Palladium-tetraphosphine complex catalysed heck reaction of vinyl bromides with alkenes: A powerful access to conjugated dienes

Article abstract of DOI:10.1055/s-2008-1032124

A wide variety of 1,3-dienes have been prepared by the Heck vinylation of vinyl bromides using [Pd(η³-C₃H₅)Cl] ₂/cis,cis,cis-1,2,3,4-tetrakis[(diphenylphosphino)methyl] cyclopentane (Tedicyp) as the catalyst precursor. Both α- and β-substituted vinyl bromides undergo the Heck reaction with functionalised alkenes such as acrylates, enones, styrenes or a vinyl sulfone, and also with nonfunctionalised alkenes such as dec-1-ene, leading stereoselectively, in most cases, to the corresponding E- or E,E-1,3-dienes in good yields. Furthermore, this catalyst can be used at low loading for several reactions. Georg Thieme Verlag Stuttgart.

Full text of DOI:10.1055/s-2008-1032124

1142
PAPER
Palladium–Tetraphosphine Complex Catalysed Heck Reaction of Vinyl
Bromides with Alkenes: A Powerful Access to Conjugated Dienes
C
onjugatedDienes by
h
the
H
eckRe
a
actionof
V
m
inyl Bromides
w
ith
eA
lkenes d Lemhadri,a Ahmed Battace,a Florian Berthiol,a Touriya Zair,b Henri Doucet,*c Maurice Santelli*a
a
Laboratoire de Synthèse Organique, Faculté des Sciences de Saint Jérôme, UMR 6180 CNRS, Université d’Aix-Marseille III,
Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex 20, France
Fax +33(4)91983865; E-mail: m.santelli@univ-cezanne.fr
Laboratoire de Chimie Organique Appliquée, Faculté des Sciences, Université Moulay Ismail, BP 4010,
Beni M’mhammed, 50000 Meknes, Morocco
Institut Sciences Chimiques de Rennes, UMR 6226 CNRS-, Université de Rennes ‘Catalyse et Organometalliques’,
Campus de Beaulieu, 35042 Rennes, France
b
c
Fax +33(2)23236939; E-mail: henri.doucet@univ-rennes1.fr
Received 17 December 2007
results have been reported for vinyl halides.8 One of the
most active catalysts for such substrates is a sulfur-con-
taining palladacycle.8a With this catalytic system, the cou-
pling of b-bromostyrene with methyl acrylate allowed
Abstract: A wide variety of 1,3-dienes have been prepared by the
Heck vinylation of vinyl bromides using [Pd(h3-C3H5)Cl]2/
cis,cis,cis-1,2,3,4-tetrakis[(diphenylphosphino)methyl]cyclopen-
tane (Tedicyp) as the catalyst precursor. Both a- and b-substituted
vinyl bromides undergo the Heck reaction with functionalised alk- formation of the corresponding conjugated diene in a high
enes such as acrylates, enones, styrenes or a vinyl sulfone, and also
turnover number (TON) of 9000, but in moderate yields
with nonfunctionalised alkenes such as dec-1-ene, leading stereose-
(18% and 40%). Tris(dibenzylideneacetone)dipalladi-
lectively, in most cases, to the corresponding E- or E,E-1,3-dienes
um(0) (1 mol%) associated with the electron-rich and ster-
in good yields. Furthermore, this catalyst can be used at low loading
ically hindered phosphine ligand tri-tert-butylphosphine
for several reactions.
efficiently promotes the reaction of 2-bromobut-2-ene
Key words: catalysis, palladium, tetraphosphine, alkenes, vinyl
with styrene in 89% yield.8b Recently, the coupling of a 2-
bromides
bromoacrylate with a 1,1-disubstituted alkene using palla-
dium(II) acetate (3 mol%) and tri-2-tolylphosphine (6
mol%) as the catalytic system was described. This reac-
The palladium-catalysed so-called Heck reaction is one of
tion allowed the stereoselective synthesis of a 1,3-diene,
the most powerful methods for the formation of carbon–
which is a precursor of a marine natural product, in 84%
carbon bonds; however, most of the results described so
yield.8c
far have been for such reactions performed using aryl ha-
lides.1 The use of vinyl halides to prepare 1,3-dienes has
attracted less attention.2,3 In fact, in many cases, 1,3-
dienes are actually prepared by cross-coupling of organo-
metallic vinyl derivatives [metal = MgX,4 ZnX,5 SnR3,6
Several results have been reported for the coupling of vi-
nyl halides with alkenes, however, the influence of sub-
stituents on the vinyl halides on the reaction yields and
rates, and also couplings with functionalised alkenes, has
not been studied in detail. Thus, an effective and selective
method for this reaction, especially using high substrate/
catalyst ratios, is still subject to significant improvements.
7
B(OR)2 ] with vinyl halides. The major drawback of these
reactions is that they require the preparation of the orga-
nometallic derivatives and also provide either an organo-
metallic compound or a salt (MX) as byproduct. The
direct coupling of vinyl halides with alkenes, especially at
low catalyst loadings, would provide a cost-effective and
environmentally attractive procedure for the preparation
of 1,3-dienes (only HX as byproduct). In general, these
couplings have been performed using palladium catalysts
associated with the triphenylphosphine ligand. However,
the efficiency of palladium associated with triphenylphos-
phine as the catalyst precursor is generally low in terms of
the substrate-to-catalyst ratio. In recent years, several
more stable and efficient palladium catalysts have been
successfully used for Heck reactions, but most of the re-
sults which have been described with these catalysts were
obtained for the coupling of aryl halides.3 Relatively few
The coordination of ligands on palladium has an impor-
tant effect on the rates and selectivities of catalysed reac-
tions. In order to find more efficient palladium catalysts
we have prepared the tetradentate phosphine ligand,
cis,cis,cis-1,2,3,4-tetrakis[(diphenylphosphino)meth-
yl]cyclopentane9 (Tedicyp, Scheme 1). The presence of
these four phosphines close to the metal centre appears to
increase the stability of the catalyst and prevents the for-
mation of ‘palladium black’. We have recently reported
several results10 obtained in allylic substitution reac-
tions,11 Suzuki,12a Sonogashira12b or Negishi couplings,13
C–H activation/functionalisation of furans14a or thio-
phenes,14b and also for the Heck vinylation,15 using
Tedicyp as ligand. We have also reported some preliminary
results for the Heck reaction using vinyl bromides and
alkenes.16 Here, in order to further establish the require-
ments for a successful Heck reaction using vinyl halide
derivatives, we wish to report on the reaction of a- or b-
SYNTHESIS 2008, No. 7, pp 1142–1152
x
x
.
x
x
.2
0
0
8
Advanced online publication: 06.03.2008
DOI: 10.1055/s-2008-1032124; Art ID: Z29107SS
© Georg Thieme Verlag Stuttgart · New York

PAPER
Conjugated Dienes by the Heck Reaction of Vinyl Bromides with Alkenes
1143
yl)styrene or 3-chlorostyrene gave the (E,E)-1,4-diarylbu-
ta-1,3-dienes 1, 3 and 5 with high regio- and
stereoselectivities, in high TONs of 4300, 3700 and 2500,
and also in good yields (Table 1, entries 1, 2, 5, 6, 9 and
10). An electron-donating substituent on the aryl ring of
styrene such as a para-methoxy group slightly decreased
the reaction rate (TON 640) (Table 1, entries 3 and 4).
