 (3l7)
0 (3l7)
—
67 (5l)
70 (5l)
56 (6l7)
54 (6l7)
—
17a
18
2l
MeI
—
c
2m
CH2vCH–CH2Br
CH2vCH–CH2Br
0 (3m4)
0 (3m4)
—
c
c
19a
2m
61 (3m4)
a
MeOLi was used instead of n-BuLi.
1.25 equiv. were introduced.
The formation of these compounds has not been quantified.
These experiments were carried out with isolated starting material.
2i was recovered quantitatively.
b
c
d
e
f
MeLi was used instead of n-BuLi.
88% of 2i were recovered.
g
of the side products 4h and 5h during the carbodemetalation
of 2h with ethyl iodide (Table 2, entry 8). This latter process
seemed to occur in the acylation reactions as well, although
it does not explain alone the modest yields in b-phenylthio
enones (Table 2, entries 5 and 6). Nevertheless, it has been
reported that simple vinylcopper species display only
limited reactivity towards acid chlorides.11 Finally, it should
be noted that the activation step can be carried out with
lithium methoxide instead of n-butyllithium without a
significant decrease in the vinyl sulfide’s yield (Table 1,
compare entries 1 and 2).
On the other hand, transmetalation of sterically hindered
alkenylboranes was unsuccessful using n-butyllithium and
only slightly better using methyllithium (Table 2, entries 10
and 11). That steric inhibition prevents the complexation of

372
J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
Scheme 6.
the base on the borane in these cases is attested by two
observations: (i) the starting b-phenylthio alkenylborane 2i
was recovered unchanged and (ii) when methyl iodide was
replaced by decanoyl chloride in the experiment of Table 2,
entry 11, 2-undecanone was formed in good yield
(Scheme 6), supporting the intermediary formation of
methylcopper instead of the desired vinylcopper.
improvement of the carbodemetalation efficiency of the
sulfur derivatives. This was achieved for most of
the unsatisfactory results shown in Table 2 by means of
the second type of experimental procedure for boron to
copper transmetalation, consisting in carrying out the
process in the presence of additives (such as HMPA or
P(OEt)3) and/or at somewhat higher temperature.12,13 Quite
spectacular improvements have been observed (Table 3).
On the basis of the above observations regarding the
synthesis of fully substituted vinyl selenides and -tellurides,
we decided to limit our further investigations to the
Remarkably, even the sterically hindered alkenylboranes
appeared to undergo efficient transmetalation (Table 3,
Table 3. Carbodeborylation of b-chalcogenovinyl boranes 2
Entry
Reagent
R4X
Condition
Yield (%)
3
4
5
6
b
1a
2a
3a
4
2i
2n
2i
MeI
A
A
A
A
B
B
B
B
69 (3i7)
—
—
CH2vCH–CH2Br
71 (3n4)
28 (3i8)
29 (3h8)
45 (3h8)
66 (3d8)
62 (3h2)
64 (3d2)
—
—
—
—
—
—
—
—
—
—
EtI
EtI
24 (5b)
33 (5h)
2h
2h
2d
2h
2d
24 (6h8)
5
EtI
21 (5h)
19 (6h8)
b
b
6
EtI
b
b
b
b
7
PhCH2Br
PhCH2Br
8
a
These experiments were carried out with isolated starting material.
The formation of these compounds has not been quantified.
b

J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
373
Scheme 7.
entries 1–3) under conditions A (MeLi, HMPA, 233 8C).
Consequently, methylation and allylation of the vinyl
copper intermediates gave the desired products in high
yield. However, ethyl iodide gave only a modest yield in
vinyl sulfide 3i8 because, in this case, the less reactive
electrophile allowed syn elimination to compete to a larger
extent. This interpretation is supported by the next three
runs (Table 3, entries 4–6). Indeed, the considerably less
hindered alkenylborane 2h gave essentially the same results
(Table 3, compare entries 3 and 4), whereas at lower
temperature (conditions B: MeLi, HMPA, P(OEt)3,
278 8C), the ethylation yield increased to 45% (Table 3,
entry 5). Applying conditions B to vinylborane 2d carrying
the poorer butylthio leaving group in b position led to
ethylation product 3d8 in good yield (Table 3, compare
entries 5 and 6). These latter conditions also allowed to
carry out benzylation reactions in a satisfactory manner
(Table 3, entries 7 and 8).
strategy gives access to a fairly large variety of fully
substituted vinyl sulfides with excellent stereochemical
control. In itself, this is an appreciable achievement taking
into account the usefulness of this class of compounds, and
especially that of the corresponding vinyl sulfoxides and
-sulfones.14
2.3. Synthesis of tetrasubstituted olefins from
vinylsulfides
We have reported on the efficient conversion of various
vinyl chalcogenides into trisubstituted olefins using the well
known nickel catalyzed coupling with Grignard reagents.1
Starting from vinyl sulfides, this transformation appeared to
occur with excellent yield and stereoselectivity by the use of
1,2-bis-(diphenylphosphinoethane) nickel chloride (NiCl2-
(dppe)). However, applying the conditions used earlier to
the coupling of fully substituted vinyl sulfide 3h7 with
phenylmagnesium bromide gave disappointing results: the
desired olefin was formed in low yield and about half of the
starting material was recovered unchanged (Scheme 7).
Prolonging the reaction time did not bring about higher
conversion.
The boron to copper transmetalation of alkenylboranes is
known to occur with almost complete retention of the
configuration.9 For all the experiments described here, the
ratio of stereoisomers in the crude product was greater than
98:2, in favour of the structures drawn in Tables 2 and 3
(vide infra for ascertainment of stereochemistry). Further-
more, in most of the cases, no trace of the other stereoisomer
could be detected after purification, neither by 1H NMR nor
GC. At this point, we can therefore conclude that the present
In addition, GC and GC–MS monitoring of the coupling
reaction revealed the presence in the reaction mixture of a
substantial amount of 5-methyldecen-6-thiol. Formation of
this thioenol (or of its magnesium salt) could be due to the
Table 4. Synthesis of tetrasubstituted olefins
Entry
Reagent
n
Conditions
Product
Yield (%)
3h7
1
2
2.4
10
Et2O, rfx, 48 h
Et2O, rt, 16 h
7A
28
13
3h7
3d7
3f4
7A
7A
7A
3
4
5
1.5
2
Et2O, rt, 15 h
Benzene, rfx, 15 h
Et2O, rt, 18 h
0a
0a
3d7
3f4
2.4
2.4
7B
26b
27
6
Et2O, rfx, 38 h
7B
a
3d7 was recovered quantitatively.
43% of 3f4 were recovered, and 59% of biphenyl were also formed.
b

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J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
Table 5. Synthesis of tetrasubstituted olefins
Entry
1
Reagent
R5
Ph
n
Conditions
Product
E/Z
Yield (%)
66
7A
3h7
5
Et2O, rfx, 16 h
.98:2
2
3
4
3h7
3h7
3h7
Ph
Ph
Ph
5
5
2.5
Et2O, rfx, 24 h
Et2O, rt, 24 h
Et2O, rfx, 14.5 h
7A
7A
7A
.96:4
.96:4
.99:1
75
36a
82
5
3h7
n-Bu
2.5
Et2O, rfx, 22.5 h
7C
—
70
6
7
8
3d7
Ph
Ph
5
3
Et2O, rfx, 16 h
Bu2O, 90 8C, 15 h
Et2O, rfx, 10 days
7A
7A
—
—
0b
0b
3d7
3h2
3f4
Me
2.5
7D
.99:1
24c
7B
9
Ph
Ph
2.5
5
Et2O, rfx, 23 h
,1:99
,1:99
38
38
10
3f4
Et2O, rfx, 22.5 h
7B
a
43% of 3h7 were recovered.
3d7 was recovered quantitatively.
60% of 3h2 were recovered.
b
c
preferential insertion of Ni(0) during the catalytic cycle into
the S–phenyl bond instead of the S–vinyl bond, itself
arising from the notably higher steric congestion of the
vinylic moiety in 3h7. The resulting thioenolate may have
led to blocking of the reaction, leaving a large part of
starting 3h7 unchanged. Furthermore, the limited perform-
ance of NiCl2(dppe) is not restricted to the case displayed in
Scheme 7; it is a poor catalyst for the coupling under
different conditions of other fully substituted vinyl sulfides
too (Table 4).
even this catalyst was found unable to couple butylvinyl
sulfide 3d7 which was recovered quantitatively from two
different runs (Table 5, entries 6 and 7). Phenylvinyl sulfides
bearing benzyl (3h2) or allyl (3f4) moieties next to the
phenylthio group represent intermediary cases in which the
conversion was not higher than 20–40% (Table 5, entries
8–10). The reason for this limited conversion is unclear, but
it is interesting to note that vinylsulfide 3f9, produced by
catalytic hydrogenation of compound 3f4, gave the olefin 7E
in high yield on coupling with PhMgBr (Scheme 8).