This catalyst is also highly active for the coupling of b-
bromostyrene with the heteroarylalkenes 2- and 4-vi-
nylpyridine (Table 1, entries 11–14). A higher reaction
rate was observed with 4-vinylpyridine (TON 7000) than
with 2-vinylpyridine (TON 550). This difference of reac-
tivity could result from a possible interaction between the
nitrogen atom of 2-vinylpyridine and the palladium com-
plex, which might have a retarding effect on the reaction
rate.
PPh2
PPh2
PPh2
PPh2
R4
(Tedicyp)
R1
R2
R1
R2
Br
[Pd(η3-C3H5)Cl]2,
R4
+
DMF, K2CO3 or NaOAc,
80–130 °C, 20 h
R3
major isomer
R3
Scheme 1
substituted vinyl bromides with a variety of alkenes such
as acrylates, enones, a vinyl sulfone, simple alkenes or
styrene derivatives using Tedicyp as the ligand at moder-
ate to very low catalyst loading.
First, we investigated the Heck reaction of b-bromosty-
rene with several alkenes in the presence of the system
[Pd(h3-C3H5)Cl]2/Tedicyp (Schemes 1 and 2, Tables 1– 3).
For this study, based on previous results,15 N,N-dimethyl- Next, we examined the influence of several functional
formamide was chosen as the solvent and potassium car- groups on the alkene, such as an ester, ketone, aldehyde or
bonate or sodium acetate as the base. The reactions were sulfone group, on the reaction rate for the coupling with b-
performed at 80–130 °C under argon. Table 1 discloses bromostyrene (Table 2). The reaction with n-butyl acry-
the results obtained using styrene derivatives as the viny- late can be performed with as little as 0.001% catalyst,
lation reactant. In Table 2, the influence of functional leading to butyl (E,E)-5-phenylpenta-2,4-dienoate (8) in
good yield and with high stereoselectivity (Table 2, en-
tries 1 and 2). For this vinylation reaction, a very high
TON of 66000 was obtained. The first attempts using con-
jugated enones, such as but-3-en-2-one or pent-1-en-3-
one, as reactants were unsuccessful (Table 2, entries 3 and
6). This is probably due to a fast polymerisation of these
enones under the reaction conditions. Commercially
available alk-1-en-3-ones are often stabilised with 0.5%
groups on the alkene has been studied. Table 3 describes
the Heck reaction of b-bromostyrene with simple alkenes
such as dec-1-ene or cyclic alkenes.
In the presence of styrene derivatives and b-bromosty-
rene, the reactions required 0.01–0.1 mol% catalyst in or-
der to obtain high yields of products (Table 1). For
example, the coupling of styrene, 3,5-bis(trifluorometh-
Table 1 Palladium–Tedicyp Complex Catalysed Heck Reaction of b-Bromostyrene with Styrene Derivativesa (Scheme 1)
Entry Alkene
Ratio substrate/catalyst Productb
Yieldc (%)
1
2
styrene
styrene
1000
10000
(95)
43
1
Ph
Ph
Ph
OMe
3
4
4-methoxystyrene
4-methoxystyrene
250
1000
100 (88)
64
2
CF3
5
6
3,5-bis(trifluoromethyl)styrene
3,5-bis(trifluoromethyl)styrene
1000
10000
100 (90)
25
3
Ph
CF3
CN
7
8
4-cyanostyrene
4-cyanostyrene
250
1000
100 (82)
65
4
Ph
Ph
Ph
Ph
9
10
3-chlorostyrene
3-chlorostyrene
1000
10000
100 (87)
37
5
Cl
11
12
2-vinylpyridine
2-vinylpyridine
250
1000
100 (86)
55
6
N
13
14
4-vinylpyridine
4-vinylpyridine
1000
10000
100 (91)
70
N
7
a Reaction conditions: b-bromostyrene (1 equiv), alkene (2 equiv), K2CO3 (2 equiv), DMF, 130 °C, 20 h.
b E,E-Isomers were obtained selectively (>95%).
c GC or NMR yields. Isolated yields are in parentheses.
Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York

1144
M. Lemhadri et al.
PAPER
hydroquinone. We had previously observed that, for Heck Then, we performed some reactions using simple linear,
reactions with aryl halides, the addition of 8% hydro- branched or cyclic alkenes (Schemes 1 and 2, Table 3).
quinone to the reaction mixture led to the arylation of such The vinylation of b-bromostyrene performed in the pres-
enones to give the corresponding (E)-1-arylalk-1-en-3- ence of dec-1-ene led to the E,E-1,3-diene 16 in 44% se-
ones in high yields and TONs.15e The addition of hydro- lectivity (Table 3, entries 1 and 2). In the course of this
quinone probably reduces the rate of polymerisation or reaction, the formation of several other isomers occurs
decomposition of these enones. Using this additive, in the due to partial migration of the double bond of dec-1-ene.
presence of b-bromostyrene, the expected (E,E)-1-phenyl- On the other hand, the reaction of b-bromostyrene with
alka-1,3-dien-5-ones 9–11 were obtained with high stere- the sterically congested 3,3-dimethylbut-1-ene led to the
oselectivities and in high yields using as little as 0.1–1 product 17 with a very high regio- and stereoselectivity in
mol% catalyst (Table 2, entries 4, 5, and 7–10). Ethyl favour of the E,E-1,3-diene and in good yield (Table 3,
pent-4-enoate and 2,2-dimethylpent-4-enal also gave the entry 3).
expected E,E-1,3-dienes 12 and 13 in moderate to good
Several reactions were also performed using cyclic alk-
yields (Table 2, entries 11–14). With these substrates, the
enes, namely, cyclopentene, cyclohexene, cycloheptene
formation of traces of side products arising from the mi-
and cyclooctene, as the coupling partners (Scheme 2,
gration of the double bond was observed. Methyl vinyl
Table 3, entries 5–9). Cyclohexene and cycloheptene led
sulfone was also found to be a suitable reactant for the
to the E-1,5- and E-1,4-dienes 20 and 21 with 94 and 80%
selectivity, respectively. With these two substrates, partial
migration of the carbon–carbon double bond of the cy-
preparation of the conjugated diene (Table 2, entries 15
and 16); the E,E-1,3-diene 14 was obtained in 81% yield
employing 1 mol% catalyst. On the other hand, when 2-
cloalkene occurs. Such migration has been previously re-
methylbut-3-en-2-ol was used, an unexpected reaction
ported.2h A suitable conformation of the palladium
was observed. With this substrate a dehydration occurred
intermediate is necessary for the b-elimination step of the
catalytic cycle. These suitable conformations can be
favoured by partial migration of the double bond of the
to give the conjugated triene 15 as the major product, but
in moderate yield (Table 2, entries 17 and 18).
cycloalkene. On the other hand, cyclopentene and cy-
Table 2 Palladium–Tedicyp Complex Catalysed Heck Reaction of b-Bromostyrene with Functionalised Alkenesa (Scheme 1)
Entry
Alkene
Ratio substrate/
catalyst
Productb
Yieldc (%)
1
2
n-butyl acrylate
n-butyl acrylate
10000
100000
100 (95)d
(66)d
8
9
CO2n-Bu
Ph
Ph
Ph
3
4
5
but-3-en-2-one
but-3-en-2-one
but-3-en-2-one
250
250
1000
0
O
100 (75)e
49e
6
7
8
pent-1-en-3-one
pent-1-en-3-one
pent-1-en-3-one
250
250
1000
0
O
10
100 (77)e
88e
O
O
O
9
10
hex-1-en-3-one
hex-1-en-3-one
100
250
100 (79)e
52e
11
12
Ph
Ph
Ph
11
12
ethyl pent-4-enoate
ethyl pent-4-enoate
250
1000
100 (66)
67
OEt
H
13
14
2,2-dimethylpent-4-enal
2,2-dimethylpent-4-enal
100
250
100 (64)
47
13
O
S
15
16
methyl vinyl sulfone
methyl vinyl sulfone
100
250
100 (81)
33
14
15
Ph
Ph
O
17
18
2-methylbut-3-en-2-ol
2-methylbut-3-en-2-ol
250
1000
100 (48)f
63f
a Reaction conditions: b-bromostyrene (1 equiv), alkene (2 equiv), NaOAc (2 equiv), DMF, 110 °C, 20 h.
b E,E-Isomers were obtained selectively (>95%).
c GC or NMR yields. Isolated yields are in parentheses.
d K2CO3 (2 equiv) was used as base, at 130 °C.
e Hydroquinone (8%) was added to the reaction mixture.
f Reaction temperature: 80 °C.
Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York

PAPER
Conjugated Dienes by the Heck Reaction of Vinyl Bromides with Alkenes
1145
Table 3 Palladium–Tedicyp Complex Catalysed Heck Reaction of b-Bromostyrene with Linear, Branched or Cyclic Alkenesa (Schemes 1
and 2)
Entry
Alkene
Ratio substrate/catalyst Product
Yieldb (%)
1
2
dec-1-ene
dec-1-ene
1000
10000
(68)c
40c
16
( )
7
Ph
3
4
5
3,3-dimethylbut-1-ene
allylbenzene
250
100
17
18
19
100 (79)d
98 (82)e
Ph
Ph
cyclopentene
1000
100 (88)d,f
Ph
Ph
6
7
cyclohexene
cycloheptene
1000
20
21
100 (84)d,g
92 (81)h,i
10000
Ph
8
9
cyclooctene
cyclooctene
1000
10000
100 (93)j
54j
22
Ph
a Reaction conditions: b-bromostyrene (1 equiv), alkene (2 equiv), K2CO3 (2 equiv), DMF, 130 °C, 20 h.
b GC or NMR yields. Isolated yields are in parentheses.
c Mixture of isomers; selectivity in favour of (E,E)-dodeca-1,3-dienylbenzene: 44%.
d Reaction performed in an autoclave.
e Mixture of isomers; selectivity in favour of (E,E)-1,5-diphenylpenta-1,3-diene: 55%.
f Mixture of isomers; selectivity in favour of (E)-1-styrylcyclopentene: 55%.
g Mixture of isomers; selectivity in favour of (E)-4-styrylcyclohexene: 94%.
h Mixture of isomers; selectivity in favour of (E)-3-styrylcycloheptene: 80%.
i Reaction temperature: 100 °C.
j Mixture of isomers; selectivity in favour of (E)-1-styrylcyclooctene: 93%.
clooctene led mainly to the expected E-1,3-dienes 19 and lyst (Table 4, entries 1–3 and 5). A higher reaction rate
22 (Table 3, entries 5, 8 and 9). It should be noted that a and TON of 2500 was obtained with the electron-poor
very high selectivity of 93% in favour of E-1,3-diene 22 alkene n-butyl acrylate (Table 4, entries 6 and 7). Using
was obtained from cyclooctene. Moreover, most of the re- pent-1-en-3-one or oct-1-en-3-one, the reactions gave a
actions with these nonfunctionalised linear or cyclic alk- simple access to the expected E-1,3-dien-5-ones 28 and
enes were performed using as little as 0.1 mol% catalyst.
29. Again, with these unstable substrates, a small amount
of hydroquinone had to be added to the reaction mixture
in order to reduce the polymerisation side reaction
(Table 4, entries 8–11).
[Pd(η3-C3H5)Cl]2, Tedicyp,
H
Br
H
( )n
H
( )n
+
DMF, K2CO3, 100–130 °C, 20 h
The other a-substituted vinyl bromide, 3-bromobut-3-en-
1-ol, in the presence of n-butyl acrylate, styrene, pent-1-
en-3-one or oct-1-en-3-one also selectively gave the ex-
pected E-1,3-dienes 30–33 (Table 5). However, with this
vinyl bromide slightly lower yields were generally ob-
tained than for 2-bromobut-1-ene. This is due to the for-
mation of minor side products.
Ph
Ph
H
n = 1–4
dienes 19–22
Scheme 2
Next, we studied the formation of 1,3-dienes using four
alternative bromoalkenes: 2-bromobut-1-ene, 3-bromo-
but-3-en-1-ol, 1-bromo-2-methylprop-1-ene and 2-bromo-
3-methylbut-2-ene (Tables 4– 7). With the a-substituted
vinyl bromide, 2-bromobut-1-ene, several reactions were
performed using styrene derivatives (Table 4, entries 1–
5). With styrene, 4-methoxystyrene, 4-cyanostyrene or 4-
vinylpyridine, the E-1,3-dienes 23–26 were obtained se-
lectively in moderate to good yields using 0.4 mol% cata-
With the b,b-disubstituted vinyl bromide, 1-bromo-2-
methylprop-1-ene, results similar to those for 2-bromo-
but-1-ene were obtained, indicating a minor influence of
the position of the alkyl substituents on the bromoalkene
on reaction rates (Table 6). Four alkenes were employed:
n-butyl acrylate, styrene, 4-cyanostyrene and 4-vinylpyri-
dine. In all cases, using only 0.4 mol% catalyst, the E-1,3-
Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York

1146
M. Lemhadri et al.
PAPER
Table 4 Palladium–Tedicyp Complex Catalysed Heck Reaction of 2-Bromobut-1-enea (Scheme 1)
Entry
1
Alkene
styrene
Ratio substrate/catalyst
250
Productb
Yieldc (%)
(58)
Ph
23
OMe
CN
2
4-methoxystyrene
250
24
25
26
(76)
3
4
4-cyanostyrene
4-cyanostyrene
250
1000
(83)
75
N
5
4-vinylpyridine
250
(69)
6
7
n-butyl acrylate
n-butyl acrylate
1000
10000
92 (80)
25
CO2n-Bu
O
27
28
8
9
pent-1-en-3-one
pent-1-en-3-one
100
250
100 (64)d
47d
O
10
11
oct-1-en-3-one
oct-1-en-3-one
100
250
100 (71)d
33d
29
a Reaction conditions: 2-bromobut-1-ene (1 equiv), alkene (2 equiv), K2CO3 (2 equiv), DMF, 80 °C, 20 h.
b E-Isomers were obtained selectively (>95%).
c GC or NMR yields. Isolated yields are in parentheses.
d NaOAc (2 equiv) was used as base, and hydroquinone (8%) was added to the reaction mixture.