In connection with the coupling of unsaturated halogen
compounds with vinylic and allylic Grignard reagents,
Kumada and co-workers found that 1,2-bis-(dimethyl-
phosphinoethane) nickel chloride (NiCl2(dmpe)15)
exhibited superior activity as compared to the correspond-
ing dppe and dppp catalysts.16 We anticipated that the more
electron donating and less bulky dmpe ligand would confer
higher activity to this catalyst in the coupling reactions of
our sterically congested vinyl sulfides too. As witnessed in
Table 5, this expectation was confirmed, at least in part.
Indeed, the reaction of 3h7 with phenylmagnesium bromide
has now produced the desired olefin 7A in excellent yield
(Table 5, entry 4; compare to Scheme 7), and it also works
well with butylmagnesium bromide (Table 5, entry 5).
Nevertheless, it can be seen (Table 5, entries 1–4) that the
reaction conditions, especially the ratio of reactants and
reaction time, play an important role in the efficiency as well
as the stereoselectivity of these couplings. Unfortunately,
Therefore, the ability of nickel to coordinate C,C double
bonds appears responsible for the above limitations,
possibly through intramolecular coordination of the
terminal double bond in the vinylnickel intermediate
(Scheme 9).
Scheme 8.

J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
375
were purchased from Aldrich and used without further
purification, except tetrakis(triphenylphosphine)pal-
ladium,17 1-halo-1-heptynes,18 and 1,2-bis-(dimethyl-
phosphinoethane) nickel chloride,15 which were
synthesized according to the reported procedures. The
synthesis and characterization of the starting b-chalcogeno
alkenylboranes has been described previously.1
Scheme 9.
4.2. Suzuki–Miyaura couplings
Finally, DiffNOE experiment carried out on olefin 7D gave
the anticipated result: irradiation of the benzylic hydrogens
(s, 3.40 ppm) brought about disappearance of almost all the
signals in the difference spectrum with the exception of a
large singlet persisting at 1.72 ppm due to the methyl group
cis to benzyl group. This shows thereby that both steps of
the transformation of b-phenylthio alkenylboranes into
tetrasubstituted olefins have taken place with retention of
configuration of the C,C double bond.
4.2.1. Representative procedure (RP-1) for the Suzuki–
Miyaura coupling of isolated alkenylboranes. Synthesis
of (Z)-1-cyclohexyl-1-phenyl-2-(phenylthio)-1-hexene
(3a1). In a 25 mL two-necked flask, equipped with an
argon inlet and a magnetic stirring bar, were successively
introduced a THF solution (3 mL) of 2a (0.450 g; 1 mmol),
tetrakis(triphenylphosphine)palladium (0.045 g; 4 mol%),
and a THF solution (2 mL) of iodobenzene (0.163 g;
0.8 mmol; 0.8 equiv.). Tetrabutylammonium fluoride
(1.6 mL of a 1 M solution in THF; 1.6 mmol; 1.6 equiv.)
was added, and the reaction mixture was heated to reflux for
13 h. After cooling to room temperature, the solution was
diluted with 15 mL of Et2O, washed with water, dried over
MgSO4, and concentrated. The crude product was purified
by column chromatography (silica gel; pentane) to afford
0.046 g of n-butylcyclohexylacetylene 5a (35% yield),
0.055 g of diphenylsulphide 6a1 (37% yield), 0.073 g of
(E)-1-cyclohexyl-2-(phenylthio)-1-hexene 4a (27% yield),1
and 0.103 g of 3a1 (37% yield) as a colorless liquid. IR
(neat): 3074, 3058, 3020, 2930, 2855, 1584, 1476, 1441,
3. Conclusion
In conclusion, we had shown that chalcogen electrophile
induced rearrangements of 1-alkynyltrialkyborates give
access with good to excellent efficiencies and in well
defined regio- and stereochemical ways to a large variety of
disubstituted vinyl sulfides, -selenides and -tellurides (see
Ref. 1). Due to the weaker vinylic C–Se and C–Te bonds
leading to higher leaving propensity of the selenium and
tellurium moieties, only trisubstituted vinyl sulfides can be
obtained in satisfactory yields through the carbodeboryl-
ation protocol (boron to copper transmetalation followed by
alkylation). With the exception of a few cases, all the
accessible vinyl sulfides can be transformed into the
corresponding tri- or tetrasubstituted olefins by means of
the nickel catalyzed coupling with aliphatic or aromatic
Grignard reagents.
1072, 1025, 909, 739, 706 cm21 1H NMR (400 MHz,
;
CDCl3): d 0.89 (3H, t, J¼7.3 Hz), 0.94–1.04 (1H, m),
1.07–1.18 (2H, m), 1.28–1.37 (4H, m), 1.51–1.61 (3H, m),
1.74 (4H, m), 2.33 (2H, t, J¼7.3 Hz), 2.77 (1H, tt, J¼12.0,
2.9 Hz), 7.00–7.30 (10H, m); 13C NMR (100.4 MHz,
CDCl3): d 14.0, 22.4, 25.7, 26.6, 31.5, 31.7, 32.0, 42.4,
125.5, 126.4, 127.5, 128.6, 129.0, 129.4, 130.6, 136.9,
141.0; MS (EI): 350 (Mþ, 100), 273 (54), 226 (8), 217 (9),
183 (14), 171 (8), 155 (13), 141 (19), 129 (20), 117 (23), 91
(33), 55 (11); HRMS: m/z for C24H30S, calcd: 350.2068.
Found: 350.2060.
4. Experimental
4.1. General
4.2.2. (Z)-2-(n-Butythio)-1-cyclohexyl-1-phenyl-1-hep-
tene (3b1). Synthesized according to RP-1 and starting
from 2b. Column chromatography (silica gel; pentane)
afforded n-pentylcyclohexylacetylene 5b (9% yield) and
3b1 (70% yield), as a colorless liquid. IR (neat): 3078, 3055,
3025, 2956, 2929, 2854, 1595, 1489, 1450, 1378, 1271,
All glassware, syringes and needles were oven dried at
120 8C for several hours prior to use. The glassware were
assembled while hot and cooled under a stream of argon. 1H
(400 and 90 MHz) and 13C (100.4 and 22.5 MHz) NMR
spectra were recorded on either a JEOL JNM EX-400 or a
JEOL JNM EX-90 with CDCl3 as solvent and Me4Si as
internal standard. IR spectra were recorded on a BIORAD
FTS-165 spectrometer. Elemental analysis were carried out
using a Carlo-Erba NA 1500 C,H,N analyser. Low
resolution mass measurements were carried out using a
Hewlett–Packard HP6890 GC–MS instrument (ionization
potential: 70 eV); relative intensities of the ions are given in
parentheses. High resolution mass spectra were recorded on
a Micromass AutoSpec 6F mass spectrometer. Merck silica
gel 9385 (0.040–0.063 mm) and 5111 (0.015–0.040 mm)
were used for column chromatography. THF and Et2O were
distilled from sodium/benzophenone. HMPA was distilled
from CaH2. Methyl iodide, ethyl iodide, iodobenzene, allyl
bromide, benzyl bromide, acetyl chloride, benzoyl chloride,
decanoyl chloride, and triethyl phosphite were purchased
from Aldrich and distilled prior to use. The other reagents
1140, 1072, 891, 769, 701 cm21 1H NMR (400 MHz,
;
CDCl3): d 0.86 (3H, t, J¼7.2 Hz), 0.96 (3H, t, J¼6.8 Hz),
0.97–1.10 (3H, m), 1.22–1.44 (10H, m), 1.60–1.73 (7H,
m), 2.38–2.45 (4H, m), 2.69 (1H, tt, J¼11.7, 3.2 Hz), 6.95–
6.98 (2H, m), 7.24–7.34 (3H, m); 13C NMR (22.5 MHz,
CDCl3): d 13.6, 14.1, 21.9, 22.6, 25.8, 26.6, 29.1, 30.5, 31.4,
31.7, 31.8, 32.1, 42.2, 126.1, 127.3, 130.0, 130.8, 141.3,
147.7; MS (EI): 344 (Mþ, 65), 287 (100), 253 (7), 231 (5),
217 (6), 205 (6), 183 (13), 171 (8), 155 (6), 141 (12), 129
(14), 115 (16), 91 (18), 55 (12). Anal. Calcd for C23H36S: C,
80.17; H, 10.53. Found: C, 79.93; H, 10.55.