Table 5 Palladium–Tedicyp Complex Catalysed Heck Reaction of 3-Bromobut-3-en-1-ola (Scheme 1)
Entry
1
Alkene
Ratio substrate/catalyst
1000
Productb
Yieldc (%)
(76)
CO2n-Bu
HO
HO
n-butyl acrylate
30
Ph
O
2
3
styrene
100
31
32
(45)
pent-1-en-3-one
1000
77 (62)d
HO
HO
O
4
oct-1-en-3-one
250
33
62 (41)d
a Reaction conditions: 3-bromobut-3-en-1-ol (1 equiv), alkene (2 equiv), K2CO3 (2 equiv), DMF, 130 °C, 20 h.
b E-Isomers were obtained selectively (>95%).
c GC or NMR yields. Isolated yields are in parentheses.
d NaOAc (2 equiv) was used as base, at 110 °C, and hydroquinone (8%) was added to the reaction mixture.
dienes 34–37 were obtained in good yields and with high and yields are very similar to those obtained with 2-bro-
regio- and stereoselectivities.
mobut-1-ene or 1-bromo-2-methylprop-1-ene. It should
be noted that, in the literature, relatively few examples of
coupling reactions of trisubstituted vinyl halides with alk-
enes have been reported.17 Therefore, the Heck reaction
represents a simple and powerful method for the prepara-
tion of such compounds.
These results were confirmed by the reactivity of the
trisubstituted vinyl bromide, 2-bromo-3-methylbut-2-ene
(Table 7). An acrylate, styrenes and enones have been
successfully employed to give the E-1,3-dienes 38–42 in
high yields and TONs of 200–850. Again, these TONs
Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York

PAPER
Conjugated Dienes by the Heck Reaction of Vinyl Bromides with Alkenes
1147
Table 6 Palladium–Tedicyp Complex Catalysed Heck Reaction of 1-Bromo-2-methylprop-1-enea (Scheme 1)
Entry
Alkene
Ratio substrate/catalyst Productb
Yieldc (%)
1
2
n-butyl acrylate
n-butyl acrylate
250
1000
100 (89)
73
34
CO2n-Bu
Ph
3
4
styrene
250
250
35
36
(78)
(75)
CN
4-cyanostyrene
N
5
4-vinylpyridine
250
37
(85)
a Reaction conditions: 1-bromo-2-methylprop-1-ene (1 equiv), alkene (2 equiv), K2CO3 (2 equiv), DMF, 100 °C, 20 h.
b E-Isomers were obtained selectively (>95%).
c GC or NMR yields. Isolated yields are in parentheses.
Table 7 Palladium–Tedicyp Complex Catalysed Heck Reaction of 2-Bromo-3-methylbut-2-enea (Scheme 1)
Entry
1
Alkene
Ratio substrate/catalyst Productb
Yieldc (%)
82
n-butyl acrylate
250
250
38
39
CO2n-Bu
2
3
styrene
88
92
Ph
N
4-vinylpyridine
250
40
O
O
4
5
pent-1-en-3-one
oct-1-en-3-one
1000
1000
41
42
57d
62d
a Reaction conditions: 2-bromo-3-methylbut-2-ene (1 equiv), alkene (2 equiv), K2CO3 (2 equiv), DMF, 100 °C, 20 h.
b E-Isomers were obtained selectively (>95%).
c Isolated yields.
d NaOAc (2 equiv) was used as base, at 110 °C, and hydroquinone (8%) was added to the reaction mixture.
In summary, in the presence of the palladium–Tedicyp vantage of such low catalyst loadings is increasingly
complex, the Heck reaction of vinyl bromides can be per- important for industrial processes.
formed with a wide variety of alkenes such as acrylates,
enones, styrene derivatives, sulfones or simple linear and
DMF analytical grade (99%) was not distilled before use. K2CO3
cyclic alkenes. Moreover, both a- and b-substituted vinyl
bromides can be employed, and relatively similar TONs
are obtained indicating a minor steric effect of the vinyl
bromide substituents on the reaction rate. A wide range of
E- and E,E-1,3-dienes have been selectively prepared in
good yields. The high levels of regio- and stereoselection
for most of the reactions, as well as the functional group
tolerance, are worthy of note. Most of these reactions can
be performed with as little as 0.01–1 mol% catalyst. To
date, few other catalytic systems have achieved this objec-
tive. Due to the high price of palladium, the practical ad-
and NaOAc (99+%) were used. All reactions were run under argon
using vacuum lines, in Schlenk tubes with oven-dried glassware. 1H
(300 MHz) and 13C (75 MHz) NMR spectra were recorded on a
Bruker Avance DPX-300 spectrometer in CDCl3 solution. Chemi-
cal shifts (d) are reported in ppm relative to CDCl3. Elemental anal-
yses were performed on a Thermo Finnigan EA 1112 apparatus.
Flash chromatography was performed on silica gel (230–400 mesh).
Palladium–Tedicyp Complex Catalyst9
An oven-dried 40-mL Schlenk tube equipped with a magnetic stir-
rer bar, under argon atmosphere, was charged with [Pd(h3-
C3H5)Cl]2 (4.2 mg, 11.6 mmol) and Tedicyp (20 mg, 23.2 mmol).
Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York

1148
M. Lemhadri et al.
PAPER
Anhyd DMF (2.5 mL) was added, then the solution was stirred at
r.t. for 10 min. This catalyst solution was used directly for the catal-
ysed reactions.
complex (0.004 mmol) at 130 °C afforded 6; yield: 0.178 g (86%).
1H NMR (300 MHz, CDCl3): d = 8.57 (d, J = 4.1 Hz, 1 H), 7.62 (td,
J = 7.5, 1.7 Hz, 1 H), 7.45 (d, J = 8.2 Hz, 2 H), 7.43–7.20 (m, 5 H),
7.10 (dd, J = 7.4, 4.9 Hz, 1 H), 6.98 (dd, J = 15.5, 10.7 Hz, 1 H),
6.78 (d, J = 15.8 Hz, 1 H), 6.72 (d, J = 15.5 Hz, 1 H).
Butyl (E,E)-5-Phenylpenta-2,4-dienoate (8) (Table 2, Entry 2);
Typical Procedure
The reaction of b-bromostyrene (1.83 g, 10 mmol), n-butyl acrylate
(2.56 g, 20 mmol) and K2CO3 (2.8 g, 20 mmol) in anhyd DMF (10
mL) in the presence of the palladium–Tedicyp complex (0.0001
mmol) under argon at 130 °C for 20 h afforded the corresponding
product 8, after extraction with CH2Cl2 (20 mL), concentration and
flash cromatography (pentane–Et2O, 1:1); yield: 1.52 g (66%).
1H NMR (300 MHz, CDCl3): d = 7.45 (d, J = 7.4 Hz, 2 H), 7.45–
7.25 (m, 4 H), 6.89 (m, 2 H), 5.98 (d, J = 15.3 Hz, 1 H), 4.15 (t,
J = 6.6 Hz, 2 H), 1.65 (m, 2 H), 1.40 (m, 2 H), 0.94 (t, J = 7.4 Hz, 3
H).
4-[(E,E)-4-Phenylbuta-1,3-dienyl]pyridine (7) (Table 1, Entry
13)
The reaction of b-bromostyrene (0.183 g, 1 mmol), 4-vinylpyridine
(0.210 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the palladium
complex (0.001 mmol) at 130 °C afforded 7; yield: 0.188 g (91%).
1H NMR (300 MHz, CDCl3): d = 8.53 (d, J = 6.0 Hz, 2 H), 7.45 (d,
J = 8.2 Hz, 2 H), 7.35 (t, J = 7.6 Hz, 2 H), 7.30–7.20 (m, 3 H), 7.12
(dd, J = 15.5, 10.2 Hz, 1 H), 6.94 (dd, J = 15.5, 10.2 Hz, 1 H), 6.77
(d, J = 15.5 Hz, 1 H), 6.57 (d, J = 15.5 Hz, 1 H).
Butyl (E,E)-5-Phenylpenta-2,4-dienoate (8) (Table 2, Entry 2)
See typical procedure.
(E,E)-1,4-Diphenylbuta-1,3-diene (1) (Table 1, Entry 1)
The reaction of b-bromostyrene (1.83 g, 10 mmol), styrene (2.08 g,
20 mmol) and K2CO3 (2.80 g, 20 mmol) with the palladium com-
plex (0.01 mmol) at 130 °C afforded 1; yield: 1.96 g (95%).
1H NMR (300 MHz, CDCl3): d = 7.40 (d, J = 8.2 Hz, 4 H), 7.30 (t,
J = 7.6 Hz, 4 H), 7.20 (t, J = 7.6 Hz, 2 H), 6.92 (m, 2 H), 6.63 (m, 2
(E,E)-6-Phenylhexa-3,5-dien-2-one (9) (Table 2, Entry 4)
The reaction of b-bromostyrene (0.183 g, 1 mmol), but-3-en-2-one
(0.140 g, 2 mmol), hydroquinone (0.009 g, 0.08 mmol) and NaOAc
(0.164 g, 2 mmol) with the palladium complex (0.004 mmol) at
110 °C afforded 9; yield: 0.129 g (75%).
H).
1H NMR (300 MHz, CDCl3): d = 7.40 (d, J = 7.7 Hz, 2 H), 7.35–
7.17 (m, 4 H), 6.90 (d, J = 16.5 Hz, 1 H), 6.81 (dd, J = 15.7, 9.6 Hz,
1 H), 6.19 (d, J = 15.7 Hz, 1 H), 2.25 (s, 3 H).
(E,E)-1-(4-Methoxyphenyl)-4-phenylbuta-1,3-diene (2) (Table
1, Entry 3)
The reaction of b-bromostyrene (1.83 g, 10 mmol), 4-methoxysty-
rene (2.68 g, 20 mmol) and K2CO3 (2.80 g, 20 mmol) with the pal-
ladium complex (0.04 mmol) at 130 °C afforded 2; yield: 2.08 g
(88%).
(E,E)-7-Phenylhepta-4,6-dien-3-one (10) (Table 2, Entry 7)
The reaction of b-bromostyrene (0.183 g, 1 mmol), pent-1-en-3-one
(0.164 g, 2 mmol), hydroquinone (0.009 g, 0.08 mmol) and NaOAc
(0.164 g, 2 mmol) with the palladium complex (0.004 mmol) at
110 °C afforded 10; yield: 0.143 g (77%).
1H NMR (300 MHz, CDCl3): d = 7.50–7.20 (m, 7 H), 7.02–6.75 (m,
4 H), 6.65 (d, J = 8.2 Hz, 2 H), 3.85 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.45 (d, J = 7.7 Hz, 2 H), 7.38–
7.27 (m, 4 H), 6.95 (d, J = 16.5 Hz, 1 H), 6.86 (dd, J = 15.7, 9.6 Hz,
1 H), 6.29 (d, J = 15.7 Hz, 1 H), 2.60 (q, J = 7.7 Hz, 2 H), 1.14 (t,
J = 7.7 Hz, 3 H).
(E,E)-1-[3,5-Bis(trifluoromethyl)phenyl]-4-phenylbuta-1,3-di-
ene (3) (Table 1, Entry 5)
The reaction of b-bromostyrene (0.183 g, 1 mmol), 3,5-bis(trifluo-
romethyl)styrene (0.480 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol)
with the palladium complex (0.001 mmol) at 130 °C afforded 3;
yield: 0.308 g (90%).
1H NMR (300 MHz, CDCl3): d = 7.85–7.25 (m, 8 H), 7.09 (dd,
J = 15.1, 10.6 Hz, 1 H), 6.95 (dd, J = 15.1, 10.6 Hz, 1 H), 6.78 (d,
J = 15.0 Hz, 1 H), 6.67 (d, J = 15.0 Hz, 1 H).
(E,E)-8-Phenylocta-5,7-dien-4-one (11) (Table 2, Entry 9)
The reaction of b-bromostyrene (0.183 g, 1 mmol), hex-1-en-3-one
(0.188 g, 2 mmol), hydroquinone (0.009 g, 0.08 mmol) and NaOAc
(0.164 g, 2 mmol) with the palladium complex (0.01 mmol) at
110 °C afforded 11; yield: 0.158 g (79%).
1H NMR (300 MHz, CDCl3): d = 7.49 (d, J = 7.7 Hz, 2 H), 7.38–
7.25 (m, 4 H), 6.97 (d, J = 16.5 Hz, 1 H), 6.88 (dd, J = 15.7, 9.6 Hz,
1 H), 6.30 (d, J = 15.7 Hz, 1 H), 2.59 (q, J = 7.7 Hz, 2 H), 1.70 (m,
2 H), 0.99 (t, J = 7.7 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 200.6, 142.3, 141.0, 136.0, 129.7,
128.9, 128.8, 127.2, 126.8, 42.6, 17.8, 13.8.
(E,E)-1-(4-Cyanophenyl)-4-phenylbuta-1,3-diene (4) (Table 1,
Entry 7)
The reaction of b-bromostyrene (0.183 g, 1 mmol), 4-cyanostyrene
(0.260 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the palladium
complex (0.004 mmol) at 130 °C afforded 4; yield: 0.190 g (82%).
1H NMR (300 MHz, CDCl3): d = 7.65–7.25 (m, 9 H), 7.07 (dd,
J = 14.9, 10.6 Hz, 1 H), 6.98 (dd, J = 14.8, 10.6 Hz, 1 H), 6.78 (d,
J = 15.1 Hz, 1 H), 6.67 (d, J = 14.8 Hz, 1 H).
Anal. Calcd for C14H16O: C, 83.96; H, 8.05. Found: C, 83.79; H,
8.01.
Ethyl (E,E)-7-Phenylhepta-4,6-dienoate (12) (Table 2, Entry 11)
The reaction of b-bromostyrene (0.183 g, 1 mmol), ethyl pent-4-
enoate (0.256 g, 2 mmol) and NaOAc (0.164 g, 2 mmol) with the
palladium complex (0.004 mmol) at 110 °C afforded 12; yield:
0.152 g (66%).
(E,E)-1-(3-Chlorophenyl)-4-phenylbuta-1,3-diene (5) (Table 1,
Entry 9)
The reaction of b-bromostyrene (0.183 g, 1 mmol), 3-chlorostyrene
(0.277 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the palladium
complex (0.001 mmol) at 130 °C afforded 5; yield: 0.209 g (87%).
1H NMR (300 MHz, CDCl3): d = 7.36 (d, J = 7.7 Hz, 2 H), 7.27 (t,
J = 7.7 Hz, 2 H), 7.19 (t, J = 7.7 Hz, 1 H), 6.73 (dd, J = 15.8, 10.4
Hz, 1 H), 6.44 (d, J = 15.8 Hz, 1 H), 6.24 (dd, J = 15.1, 10.4 Hz, 1
H), 5.80 (dt, J = 15.1, 6.8 Hz, 1 H), 4.14 (q, J = 7.7 Hz, 2 H), 2.45
(m, 4 H), 1.18 (t, J = 7.7 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 172.9, 137.4, 132.9, 131.5, 130.9,
128.9, 128.5, 127.2, 126.2, 60.4, 33.9, 28.1, 14.2.
1H NMR (300 MHz, CDCl3): d = 7.50–7.15 (m, 9 H), 6.97 (m, 2 H),
6.75–6.55 (m, 2 H).