4.2.3. (E)-3-(n-Butylthio)-2-cyclohexyl-1-phenyl-2-
octene (3b2). The attempted synthesis of 3b2 was performed
according to RP-1 and starting from 2b. Traces of 3b2 were

376
J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
detected by GC–MS in the crude product. Column
chromatography (silica gel; pentane) afforded 2b (36%
yield), n-pentylcyclohexylacetylene 5b (54% yield) and
benzyl-n-butylthioether 6b2 (55% yield; 1H NMR (90 MHz,
CDCl3): d 0.88 (3H, t, J¼7.0 Hz), 1.26–1.63 (4H, m), 2.41
(2H, t, J¼6.9 Hz), 3.70 (2H, s), 7.25–7.32 (5H, m); MS
(EI): 180 (Mþ, 29), 91 (100), 65 (8)).
fluoride, and the mixture was heated to reflux for 16 h.
Column chromatography (silica gel; pentane) afforded (E)-
4-(phenylseleno)-3-tetradecene 4c (61% yield), as a yellow-
ish liquid. IR (neat): 3071, 2961, 2927, 2854, 1580, 1475,
1
1462, 1439, 1377, 1144, 1068, 1023, 725 cm21; H NMR
(400 MHz, CDCl3): d 0.88 (3H, t, J¼6.8 Hz), 1.01 (3H, t,
J¼7.3 Hz), 1.21–1.37 (14H, m), 1.47 (2H, m), 2.14 (2H,
quint., J¼7.6 Hz), 2.24 (2H, t, J¼7.6 Hz), 5.93 (1H, t,
J¼7.3 Hz), 7.21–7.27 (3H, m), 7.45 (2H, m); 13C NMR
(22.5 MHz, CDCl3): d 14.1, 22.7, 22.8, 29.0, 29.1, 29.3,
29.5, 29.6, 31.9, 32.8, 126.7, 129.0, 131.1, 131.6, 132.5,
139.7; MS (EI): 352 (Mþ, 76), 226 (99), 198 (32), 183 (15),
158 (67), 145 (13), 111 (17), 97 (38), 83 (51), 69 (100), 55
(99); HRMS: m/z for C20H32Se, calcd: 352.1669. Found:
352.1674.
4.2.4. (Z)-6-(n-Butylthio)-7-cyclohexyl-6-tetradecene-8-
yne (3b3). Synthesized according to RP-1 and starting
from 2b. Column chromatography (silica gel; pentane/Et2O,
99:1) afforded 3b3 (75% yield), as a yellow liquid. IR (neat):
2958, 2930, 2856, 2212, 1570, 1463, 1452, 1380, 1262,
1101, 890 cm21; 1H NMR (400 MHz, CDCl3): d 0.91 (9H,
m), 1.10–1.67 (24H, m), 1.74–1.78 (2H, m), 2.30 (2H, t,
J¼7.8 Hz), 2.35 (1H, m), 2.41 (2H, t, J¼6.8 Hz), 2.73 (2H,
t, J¼7.4 Hz); 13C NMR (22.5 MHz, CDCl3): d 13.7, 14.0,
14.0, 19.8, 22.1, 22.2, 22.5, 25.9, 26.4, 28.7, 29.1, 31.2,
31.6, 31.8, 31.9, 41.0, 79.0, 97.6, 127.5, 139.1; MS (EI): 362
(Mþ, 23), 305 (100), 249 (55), 223 (33), 181 (36), 167 (14),
115 (7), 91 (13), 81 (26), 55 (21); HRMS: m/z for C24H42S,
calcd: 362.3007. Found: 362.3013.
4.3. Boron to copper transmetalation
4.3.1. Representative procedure (RP-3) for the boron to
copper transmetalation (Scheme 6). Synthesis of (Z)-4-
ethyl-5-(phenylthio)-1,4-decadiene (3f4). A 100 mL two-
necked flask, equipped with a reflux condenser, an argon
inlet and a magnetic stirring bar, was charged with a THF
solution (26 mL) of 1-heptyne (1.538 g; 16 mmol). At
220 8C were added 10 mL of n-butyllithium (1.6 M in
hexane; 16 mmol). After 1 h of stirring at 220 8C, 16 mL of
triethylborane (1 M solution in THF; 16 mmol) were
introduced and the reaction mixture was allowed to warm
to room temperature for 1 h. After cooling to 278 8C, a THF
solution (18 mL) of benzenesulfenyl chloride (2.312 g;
16 mmol) was added dropwise. The cooling bath was then
removed and the mixture was stirred for 30 min at room
temperature. The reaction flask was cooled to 278 8C and
10 mL of n-butyllithium (1.6 M in hexane; 16 mmol) were
introduced. After 20 min, the mixture was transferred via
cannula to a separate reaction flask containing 3.290 g of
CuBr·SMe2 (16 mmol) in 16 mL of THF maintained at
278 8C. After an additional hour of stirring at 278 8C,
4.15 mL of allyl bromide (48 mmol; 3 equiv.) were added,
and the reaction flask was gradually warmed to room
temperature. The mixture was then diluted with 80 mL of
Et2O, and washed three times with 30 mL of a mixture of
saturated aqueous NH4Cl and NH4OH (4:1, v/v), and two
times with 20 mL of water. The organic phase was dried
over MgSO4, and concentrated. The crude product was
purified by column chromatography (silica gel; pentane) to
afford 3.568 g of 3f4 (81% yield) as a colorless liquid. IR
(neat): 3075, 2960, 2873, 1639, 1584, 1477, 1439, 1376,
1086, 1025, 994, 912, 739, 692 cm21; 1H NMR (400 MHz,
CDCl3): d 0.85 (3H, t, J¼7.1 Hz), 1.09 (3H, t, J¼7.6 Hz),
1.18–1.29 (4H, m), 1.50 (2H, m), 2.21 (2H, t, J¼7.8 Hz),
2.24 (2H, q, J¼7.6 Hz), 3.20 (2H, d, J¼6.4 Hz), 4.99–5.05
(2H, m), 5.77 (1H, ddt, J¼16.9, 10.0, 6.3 Hz), 7.10–7.15
(1H, m), 7.17–7.26 (4H, m); 13C NMR (22.5 MHz, CDCl3):
d13.3, 14.0, 22.5, 25.4, 29.0, 31.6, 32.9, 38.6, 115.5, 125.2,
128.2, 128.4, 128.7, 136.3, 137.1, 147.1; MS (EI): 274 (Mþ,
39), 197 (100), 183 (6), 127 (16), 109 (11), 91 (17), 79 (21),
67 (12), 55 (10). Anal. Calcd for C18H26S: C, 78.77; H, 9.55.
Found: C, 78.22; H, 9.66.
4.2.5. Representative procedure (RP-2) for the in situ
Suzuki–Miyaura coupling of air-sensitive alkenyl-
boranes. Synthesis of (Z)-6-(n-butylthio)-5-phenyl-5-
decene (3d1). A 50 mL two-necked flask, equipped with a
reflux condenser, an argon inlet and a magnetic stirring bar,
was charged with a THF solution (4 mL) of 1-hexyne
(0.164 g; 2 mmol). At 220 8C were added 1.25 mL of
n-butyllithium (1.6 M in hexane; 2 mmol). After 1 h of
stirring at 220 8C, 2 mL of tributylborane (1 M solution in
THF; 2 mmol) were introduced and the reaction mixture
was allowed to warm to room temperature for 1 h. After
cooling to 278 8C, a THF solution (4 mL) of n-butyl-
sulfenyl chloride (0.249 g; 2 mmol) was added dropwise.
The cooling bath was then removed and the mixture was
stirred for 30 min at room temperature. To this solution was
successively added tetrakis(triphenylphosphine)palladium
(0.092 g; 4 mol%), a THF solution (1 mL) of iodobenzene
(0.367 g; 1.8 mmol; 0.9 equiv.) and 3.6 mL of tetrabutyl-
ammonium fluoride (1 M in THF; 3.6 mmol; 1.8 equiv.).
The reaction mixture was heated to reflux for 20 h. After
cooling to room temperature, the solution was diluted with
15 mL of Et2O, washed with water, dried over MgSO4, and
concentrated. The crude product was purified by column
chromatography (silica gel; pentane) to afford 0.204 g of
3d1 (37% yield) as a colorless liquid. IR (neat): 3055, 3020,
2958, 2930, 2871, 1597, 1490, 1463, 1441, 1379, 1135,
1101, 1070, 769, 700 cm21; 1H NMR (90 MHz, CDCl3): d
0.77–1.05 (9H, m), 1.14–1.71 (12H, m), 2.38 (6H, m),
7.04–7.33 (5H, m); 13C NMR (22.5 MHz, CDCl3): d 13.6,
13.9, 14.1, 21.9, 22.6, 22.7, 30.5, 31.3, 31.4, 31.6, 31.8,
35.2, 126.2, 127.7, 128.8, 130.8, 142.9, 143.5; MS (EI): 304
(Mþ, 100), 261 (35), 247 (94), 205 (10), 191 (20), 171 (9),
157 (10), 143 (15), 129 (42), 115 (21), 91 (27), 57 (13).
Anal. Calcd for C20H32S: C, 78.88; H, 10.59. Found: C,
79.05; H, 10.20.
4.2.6. (Z)-3-Phenyl-4-(phenylseleno)-3-tetradecene (3c1).
The attempted synthesis of 3c1 was performed according to
RP-2, through the preparation of 2c. Sodium hydroxide
(3.0 equiv.) was used instead of tetrabutylammonium
4.3.2. (Z)-4-Ethyl-5-(phenylthio)-1,4-nonadiene (3g4).
Synthesized according to RP-3, through the preparation of
2g. The activation step was performed by transfer (through

J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
377
cannula) of the alkenylborane mixture on a suspension of
lithium methoxide in THF, previously cooled to 278 8C
(prepared by addition of 1 equiv. of n-butyllithium over a
THF solution of methanol at 278 8C, followed by stirring at
room temperature for 1 h). Column chromatography (silica
gel; pentane) afforded 3g4 (74% yield), as a colorless liquid.
IR (neat): 3075, 2961, 2932, 2873, 1638, 1614, 1584, 1477,
1459, 1439, 1376, 1215, 1086, 1025, 942, 912, 739,
(12), 69 (21), 67 (21), 55 (24); HRMS: m/z for C15H30S,
calcd: 242.2068. Found: 242.2063.
4.3.6. (E)-5-Methyl-6-(phenylthio)-5-decene (3h7). Syn-
thesized according to RP-3, through the preparation of 2h
and the use of methyl iodide as electrophile. Column
chromatography (silica gel; pentane) afforded 3h7 (72%
yield), as a colorless liquid. IR (neat): 3072, 2958, 2930,
2861, 1620, 1584, 1477, 1466, 1440, 1377, 1086, 1025, 738,
692 cm21 1H NMR (90 MHz, CDCl3): d 0.85 (3H, t,
;
J¼6.8 Hz), 1.09 (3H, t, J¼7.5 Hz), 1.13–1.59 (4H, m),
2.15–2.29 (4H, m), 3.21 (2H, d, J¼6.4 Hz), 4.91–5.12 (2H,
m), 5.78 (1H, ddt, J¼17.4, 9.4, 6.2 Hz), 7.15–7.28 (5H, m);
13C NMR (22.5 MHz, CDCl3): d13.3, 14.0, 22.5, 25.4, 31.5,
32.7, 38.6, 115.5, 125.2, 128.2, 128.3, 128.7, 136.3, 137.1,
147.1; MS (EI): 260 (Mþ, 42), 183 (100), 127 (17), 109 (13),
91 (18), 79 (23), 67 (13), 55 (9). Anal. Calcd for C17H24S: C,
78.40; H, 9.29. Found: C, 77.91; H, 9.32.
692 cm21 1H NMR (400 MHz, CDCl3): d 0.86 (3H, t,
;
J¼7.4 Hz), 0.96 (3H, t, J¼7.0 Hz), 1.26 (2H, m), 1.39 (2H,
m), 1.43–1.50 (4H, m), 1.98 (3H, s), 2.24 (2H, t, J¼7.6 Hz),
2.25 (2H, t, J¼7.6 Hz), 7.09–7.13 (1H, m), 7.17 (2H, m),
7.22–7.26 (2H, m); 13C NMR (22.5 MHz, CDCl3): d14.0,
14.0, 21.2, 22.5, 22.9, 30.7, 31.4, 33.4, 34.6, 124.9, 126.5,
127.5, 128.7, 137.6, 144.8; MS (EI): 262 (Mþ, 100), 219
(32), 164 (39), 149 (32), 135 (19), 123 (16), 109 (19), 95
(13), 81 (12), 67 (21), 55 (28). Anal. Calcd for C17H26S: C,
77.80; H, 9.98. Found: C, 77.41; H, 10.44.
4.3.3. (Z)-5-(n-Butylthio)-4-ethyl-1,4-nonadiene (3j4).
Synthesized according to RP-3, through the preparation of
2j. Column chromatography (silica gel; pentane) afforded
3j4 (74% yield), as a colorless liquid. IR (neat): 3078, 2961,
2932, 2873, 1638, 1609, 1461, 1434, 1377, 1216, 994,
4.3.7. (Z)-6-Ethyl-5-(phenylthio)-5-tridecene-7-yne (3g3).
Synthesized according to RP-3, through the preparation of
2g and the use of 1-iodo-1-heptyne (1.25 equiv.) as
electrophile. Column chromatography (silica gel; pentane)
afforded 3g3 (63% yield), as a yellowish liquid. IR (neat):
3072, 3060, 2959, 2932, 2861, 2218, 1731, 1583, 1475,
1
909 cm21; H NMR (90 MHz, CDCl3): d 0.88–1.06 (9H,
m), 1.14–1.67 (8H, m), 2.13 (2H, q, J¼7.4 Hz), 2.26 (2H, t,
J¼7.7 Hz), 2.55 (2H, t, J¼7.2 Hz), 3.16 (2H, d, J¼6.2 Hz),
4.88–5.09 (2H, m), 5.77 (1H, ddt, J¼17.6, 9.3, 6.2 Hz);
13C NMR (22.5 MHz, CDCl3): d13.3, 13.7, 14.1, 22.0,
22.6, 25.3, 31.1, 31.5, 31.8, 31.9, 38.3, 114.9, 129.5, 136.7,
142.1; MS (EI): 240 (Mþ, 9), 183 (100), 169 (8), 149 (8),
127 (31), 107 (19), 93 (20), 79 (19), 67 (13), 55 (12);
HRMS: m/z for C15H28S, calcd: 240.1912. Found:
240.1919.
1465, 1440, 1377, 1329, 1068, 1086, 1025, 743, 692 cm21
;
1H NMR (90 MHz, CDCl3): d 0.78–0.94 (6H, m), 1.15 (3H,
t, J¼7.5 Hz), 1.20–1.57 (10H, m), 2.11–2.41 (6H, m),
7.16–7.38 (5H, m); 13C NMR (22.5 MHz, CDCl3): d13.5,
13.7, 13.9, 19.6, 22.2, 22.3, 26.8, 28.5, 31.0, 31.1, 31.5,
80.4, 96.3, 126.5, 127.3, 128.6, 131.2, 135.3, 138.5; MS
(EI): 314 (Mþ, 25), 258 (7), 237 (37), 205 (12), 181 (100),
149 (7), 119 (7), 105 (10), 91 (21), 77 (12), 55 (9); HRMS:
m/z for C21H30S, calcd: 314.2068. Found: 314.2072.
4.3.4. (Z)-4-Ethyl-5-(phenylseleno)-1,4-decadiene (3k4).
Synthesized according to RP-3, through the preparation of
2k. Column chromatography (silica gel; pentane) afforded
3k4 (71% yield), as a yellowish liquid. IR (neat): 3072,
2960, 2931, 2868, 1638, 1580, 1438, 1376, 1069, 1023, 994,
4.3.8. (Z)-5-(n-Butylthio)-6-ethyl-5-tridecene-7-yne (3j3).