2-[(E,E)-4-Phenylbuta-1,3-dienyl]pyridine (6) (Table 1, Entry
11)
The reaction of b-bromostyrene (0.183 g, 1 mmol), 2-vinylpyridine
(0.210 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the palladium
Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York

PAPER
Conjugated Dienes by the Heck Reaction of Vinyl Bromides with Alkenes
1149
Anal. Calcd for C15H18O2: C, 78.23; H, 7.88. Found: C, 78.04; H,
8.03.
(2.36 g, 20 mmol) and K2CO3 (2.80 g, 20 mmol) with the palladium
complex (0.1 mmol) at 130 °C afforded a mixture of product 18
with other regio- and stereoisomers in 82% (1.81 g) isolated yield
and in 55% selectivity in favour of 18.
1H NMR (300 MHz, CDCl3): d = 7.30–7.15 (m, 10 H), 6.80 (dd,
J = 15.0, 10.2 Hz, 1 H), 6.51 (d, J = 15.0 Hz, 1 H), 6.29 (dd,
J = 15.0, 10.2 Hz, 1 H), 6.01 (dt, J = 15.0, 7.5 Hz, 1 H), 3.51 (d,
J = 7.5 Hz, 2 H).
(E,E)-2,2-Dimethyl-7-phenylhepta-4,6-dienal (13) (Table 2,
Entry 13)
The reaction of b-bromostyrene (0.183 g, 1 mmol), 2,2-dimethyl-
pent-4-enal (0.224 g, 2 mmol) and NaOAc (0.164 g, 2 mmol) with
the palladium complex (0.01 mmol) at 110 °C afforded 13; yield:
0.137 g (64%).
1H NMR (300 MHz, CDCl3): d = 9.53 (s, 1 H), 7.40 (d, J = 7.7 Hz,
2 H), 7.31 (t, J = 7.7 Hz, 2 H), 7.19 (t, J = 7.7 Hz, 1 H), 6.75 (dd,
J = 15.8, 10.4 Hz, 1 H), 6.49 (d, J = 15.8 Hz, 1 H), 6.27 (dd,
J = 15.1, 10.4 Hz, 1 H), 5.74 (dt, J = 15.1, 6.8 Hz, 1 H), 2.32 (d,
J = 7.8 Hz, 2 H), 1.11 (s, 6 H).
13C NMR (75 MHz, CDCl3): d = 205.8, 137.3, 134.1, 131.3, 129.1,
128.7, 128.6, 127.4, 126.2, 46.3, 40.4, 21.3.
(E)-1-Styrylcyclopentene (19) (Table 3, Entry 5)
The reaction of b-bromostyrene (1.83 g, 10 mmol), cyclopentene
(1.36 g, 20 mmol) and K2CO3 (2.80 g, 20 mmol) with the palladium
complex (0.01 mmol) at 130 °C in an autoclave afforded a mixture
of product 19 with other regio- and stereoisomers in 88% (1.50 g)
isolated yield and in 55% selectivity in favour of 19.
1H NMR (300 MHz, CDCl3): d = 7.43 (d, J = 8.2 Hz, 2 H), 7.39–
7.25 (m, 3 H), 7.04 (d, J = 16.0 Hz, 1 H), 6.43 (d, J = 16.0 Hz, 1 H),
5.89 (m, 1 H), 2.65–2.40 (m, 4 H), 2.00 (quin, J = 7.5 Hz, 2 H).
Anal. Calcd for C15H18O: C, 84.07; H, 8.47. Found: C, 84.31; H,
8.57.
(E)-4-Styrylcyclohexene (20) (Table 3, Entry 6)
[(E,E)-4-(Methylsulfonyl)buta-1,3-dienyl]benzene (14) (Table
2, Entry 15)
The reaction of b-bromostyrene (0.183 g, 1 mmol), methyl vinyl
sulfone (0.212 g, 2 mmol) and NaOAc (0.164 g, 2 mmol) with the
palladium complex (0.01 mmol) at 110 °C afforded 14; yield: 0.169
g (81%).
1H NMR (300 MHz, CDCl3): d = 7.46 (d, J = 7.7 Hz, 2 H), 7.40–
7.30 (m, 4 H), 6.99 (d, J = 15.3 Hz, 1 H), 6.81 (dd, J = 15.5, 10.8
Hz, 1 H), 6.48 (d, J = 15.3 Hz, 1 H), 2.98 (s, 3 H).
The reaction of b-bromostyrene (1.83 g, 10 mmol), cyclohexene
(1.50 g, 20 mmol) and K2CO3 (2.80 g, 20 mmol) with the palladium
complex (0.01 mmol) at 130 °C in an autoclave afforded a mixture
of product 20 with other regio- and stereoisomers in 84% (1.55 g)
isolated yield and in 94% selectivity in favour of 20.
1H NMR (300 MHz, CDCl3): d = 7.40 (d, J = 8.2 Hz, 2 H), 7.35–
7.15 (m, 3 H), 6.43 (d, J = 16.0 Hz, 1 H), 6.26 (dd, J = 16.0, 7.1 Hz,
1 H), 5.73 (m, 2 H), 2.55–1.45 (m, 7 H).
(E)-3-Styrylcycloheptene (21) (Table 3, Entry 7)
[(E,E)-5-Methylhexa-1,3,5-trienyl]benzene (15) (Table 2, Entry
17)
The reaction of b-bromostyrene (0.183 g, 1 mmol), 2-methylbut-3-
en-2-ol (0.172 g, 2 mmol) and NaOAc (0.164 g, 2 mmol) with the
palladium complex (0.004 mmol) at 80 °C afforded the correspond-
ing dehydrated product 15; yield: 0.081 g (48%).
1H NMR (300 MHz, CDCl3): d = 7.40 (d, J = 7.7 Hz, 2 H), 7.31 (t,
J = 7.7 Hz, 2 H), 7.19 (t, J = 7.7 Hz, 1 H), 6.84 (dd, J = 15.5, 9.4 Hz,
1 H), 6.57 (d, J = 15.5 Hz, 1 H), 6.45 (d, J = 15.3 Hz, 1 H), 5.40 (dd,
J = 15.3, 9.4 Hz, 1 H), 5.03 (s, 1 H), 5.01 (s, 1 H), 1.91 (s, 3 H).
The reaction of b-bromostyrene (1.83 g, 10 mmol), cycloheptene
(1.64 g, 20 mmol) and K2CO3 (2.80 g, 20 mmol) with the palladium
complex (0.001 mmol) at 100 °C afforded a mixture of product 21
with other regio- and stereoisomers in 81% (1.60 g) isolated yield
and in 80% selectivity in favour of 21.
1H NMR (300 MHz, CDCl3): d = 7.35–7.28 (m, 4 H), 7.22 (t,
J = 7.5 Hz, 1 H), 6.44 (d, J = 15.8 Hz, 1 H), 6.28 (dd, J = 15.8, 7.3
Hz, 1 H), 5.83 (dt, J = 11.2, 5.1 Hz, 1 H), 5.69 (dd, J = 11.2, 4.5 Hz,
1 H), 3.17 (m, 1 H), 2.30–1.40 (m, 8 H).
(E)-1-Styrylcyclooctene (22) (Table 3, Entry 8)
(E,E)-Dodeca-1,3-dienylbenzene (16) (Table 3, Entry 1)
The reaction of b-bromostyrene (1.83 g, 10 mmol), dec-1-ene (2.80
g, 20 mmol) and K2CO3 (2.80 g, 20 mmol) with the palladium com-
plex (0.01 mmol) at 130 °C afforded a mixture of product 16 with
other regio- and stereoisomers in 68% (1.65 g) isolated yield and in
44% selectivity in favour of 16.