Synthesized according to RP-3, through the preparation of
2j and the use of 1-iodo-1-heptyne (1.25 equiv.) as
electrophile. Column chromatography (silica gel; pentane/
Et2O, 99.5:0.5) afforded 3j3 (59% yield), as a colorless
liquid. IR (neat): 2959, 2931, 2861, 2218, 1580, 1462, 1378,
1
912, 735, 692 cm21; H NMR (400 MHz, CDCl3): d 0.84
(3H, t, J¼7.1 Hz), 1.07 (3H, t, J¼7.6 Hz), 1.19–1.31 (4H,
m), 1.49 (2H, m), 2.23 (2H, q, J¼7.3 Hz), 2.26 (2H, t,
J¼7.8 Hz), 3.20 (2H, d, J¼6.4 Hz), 4.99–5.05 (2H, m),
5.77 (1H, ddt, J¼16.8, 10.0, 6.8 Hz), 7.18–7.26 (3H, m),
7.36 (2H, m); 13C NMR (100.4 MHz, CDCl3): d 13.4, 14.0,
22.5, 25.2, 29.4, 31.5, 34.7, 41.0, 115.5, 126.1, 128.7, 128.9,
131.4, 131.9, 136.4, 145.3; MS (EI): 322 (Mþ, 50), 245
(100), 175 (7), 157 (11), 123 (8), 109 (25), 95 (54), 91 (32),
79 (40), 67 (51), 55 (41); HRMS: m/z for C18H26Se, calcd:
322.1200. Found: 322.1202.
1329, 1271, 1133, 1101, 1061, 746 cm21
;
1H NMR
(90 MHz, CDCl3): d 0.84–0.99 (9H, m), 1.08 (3H, t,
J¼7.6 Hz), 1.19–1.62 (14H, m), 2.08–2.48 (6H, m), 2.74
(3H, t, J¼7.6 Hz); 13C NMR (22.5 MHz, CDCl3): d 13.5,
13.7, 13.9, 14.0, 19.7, 22.0, 22.2, 22.6, 26.7, 28.6, 31.1,
31.3, 31.6, 31.8, 80.4, 96.5, 123.3, 139.7; MS (EI): 294 (Mþ,
23), 237 (35), 205 (8), 181 (100), 125 (11), 107 (7), 91 (9),
55 (5); HRMS: m/z for C19H34S, calcd: 294.2381. Found:
294.2387.
4.3.5. (E)-6-(n-Butylthio)-5-methyl-5-decene (3d7). Syn-
thesized according to RP-3, through the preparation of 2d
and the use of methyl iodide as electrophile. Column
chromatography (silica gel; pentane) afforded 3d7 (68%
yield), as a colorless liquid. IR (neat): 2959, 2931, 2861,
4.3.9. (Z)-3-Benzyl-4-(phenylthio)-3-octene (3g2). Syn-
thesized according to RP-3, through the preparation of 2g
and the use of benzyl bromide as electrophile. Kugelrohr
distillation followed by column chromatography (silica gel;
pentane) afforded 3g2 (13% yield), as a yellowish liquid. IR
(neat): 3062, 3027, 2960, 2931, 2872, 1601, 1584, 1494,
1
1619, 1464, 1377, 1273, 1222, 1103, 993, 744 cm21; H
NMR (90 MHz, CDCl3): d 0.83–0.98 (9H, m), 1.13–1.65
(12H, m), 1.92 (3H, s), 2.04–2.33 (4H, m), 2.55 (2H, t,
J¼7.0 Hz); 13C NMR (22.5 MHz, CDCl3): d 13.7, 14.0,
20.8, 22.0, 22.6, 22.8, 30.7, 31.4, 31.9, 31.9, 32.1, 34.6,
127.9, 139.3; MS (EI): 242 (Mþ, 75), 199 (50), 185 (100),
143 (26), 129 (10), 109 (19), 101 (23), 95 (16), 87 (17), 81
1
1477, 1454, 1441, 1117, 1089, 1027, 739, 699 cm21; H
NMR (400 MHz, CDCl3): d 0.86 (3H, t, J¼7.2 Hz), 1.06
(3H, t, J¼7.6 Hz), 1.26 (2H, m), 1.53 (2H, m), 2.17 (2H, q,
J¼7.5 Hz), 2.27 (2H, t, J¼7.8 Hz), 3.86 (2H, s), 7.10–7.28
(10H, m); 13C NMR (100.4 MHz, CDCl3): d 13.4, 14.0,

378
J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
22.5, 25.0, 31.6, 32.6, 39.6, 125.3, 125.9, 128.3, 128.3,
128.7, 128.8, 137.1, 140.2, 148.0; MS (EI): 310 (Mþ, 100),
281 (9), 219 (10), 177 (8), 167 (8), 157 (11), 145 (23), 129
(44), 117 (21), 105 (8), 91 (65), 65 (8). Anal. Calcd for
C21H26S: C, 81.23; H, 8.44. Found: C, 81.10; H, 8.73.
3i7 (69% yield). IR (neat): 3071, 3061, 2930, 2854, 1611,
1584, 1476, 1448, 1376, 1143, 1086, 1025, 738, 691 cm21
;
1H NMR (90 MHz, CDCl3): d 0.86 (3H, t, J¼6.2 Hz), 1.15–
1.85 (16H, m), 1.89 (3H, s), 2.27 (2H, t, J¼7.4 Hz), 2.60
(1H, m), 7.09–7.24 (5H, m); 13C NMR (22.5 MHz, CDCl3):
d 14.0, 16.6, 22.5, 26.1, 26.6, 29.1, 31.2, 31.5, 33.6, 42.5,
124.8, 125.7, 127.3, 128.7, 137.7, 149.3; MS (EI): 302 (Mþ,
100), 287 (7), 225 (65), 164 (46), 149 (12), 135 (18), 123
(13), 109 (22), 91 (18), 81 (28), 67 (18), 55 (29). Anal. Calcd
for C20H30S: C, 79.41; H, 9.99. Found: C, 79.36; H, 10.01.
4.3.10. (Z)-3-Ethyl-4-(phenylthio)-3-octen-2-one (3g5).
Synthesized according to RP-3, through the preparation of
2g and the use of acetyl chloride as electrophile. Column
chromatography (silica gel; pentane/Et2O, 95:5) afforded
3g5 (29% yield), as a yellow liquid. IR (neat): 3060, 2960,
2933, 2873, 1692, 1583, 1478, 1440, 1377, 1350, 1241,
4.3.13. (E)-4-sec-Butyl-5-(n-butylthio)-1,4-nonadiene
(3n4). Synthesized according to RP-4, starting from 2n
and using allyl bromide as electrophile. Column chroma-
tography (silica gel; pentane) afforded 3n4 (71% yield), as a
colorless liquid. IR (neat): 3079, 2961, 2931, 2874, 1637,
1
1140, 1096, 1025, 744, 692 cm21; H NMR (400 MHz,
CDCl3): d 0.80 (3H, t, J¼7.3 Hz), 1.10 (3H, t, J¼7.6 Hz),
1.21 (2H, m), 1.45 (2H, m), 2.18 (2H, t, J¼7.8 Hz), 2.40
(3H, s), 2.41 (2H, q, J¼7.5 Hz), 7.22–7.32 (5H, m); 13C
NMR (100.4 MHz, CDCl3): d 13.4, 13.8, 22.3, 24.2, 30.5,
31.1, 31.2, 126.9, 129.0, 130.4, 134.6, 134.8, 147.7, 204.7;
MS (EI): 262 (Mþ, 60), 247 (7), 185 (6), 153 (100), 135 (6),
110 (19); HRMS: m/z for C16H22OS, calcd: 262.1391.
Found: 262.1395.
1
1601, 1461, 1425, 1378, 1215, 993, 907 cm21; H NMR
(400 MHz, CDCl3): d 0.82 (3H, t, J¼7.4 Hz), 0.89–0.99
(9H, m), 1.34–1.52 (10H, m), 2.21 (1H, m), 2.39 (1H, m),
2.49–2.73 (3H, m), 2.97 (1H, dd, J¼15.2, 6.4 Hz), 3.15
(1H, dd, J¼15.2, 6.4 Hz), 4.94–5.02 (2H, m), 5.11 (1H, ddt,
J¼16.9, 10.5, 6.2 Hz); 13C NMR (22.5 MHz, CDCl3): d
12.4, 13.7, 14.1, 19.6, 22.0, 22.6, 28.2, 30.6, 31.4, 31.9,
32.0, 33.9, 38.6, 114.5, 130.6, 138.2, 143.4; MS (EI): 268
(Mþ, 10), 239 (23), 211 (75), 183 (66), 169 (9), 155 (100),
141 (7), 121 (13), 107 (18), 93 (23), 79 (23), 67 (16), 57
(22). Anal. Calcd for C17H32S: C, 76.05; H, 12.01. Found:
C, 76.07; H, 11.98.
4.3.11. (Z)-2-Ethyl-1-phenyl-3-(phenylthio)-hept-2-ene-
1-one (3g6). Synthesized according to RP-3, through the
preparation of 2g and the use of benzoyl chloride as
electrophile. Column chromatography (silica gel; pentane/
Et2O, 95:5) afforded 3g5 (32% yield), as a yellowish liquid.
IR (neat): 3060, 2959, 2932, 2873, 1665, 1597, 1581, 1478,
1449, 1315, 1279, 1245, 1026, 1168, 1024, 897, 743, 711,
691 cm21
;
1H NMR (400 MHz, CDCl3): d 0.89 (3H, t,
4.3.14. (E)-3-Cyclohexyl-4-(phenylthio)-3-nonene (3i8).
Synthesized according to RP-4, starting from 2i and using
ethyl iodide as electrophile. The purification by column
chromatography (silica gel; pentane) gave a mixture of 3i8
and n-pentylcyclohexylacetylene 5b. The latter was
removed by Kugelrohr distillation under reduced pressure
(24% yield of 5b) to give essentially pure 3i8 (28% yield), as
a colorless liquid. IR (neat): 3071, 2930, 2854, 1584, 1476,
J¼7.3 Hz), 1.10 (3H, t, J¼7.6 Hz), 1.33 (2H, m), 1.59 (2H,
m), 2.29 (2H, t, J¼7.8 Hz), 2.51 (2H, q, J¼7.6 Hz), 7.15–
7.25 (5H, m), 7.46 (2H, m), 7.54 (1H, m), 7.95 (2H, m); 13C
NMR (100.4 MHz, CDCl3): d 13.1, 13.9, 22.5, 25.1, 30.7,
30.8, 31.1, 126.7, 128.6, 128.8, 129.1, 130.5, 132.9, 133.0,
134.5, 137.0, 146.6, 198.1; MS (EI): 324 (Mþ, 35), 281 (11),
247 (8), 215 (79), 173 (31), 159 (12), 145 (14), 105 (100), 77
(57); HRMS: m/z for C21H24OS, calcd: 324.1548. Found:
324.1552.
1
1450, 1376, 1085, 1025, 892, 738, 691 cm21; H NMR
(400 MHz, CDCl3): d 0.86 (3H, t, J¼7.1 Hz), 1.02 (3H, t,
J¼7.3 Hz), 1.15–1.48 (11H, m), 1.59–1.83 (5H, m), 2.19
(2H, t, J¼7.8 Hz), 2.32 (2H, q, J¼7.5 Hz), 2.60 (1H, tt,
J¼11.6, 3.4 Hz), 7.08–7.25 (5H, m); 13C NMR (22.5 MHz,
CDCl3): d 14.0, 15.5, 22.5, 24.0, 26.1, 26.7, 29.4, 31.4, 31.7,
32.8, 42.9, 124.9, 126.6, 127.8, 128.7, 137.7, 154.7; MS
(EI): 316 (Mþ, 100), 287 (86), 239 (46), 178 (27), 163 (9),
149 (8), 135 (13), 123 (16), 109 (17), 95 (24), 81 (25), 67
(21), 55 (29); HRMS: m/z for C21H32S, calcd: 316.2225.
Found: 316.2218.
4.3.12. Representative procedure (RP-4) for the boron to
copper transmetalation (Scheme 7, conditions A).
Synthesis of (E)-2-cyclohexyl-3-(phenylthio)-2-octene
(3i7). A three-necked 25 mL flask equipped with a septum
and a flexible side-arm containing 0.191 g (1 mmol) of
copper(I) iodide was placed under argon, and charged with a
THF solution (3 mL) of 2i and 0.5 mL of HMPA. At
233 8C, 1.42 mL of methyllithium were introduced (1.4 M
in ether; 2 mmol; 2 equiv.) and the flask was keeped at this
temperature for 30 min before the addition of the copper
iodide. The mixture was maintained at 233 8C for 3 h under
vigorous stirring before the introduction of methyl iodide
(0.19 mL; 3 mmol; 3 equiv.). The stirring was continued for
4 h at 233 8C and then the cooling bath was removed. The
reaction mixture was diluted with 20 mL of Et2O and
washed with a mixture (4:1, v/v) of saturated aqueous
ammonium chloride and aqueous ammonium hydroxide
(28%), and with water; the organic phase was dried over
MgSO4 and made free of solvent under reduced pressure.
The purification by column chromatography (silica gel;
pentane) gave a mixture of 3i7 and n-pentylcyclohexyl-
acetylene 5b. The latter was removed by Kugelrohr
distillation under reduced pressure to give essentially pure
4.3.15. Representative procedure (RP-5) for the boron to
copper transmetalation (Scheme 7, conditions B).
Synthesis of (E)-5-ethyl-6-(phenylthio)-5-decene (3h8).
A three-necked 50 mL flask equipped with a septum and a
flexible side-arm containing 0.382 g (2 mmol) of copper(I)
iodide was placed under argon. A THF solution (3 mL) of
1-hexyne (0.164 g; 2 mmol) was introduced and cooled to
220 8C; n-butyllithium (1.6 M in hexane; 1.25 mL;
2 mmol) was added and the mixture was stirred for 1 h.
2 mL of tri-n-butylborane (1 M in THF; 2 mmol) were then
introduced, the cooling bath was removed and the mixture
was stirred for 1 h at room temperature. After cooling to
278 8C, a solution of benzenesulfenyl chloride (0.289 g;
2 mmol) in 3 mL THF was added dropwise; the flask was

J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
379
warmed to room temperature for 15 min, and cooled again
to 278 8C. Methyllithium (1.4 M in ether; 2.9 mL; 4 mmol;
2 equiv.) was introduced and the mixture was stirred for
15 min before successive addition of copper iodide, HMPA
(2 mL), triethylphosphite (0.41 mL; 2.4 mmol; 1.2 equiv.)
and ethyl iodide (0.24 mL; 3 mmol; 1.5 equiv.). The cooling
bath was allowed to warm-up to room temperature and
stirring was continued overnight. The reaction mixture was
diluted with 20 mL of Et2O and washed with a mixture (4:1,
v/v) of saturated aqueous ammonium chloride and aqueous
ammonium hydroxide (28%), and with water; the organic
phase was dried over MgSO4 and made free of solvent under
reduced pressure. GC analysis via calibration using
tridecane as internal standard revealed the presence of
5-decyne 5h (21% yield) and ethylthiobenzene 6h8 (19%
yield). Kugelrohr distillation followed by column chroma-
tography (silica gel; pentane) afforded 3h8 (45% yield), as a
colorless liquid. IR (neat): 3069, 2959, 2931, 2872, 1583,
pentane) afforded 3d2 (64% yield), as a yellowish liquid. IR
(neat): 3083, 3062, 3027, 2958, 2930, 2862, 1602, 1494,
1456, 1379, 1273, 1221, 1100, 1030, 957, 729, 700 cm21
;
1H NMR (90 MHz, CDCl3): d 0.93–1.00 (9H, m), 1.14–
1.66 (12H, m), 2.02 (2H, t, J¼7.3 Hz), 2.33 (2H, t,
J¼7.4 Hz), 2.54 (2H, t, J¼6.9 Hz), 3.82 (2H, s), 7.03–
7.24 (5H, m); 13C NMR (22.5 MHz, CDCl3): d 13.7, 13.9,
14.1, 21.9, 22.7, 22.8, 30.9, 31.2, 31.4, 31.7, 31.9, 39.7,
125.7, 128.2, 128.6, 130.4, 140.7, 141.9; MS (EI): 318 (Mþ,
100), 275 (16), 261 (32), 227 (39), 185 (31), 171 (22), 143
(24), 129 (63), 91 (68); HRMS: m/z for C21H34S, calcd:
318.2381. Found: 318.2377.
4.4.. Nickel catalyzed coupling of vinylsulfides
4.4.1. Representative procedure (RP-6) for the cross-
coupling of vinylsulfides with Grignard reagents. Syn-
thesis of (E)-5-methyl-6-phenyl-5-decene (7A). In a
25 mL two-necked flask, equipped with an argon inlet and
a magnetic stirring bar, were introduced a solution of 3h7
(0.210 g; 0.8 mmol) in Et2O (7 mL) and NiCl2(dmpe)
(0.007 g; 0.025 mmol; 3% mol.). Phenylmagnesium
bromide (0.67 mL of a 3 M solution in Et2O; 2 mmol;
2.5 equiv.) was added and the reaction mixture was stirred at
room temperature for 14.5 h before the addition of 1 mL of
saturated aqueous NH4Cl. After dilution with Et2O, the
organic layer was separated, washed with 10 mL of aqueous
NaOH (1 M) and with water, dried over MgSO4, and
concentrated. The crude product was purified by column
chromatography (silica gel; pentane) providing 0.152 g of
biphenyl and 0.151 g of 7A (82% yield) as a colorless
liquid. IR (neat): 3078, 3058, 3022, 2958, 2929, 2860, 1600,
1574, 1492, 1465, 1442, 1378, 1133, 1105, 1071, 771, 744,
1
1477, 1459, 1439, 1377, 1085, 1025, 738, 691 cm21; H
NMR (90 MHz, CDCl3): d 0.85–1.08 (9H, m), 1.19–1.50
(8H, m), 2.08–2.36 (4H, m), 2.41 (2H, q, J¼7.6 Hz), 7.07–
7.25 (5H, m); 13C NMR (22.5 MHz, CDCl3): d 13.7, 14.0,
22.4, 23.1, 27.7, 31.2, 31.5, 32.0, 32.8, 124.9, 126.2, 127.7,
128.7, 137.6, 150.7; MS (EI): 276 (Mþ, 100), 233 (34), 178
(37), 163 (22), 149 (8), 135 (19), 123 (23), 109 (14), 95 (15),
81 (24), 69 (23), 55 (24); HRMS: m/z for C18H28S, calcd:
276.1912. Found: 276.1910.
4.3.16. (E)-6-(n-Butylthio)-5-ethyl-5-decene (3d8). Syn-
thesized according to RP-5, through the preparation of 2d.