1H NMR (300 MHz, CDCl3): d = 7.50–7.15 (m, 5 H), 6.75 (dd,
J = 10.9, 15.7 Hz, 1 H), 6.43 (d, J = 15.7 Hz, 1 H), 6.19 (dd,
J = 10.9, 15.1 Hz, 1 H), 5.82 (dt, J = 15.1, 7.0 Hz, 1 H), 1.50–1.15
(m, 12 H), 1.15 (m, 2 H), 0.88 (t, J = 6.8 Hz, 3 H).
The reaction of b-bromostyrene (1.83 g, 10 mmol), cyclooctene
(1.78 g, 20 mmol) and K2CO3 (2.80 g, 20 mmol) with the palladium
complex (0.01 mmol) at 130 °C afforded a mixture of product 22
with other regio- and stereoisomers in 93% (1.97 g) isolated yield
and in 93% selectivity in favour of 22.
1H NMR (300 MHz, CDCl3): d = 7.40 (d, J = 7.7 Hz, 2 H), 7.29 (t,
J = 7.2 Hz, 2 H), 7.17 (t, J = 7.2 Hz, 1 H), 6.74 (d, J = 16.2 Hz, 1
H), 6.47 (d, J = 16.2 Hz, 1 H), 5.86 (t, J = 8.3 Hz, 1 H), 2.51 (m, 2
H), 2.25 (m, 2 H), 1.70–1.40 (m, 8 H).
13C NMR (75 MHz, CDCl3): d = 139.3, 138.0, 133.8, 132.2, 128.5,
126.8, 126.1, 125.1, 30.4, 28.6, 27.4, 26.9, 26.0, 24.3.
[(E,E)-5,5-Dimethylhexa-1,3-dienyl]benzene (17) (Table 3,
Entry 3)
The reaction of b-bromostyrene (1.83 g, 10 mmol), 3,3-dimethyl-
but-1-ene (1.68 g, 20 mmol) and K2CO3 (2.80 g, 20 mmol) with the
palladium complex (0.04 mmol) at 130 °C in an autoclave afforded
17; yield: 1.47 g (79%).
1H NMR (300 MHz, CDCl3): d = 7.36 (d, J = 8.2 Hz, 2 H), 7.29 (t,
J = 7.6 Hz, 2 H), 7.18 (t, J = 7.6 Hz, 1 H), 6.74 (dd, J = 15.5, 10.0
Hz, 1 H), 6.45 (d, J = 15.7 Hz, 1 H), 6.14 (dd, J = 15.5, 10.0 Hz, 1
H), 5.84 (d, J = 15.4 Hz, 1 H), 1.05 (s, 9 H).
Anal. Calcd for C16H20: C, 90.51; H, 9.49. Found: C, 91.30; H, 9.37.
[(E)-3-Ethylbuta-1,3-dienyl]benzene (23) (Table 4, Entry 1)
The reaction of 2-bromobut-1-ene (0.135 g, 1 mmol), styrene (0.208
g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the palladium com-
plex (0.004 mmol) at 80 °C afforded 23; yield: 0.092 g (58%).
1H NMR (300 MHz, CDCl3): d = 7.42 (d, J = 7.7 Hz, 2 H), 7.31 (t,
J = 7.2 Hz, 2 H), 7.19 (t, J = 7.2 Hz, 1 H), 6.82 (d, J = 16.1 Hz, 1
H), 6.57 (d, J = 16.1 Hz, 1 H), 5.12 (s, 1 H), 5.07 (s, 1 H), 2.36 (q,
J = 7.3 Hz, 2 H), 1.15 (t, J = 7.3 Hz, 3 H).
(E,E)-1,5-Diphenylpenta-1,3-diene (18) (Table 3, Entry 4)
The reaction of b-bromostyrene (1.83 g, 10 mmol), allylbenzene
Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York

1150
M. Lemhadri et al.
PAPER
1-[(E)-3-Ethylbuta-1,3-dienyl]-4-methoxybenzene (24) (Table
4, Entry 2)
NaOAc (0.164 g, 2 mmol) with the palladium complex (0.01 mmol)
at 80 °C afforded 28; yield: 0.088 g (64%).
The reaction of 2-bromobut-1-ene (0.135 g, 1 mmol), 4-methoxy-
styrene (0.268 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the
palladium complex (0.004 mmol) at 80 °C afforded 24; yield: 0.143
g (76%).
1H NMR (300 MHz, CDCl3): d = 7.34 (d, J = 8.7 Hz, 2 H), 6.86 (d,
J = 8.7 Hz, 2 H), 6.70 (d, J = 16.2 Hz, 1 H), 6.53 (d, J = 16.2 Hz, 1
H), 5.07 (s, 1 H), 5.01 (s, 1 H), 3.80 (s, 3 H), 2.34 (q, J = 7.3 Hz, 2
H), 1.15 (t, J = 7.3 Hz, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.18 (d, J = 16.3 Hz, 1 H), 6.19 (d,
J = 16.3 Hz, 1 H), 5.39 (s, 1 H), 5.36 (s, 1 H), 2.61 (q, J = 7.5 Hz, 2
H), 2.24 (q, J = 7.5 Hz, 2 H), 1.11 (m, 6 H).
13C NMR (75 MHz, CDCl3): d = 201.5, 146.5, 144.3, 125.8, 122.7,
33.7, 24.3, 12.3, 8.2.
Anal. Calcd for C9H14O: C, 78.21; H, 10.21. Found: C, 78.30; H,
10.07.
13C NMR (75 MHz, CDCl3): d = 159.1, 147.8, 130.2, 129.1, 127.5,
(E)-2-Ethyldeca-1,3-dien-5-one (29) (Table 4, Entry 10)
The reaction of 2-bromobut-1-ene (0.135 g, 1 mmol), oct-1-en-3-
one (0.206 g, 2 mmol), hydroquinone (0.009 g, 0.08 mmol) and
NaOAc (0.164 g, 2 mmol) with the palladium complex (0.01 mmol)
at 80 °C afforded 29; yield: 0.128 g (71%).
127.2, 114.1, 114.0, 55.3, 24.7, 12.8.
Anal. Calcd for C13H16O: C, 82.94; H, 8.57. Found: C, 82.71; H,
8.68.
4-[(E)-3-Ethylbuta-1,3-dienyl]benzonitrile (25) (Table 4, Entry
3)
The reaction of 2-bromobut-1-ene (0.135 g, 1 mmol), 4-cyanosty-
rene (0.260 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the pal-
ladium complex (0.004 mmol) at 80 °C afforded 25; yield: 0.152 g
(83%).
1H NMR (300 MHz, CDCl3): d = 7.21 (d, J = 16.3 Hz, 1 H), 6.22 (d,
J = 16.3 Hz, 1 H), 5.43 (s, 1 H), 5.40 (s, 1 H), 2.60 (t, J = 7.5 Hz, 2
H), 2.27 (q, J = 7.5 Hz, 2 H), 1.75–0.78 (m, 12 H).
13C NMR (75 MHz, CDCl3): d = 202.0, 147.3, 145.2, 126.9, 123.5,
41.3, 32.3, 25.1, 24.8, 23.2, 14.7, 13.1.