Column chromatography (silica gel; pentane) afforded 3d8
(66% yield), as a colorless liquid. IR (neat): 2960, 2931,
1
2862, 1611, 1461, 1378, 1272, 1222, 1102, 745 cm21; H
NMR (90 MHz, CDCl3): d 0.87–1.03 (12H, m), 1.13–1.64
(12H, m), 2.01–2.33 (4H, m), 2.37 (2H, q, J¼7.6 Hz), 2.54
(2H, t, J¼7.0 Hz); 13C NMR (22.5 MHz, CDCl3): d 13.4,
13.7, 14.0, 14.1, 22.0, 22.6, 22.9, 27.2, 31.1, 31.4, 31.7,
31.9, 31.9, 127.5, 145.4; MS (EI): 256 (Mþ, 61), 213 (37),
199 (100), 157 (16), 143 (7), 123 (7), 109 (7), 101 (15), 95
(12), 81 (21), 69 (17), 67 (15), 55 (20). Anal. Calcd for
C16H32S: C, 74.92; H, 12.57. Found: C, 74.71; H, 12.48.
702 cm21 1H NMR (400 MHz, CDCl3): d 0.85 (3H, t,
;
J¼7.2 Hz), 0.97 (3H, t, J¼7.1 Hz), 1.19–1.28 (4H, m),
1.36–1.49 (4H, m), 1.50 (3H, s), 2.18 (2H, t, J¼7.7 Hz),
2.34 (2H, t, J¼7.3 Hz), 7.07–7.10 (2H, m), 7.19–7.23 (1H,
m), 7.27–7.33 (2H, m); 13C NMR (22.5 MHz, CDCl3): d
14.0, 14.2, 19.9, 22.7, 22.9, 30.8, 33.7, 33.7, 125.6, 127.8,
129.0, 131.3, 135.8, 144.4; MS (EI): 230 (Mþ, 65), 187 (16),
173 (27), 145 (35), 131 (100), 117 (40), 105 (13), 91 (43).
Anal. Calcd for C17H26: C, 88.63; H, 11.37. Found: C,
88.59; H, 11.13.
4.3.17. (Z)-5-Benzyl-6-(phenylthio)-5-decene (3h2). Syn-
thesized according to RP-5, through the preparation of 2h
and the use of benzyl bromide as electrophile. Kugelrohr
distillation followed by column chromatography (silica gel;
pentane) afforded 3h2 (62% yield). IR (neat): 3062, 3027,
2958, 2931, 2862, 1601, 1584, 1494, 1477, 1451, 1440,
4.4.2. (Z)-4-Ethyl-5-phenyl-1,4-decadiene (7B). Syn-
thesized according to RP-6, starting from 3f4. The reaction
mixture was heated to reflux for 23 h. Column chromato-
graphy (silica gel; pentane) afforded 7B (38% yield), as a
colorless liquid. IR (neat): 3078, 3058, 3021, 2962, 2931,
2873, 2861, 1636, 1600, 1491, 1460, 1440, 1376, 1071, 994,
1
1379, 1088, 1026, 739, 699 cm21; H NMR (400 MHz,
CDCl3): d 0.86 (3H, t, J¼7.3 Hz), 0.91 (3H, t, J¼7.3 Hz),
1.27 (2H, m), 1.33 (2H, m), 1.45 (2H, m), 1.54 (2H, m), 2.13
(2H, t, J¼7.8 Hz), 2.27 (2H, t, J¼7.8 Hz), 3.86 (2H, s),
7.11–7.28 (10H, m); 13C NMR (100.4 MHz, CDCl3): d
14.0, 22.5, 22.9, 31.0, 31.5, 31.7, 32.6, 40.0, 125.3, 125.9,
128.2, 128.3, 128.6, 128.8, 129.1, 137.1, 140.2, 146.7; MS
(EI): 338 (Mþ, 100), 281 (9), 247 (13), 185 (14), 143 (17),
129 (38), 117 (22), 91 (73). Anal. Calcd for C23H30S: C,
81.60; H, 8.93. Found: C, 81.64; H, 9.05.
1
910, 766, 702 cm21; H NMR (90 MHz, CDCl3): d 0.83
(3H, t, J¼6.4 Hz), 1.04 (3H, t, J¼7.4 Hz), 1.15–1.30 (6H,
m), 2.18 (2H, q, J¼7.4 Hz), 2.31 (2H, t, J¼7.6 Hz), 2.58
(2H, d, J¼6.4 Hz), 4.78–5.02 (2H, m), 5.77 (1H, ddt,
J¼18.2, 8.6, 6.1 Hz), 7.02–7.31 (5H, m); 13C NMR
(22.5 MHz, CDCl3): d 13.4, 14.0, 22.6, 23.7, 28.1, 31.8,
34.0, 37.2, 114.9, 125.9, 127.8, 128.7, 134.7, 137.3, 137.7,
143.7; MS (EI): 242 (Mþ, 100), 213 (27), 185 (10), 171 (99),
157 (20), 143 (64), 129 (67), 115 (20), 105 (12), 91 (55);
HRMS: m/z for C18H26, calcd: 242.2035. Found: 242.2033.
4.3.18. (Z)-5-Benzyl-6-(n-butylthio)-5-decene (3d2). Syn-
thesized according to RP-5, through the preparation of 2d
and the use of benzyl bromide as electrophile. Kugelrohr
distillation followed by column chromatography (silica gel;
4.4.3. 5-n-Butyl-6-methyl-5-decene (7C). Synthesized
according to RP-6, using n-butylmagnesium bromide

380
J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
(0.5 M in Et2O) as the Grignard reagent. The reaction
mixture was heated to reflux for 22.5 h. Column chroma-
tography (silica gel; pentane) afforded 7C (70% yield), as a
colorless liquid. IR (neat): 2958, 2929, 2861, 1656, 1465,
liquid. IR (neat): 3072, 2961, 2932, 2872, 1584, 1477, 1463,
1
1440, 1377, 1133, 1087, 1067, 1025, 739, 691 cm21; H
NMR (400 MHz, CDCl3): d 0.84 (3H, t, J¼7.1 Hz), 0.90
(3H, t, J¼7.6 Hz), 1.09 (3H, t, J¼7.3 Hz), 1.17–1.29 (4H,
m), 1.39–1.52 (4H, m), 2.19 (2H, t, J¼7.8 Hz), 2.23 (2H, q,
J¼7.3 Hz), 2.38 (2H, t, J¼7.8 Hz), 7.09–7.13 (1H, m), 7.17
(2H, m), 7.21–7.25 (2H, m); 13C NMR (22.5 MHz, CDCl3):
d 13.5, 14.0, 14.2, 22.3, 22.6, 22.6, 29.1, 31.6, 32.9, 36.1,
125.0, 126.8, 127.8, 128.7, 137.6, 150.3; MS (EI): 276
(Mþ, 100), 247 (34), 178 (50), 163 (19), 149 (7), 135 (17),
123 (21), 109 (12), 95 (22), 81 (22), 69 (23), 55 (30). Anal.
Calcd for C18H28S: C, 78.20; H, 10.21. Found: C, 77.83; H,
10.21.
1
1341, 1289, 1222, 1151, 1106, 896, 727 cm21; H NMR
(90 MHz, CDCl3): d 0.90 (9H, m), 1.11–1.41 (12H, m),
1.61 (3H, s), 1.98 (6H, m); 13C NMR (22.5 MHz, CDCl3): d
14.1, 17.9, 22.8, 23.0, 23.1, 31.0, 31.1, 31.5, 31.8, 32.1,
33.9, 128.4, 133.3; MS (EI): 210 (Mþ, 38), 153 (13), 125
(12), 112 (45), 97 (58), 83 (50), 69 (100), 55 (69); HRMS:
m/z for C15H30, calcd: 210.2348. Found: 210.2354.
4.4.4. (E)-5-Benzyl-6-methyl-5-decene (7D). Synthesized
according to RP-6, starting from 3h2, and using methyl-
magnesium bromide (3 M in Et2O) as the Grignard reagent.
The reaction mixture was heated to reflux for 10 days.
Column chromatography (silica gel; pentane) afforded 3h2
(60% yield), and a mixture of (E)-5-benzyl-5-decene (2%
yield) and 7D (24% yield) in a 8:92 ratio (determined by 1H
NMR), as a colorless liquid. IR (neat): 3084, 3063, 3028,
2958, 2929, 2861, 1603, 1494, 1455, 1378, 1103, 1074,
1030, 727, 698 cm21; 1H NMR (400 MHz, CDCl3): d 0.86
(3H, t, J¼7.1 Hz), 0.93 (3H, t, J¼7.3 Hz), 1.23–1.44 (8H,
m), 1.72 (3H, s), 1.95 (2H, t, J¼7.8 Hz), 2.09 (2H, t,
J¼7.8 Hz), 3.40 (2H, s), 7.13–7.18 (3H, m), 7.24–7.28
(2H, m); 13C NMR (22.5 MHz, CDCl3): d 14.0, 14.1, 18.6,
23.0, 31.0, 31.2, 31.6, 34.0, 37.6, 125.5, 128.2, 128.4, 131.0,
131.3, 141.2; MS (EI): 244 (Mþ, 80), 187 (97), 145 (38),
131 (72), 117 (50), 105 (21), 97 (32), 91 (10%), 83 (20), 69
(23), 55 (72); HRMS: m/z for C18H28, calcd: 244.2191.
Found: 244.2198.
References and notes
1. Gerard, J.; Hevesi, L. Tetrahedron 2001, 57, 9109–9121.
2. (a) Suzuki, A. In Metal-catalyzed cross-coupling reactions;
Diederich, F., Stang, P. J., Eds.; Wiley-VCH: Weinheim,
1998; pp 49–97. (b) Miyaura, N.; Yamada, K.; Suzuki, A.
Tetrahedron Lett. 1979, 20, 3437. (c) Miyaura, N.; Suzuki, A.
Chem. Rev. 1995, 95, 2457. (d) Tsuji, J. Palladium reagents
and catalysts; Wiley: Chichester, 1995; pp 218–227.
(e) Suzuki, A. J. Organomet. Chem. 1999, 576, 147.
3. This reaction is probably the selenium analogue of the Pd-
catalyzed substitution of aromatic halides by thiolates: Migita,
T.; Shimizu, T.; Asami, Y.; Shiobara, J.-I.; Kato, Y.; Kosugi,
M. Bull. Chem. Soc. Jpn 1980, 53, 1385.
4. See Ref. 1 and references therein.
5. Such catalysis does have precedents: (a) Yatagai, H.;
Yamamoto, Y.; Maruyama, K. J. Chem. Soc., Chem. Commun.
1978, 702. (b) Yatagai, H. Bull. Chem. Soc. Jpn 1980, 53,
1670.
4.4.5. (Z)-4-Ethyl-5-phenyl-4-decene (7E). Synthesized
according to RP-6, starting from 3f9. The reaction mixture
was heated to reflux for 15 h. Column chromatography
(silica gel; pentane) afforded 7E (76% yield), as a colorless
liquid. IR (neat): 3078, 3057, 3021, 2961, 2930, 2871, 1600,
6. (a) Soderquist, J. A.; Najafi, M. R. J. Org. Chem. 1986, 51,
1330. (b) Soderquist, J. A.; Santiago, B. Tetrahedron Lett.
1990, 31, 5541. (c) Soderquist, J. A.; Leon-Colon, G.
Tetrahedron Lett. 1991, 32, 43. (d) Rivera, I.; Soderquist,
J. A. Tetrahedron Lett. 1991, 32, 2311.
1575, 1491, 1465, 1442, 1377, 1133, 1071, 770, 702 cm21
;
1H NMR (400 MHz, CDCl3): d 0.72 (3H, t, J¼7.3 Hz), 0.83
(3H, t, J¼6.8 Hz), 1.05 (3H, t, J¼7.3 Hz), 1.21–1.26 (6H,
m), 1.28 (2H, m), 1.78 (2H, t, J¼7.8 Hz), 2.17 (2H, q,
J¼7.5 Hz), 2.28 (2H, t, J¼6.8 Hz), 7.05 (2H, m), 7.17–7.21
(1H, m), 7.26–7.30 (2H, m); 13C NMR (22.5 MHz, CDCl3):
d 13.7, 14.1, 14.2, 22.0, 22.6, 23.7, 28.1, 31.9, 34.1, 34.5,
125.6, 127.7, 129.0, 136.0, 137.2, 144.3; MS (EI): 244 (Mþ,
100), 215 (23), 201 (10), 187 (6), 173 (45), 159 (18), 145
(84), 131 (98), 117 (84), 105 (21), 91 (69), 77 (10), 69 (9),
55 (13). Anal. Calcd for C18H28: C, 88.45; H, 11.55. Found:
C, 88.87; H, 11.72.
7. Ichikawa, J.; Minami, T.; Sonoda, T.; Kobayashi, H.
Tetrahedron Lett. 1992, 33, 3779.
8. Miyaura, N.; Yamada, K.; Suginome, H.; Suzuki, A. J. Am.
Chem. Soc. 1985, 107, 972.
9. For a review, see: (a) Knochel, P.; Betzemeier, B. In Modern
organocopper chemistry; Krause, N., Ed.; Wiley-VCH:
Weinheim, 2002; pp 51–53. see also: (b) Miyaura, N.; Itoh,
M.; Suzuki, A. Synthesis 1976, 618. (c) Brown, H. C.;
Campbell, J. B., Jr. J. Org. Chem. 1980, 45, 550. (d) Yatagai,
H. J. Org. Chem. 1980, 45, 1640. (e) Hoshi, M.; Masuda, Y.;
Arase, A. Bull. Chem. Soc. Jpn 1986, 59, 659. (f) Wang, K. K.;
Chu, K.-H.; Lin, Y.; Chen, J.-H. Tetrahedron 1989, 45, 1105.
10. In a similar context it was suggested that syn elimination took
place at the level of the vinylcopper intermediate: see Ref. 9f.
11. Jabri, N.; Alexakis, A.; Normant, J.-F. Tetrahedron Lett. 1983,
24, 5081.
4.4.6. Catalytic hydrogenation of 3f4. Synthesis of (Z)-4-
ethyl-5-(phenylthio)-4-decene (3f9). A two-necked 25 mL
flask equipped with a septum was placed under hydrogen
atmosphere. A solution of 3f4 (1.067 g; 3.89 mmol) in
hydrogen flushed benzene and chlorotris(triphenylphos-
phine)rhodium(I) (0.111 g; 0.12 mmol; 3 mol%) were
successively introduced, and the resulting brown solution
was stirred at room temperature for 12 h. The solvent was
removed under reduced pressure, and the residue was
extracted with Et2O (3£15 mL). The combined organic
layers were filtered over celite, and then concentrated under
reduced pressure. Column chromatography (silica gel;
pentane) afforded 0.962 g of 3f9 (90% yield), as a colorless
12. Normant, J.-F.; Cahiez, G.; Chuit, C.; Villieras, J. Organomet.
Chem. 1974, 77, 269.
13. (a) Uchida, K.; Utimoto, K.; Nozaki, H. J. Org. Chem. 1976,
41, 2941. (b) Uchida, K.; Utimoto, K.; Nozaki, H. Tetrahedron
1977, 33, 2987.
14. See for example: (a) De Lucchi, O.; Pasquato, L. Tetrahedron
1988, 44, 6755–6794. (b) selective oxidation of these vinyl

J. Gerard, L. Hevesi / Tetrahedron 60 (2004) 367–381
381
sulfides into vinyl sulfoxides or vinyl sulfones has been carried
´
out successfully by means of dimethyldioxirane: Levai, A.;
17. Heck, R. F. In Palladium reagents in organic syntheses;
Katritzky, A. R., Meth-Cohn, O., Rees, C. W., Eds.;
Academic: London, 1985; pp 2–3.
Hevesi, L.; Gerard, J. Results to be published.
15. Booth, G.; Chatt, J. Chem. Soc. 1965, 3238.
16. Tamao, K.; Sumitani, K.; Kiso, Y.; Zembayashi, M.; Fujioka,
A.; Kodama, S.-I.; Nakajima, I.; Minato, A.; Kumada, M. Bull.
Chem. Soc. Jpn 1976, 49, 1958.
18. Brandsma, L. Preparative acetylenic chemistry; Elsevier:
Amsterdam, 1988; pp 143–157.