1H NMR (300 MHz, CDCl3): d = 7.58 (d, J = 8.5 Hz, 2 H), 7.48 (d,
J = 8.5 Hz, 2 H), 6.90 (d, J = 16.4 Hz, 1 H), 6.55 (d, J = 16.4 Hz, 1
H), 5.22 (s, 1 H), 5.19 (s, 1 H), 2.36 (q, J = 7.3 Hz, 2 H), 1.16 (t,
J = 7.3 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 147.1, 142.0, 134.8, 132.4, 126.7,
125.9, 119.0, 117.7, 110.3, 24.5, 12.6.
Anal. Calcd for C12H20O: C, 79.94; H, 11.18. Found: C, 79.87; H,
11.34.
Butyl (E)-4-(2-Hydroxyethyl)penta-2,4-dienoate (30) (Table 5,
Entry 1)
The reaction of 3-bromobut-3-en-1-ol (0.151 g, 1 mmol), n-butyl
acrylate (0.256 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the
palladium complex (0.001 mmol) at 130 °C afforded 30; yield:
0.151 g (76%).
Anal. Calcd for C13H13N: C, 85.21; H, 7.15. Found: C, 85.43; H,
7.06.
1H NMR (300 MHz, CDCl3): d = 7.29 (d, J = 16.0 Hz, 1 H), 5.92 (d,
J = 16.0 Hz, 1 H), 5.48 (s, 1 H), 5.41 (s, 1 H), 4.15 (t, J = 7.5 Hz, 2
H), 3.76 (t, J = 7.5 Hz, 2 H), 2.52 (t, J = 7.5 Hz, 2 H), 1.64 (m, 2 H),
1.41 (m, 2 H), 0.93 (t, J = 7.5 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 167.1, 145.9, 141.0, 125.0, 118.7,
64.4, 60.8, 34.9, 30.7, 19.1, 13.7.
4-[(E)-3-Ethylbuta-1,3-dienyl]pyridine (26) (Table 4, Entry 5)
The reaction of 2-bromobut-1-ene (0.135 g, 1 mmol), 4-vinylpyri-
dine (0.210 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the pal-
ladium complex (0.004 mmol) at 80 °C afforded 26; yield: 0.110 g
(69%).
1H NMR (300 MHz, CDCl3): d = 8.52 (d, J = 6.4 Hz, 2 H), 7.26 (d,
J = 6.4 Hz, 2 H), 6.99 (d, J = 16.4 Hz, 1 H), 6.47 (d, J = 16.4 Hz, 1
H), 5.23 (s, 1 H), 5.20 (s, 1 H), 2.34 (q, J = 7.3 Hz, 2 H), 1.16 (t,
J = 7.3 Hz, 3 H).
Anal. Calcd for C11H18O3: C, 66.64; H, 9.15. Found: C, 66.79; H,
9.26.
(E)-3-Methylene-5-phenylpent-4-en-1-ol (31) (Table 5, Entry 2)
The reaction of 3-bromobut-3-en-1-ol (0.151 g, 1 mmol), styrene
(0.208 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the palladium
complex (0.01 mmol) at 130 °C afforded 31; yield: 0.078 g (45%).
1H NMR (300 MHz, CDCl3): d = 7.41 (d, J = 7.4 Hz, 2 H), 7.31 (t,
J = 7.4 Hz, 2 H), 7.23 (t, J = 7.4 Hz, 1 H), 6.81 (d, J = 16.2 Hz, 1
H), 6.60 (d, J = 16.2 Hz, 1 H), 5.26 (s, 1 H), 5.14 (s, 1 H), 3.82 (t,
J = 6.5 Hz, 2 H), 2.64 (t, J = 6.5 Hz, 2 H).
13C NMR (75 MHz, CDCl3): d = 149.8, 147.0, 145.0, 135.7, 125.1,
120.8, 118.1, 24.4, 12.5.
Anal. Calcd for C11H13N: C, 82.97; H, 8.23. Found: C, 82.99; H,
8.31.
Butyl (E)-4-Ethylpenta-2,4-dienoate (27) (Table 4, Entry 6)
The reaction of 2-bromobut-1-ene (0.135 g, 1 mmol), n-butyl acry-
late (0.256 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the pal-
ladium complex (0.001 mmol) at 80 °C afforded 27; yield: 0.146 g
(80%).
1H NMR (300 MHz, CDCl3): d = 7.32 (d, J = 15.9 Hz, 1 H), 5.93 (d,
J = 15.9 Hz, 1 H), 5.36 (s, 1 H), 5.33 (s, 1 H), 4.15 (t, J = 6.8 Hz, 2
H), 2.24 (q, J = 7.3 Hz, 2 H), 1.65 (m, 2 H), 1.42 (m, 2 H), 1.11 (t,
J = 7.3 Hz, 3 H), 0.94 (t, J = 7.3 Hz, 3 H).
(E)-6-(2-Hydroxyethyl)hepta-4,6-dien-3-one (32) (Table 5,
Entry 3)
The reaction of 3-bromobut-3-en-1-ol (0.151 g, 1 mmol), pent-1-en-
3-one (0.164 g, 2 mmol), hydroquinone (0.009 g, 0.08 mmol) and
NaOAc (0.164 g, 2 mmol) with the palladium complex (0.001
mmol) at 110 °C afforded 32; yield: 0.096 g (62%).
13C NMR (75 MHz, CDCl3): d = 167.3, 146.6, 146.1, 122.0, 117.9,
1H NMR (300 MHz, CDCl3): d = 7.18 (d, J = 16.0 Hz, 1 H), 6.22 (d,
J = 16.0 Hz, 1 H), 5.53 (s, 1 H), 5.46 (s, 1 H), 3.77 (t, J = 7.5 Hz, 2
H), 2.62 (q, J = 7.5 Hz, 3 H), 2.54 (t, J = 7.5 Hz, 2 H), 1.12 (t,
J = 7.5 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 201.2, 143.6, 141.4, 126.4, 125.6,
60.8, 34.8, 33.9, 8.1.
64.3, 30.7, 24.3, 19.1, 13.7, 12.3.
Anal. Calcd for C11H18O2: C, 72.49; H, 9.95. Found: C, 72.61; H,
10.08.
(E)-6-Ethylhepta-4,6-dien-3-one (28) (Table 4, Entry 8)
The reaction of 2-bromobut-1-ene (0.135 g, 1 mmol), pent-1-en-3-
one (0.164 g, 2 mmol), hydroquinone (0.009 g, 0.08 mmol) and
Anal. Calcd for C9H14O2: C, 70.10; H, 9.15. Found: C, 70.21; H,
9.04.
Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York

PAPER
Conjugated Dienes by the Heck Reaction of Vinyl Bromides with Alkenes
1151
(E)-2-(2-Hydroxyethyl)deca-1,3-dien-5-one (33) (Table 5, Entry
4)
the palladium complex (0.004 mmol) at 100 °C afforded 38; yield:
0.161 g (82%).
The reaction of 3-bromobut-3-en-1-ol (0.151 g, 1 mmol), oct-1-en-
3-one (0.206 g, 2 mmol), hydroquinone (0.009 g, 0.08 mmol) and
NaOAc (0.164 g, 2 mmol) with the palladium complex (0.004
mmol) at 110 °C afforded 33; yield: 0.080 g (41%).
1H NMR (300 MHz, CDCl3): d = 7.17 (d, J = 16.0 Hz, 1 H), 6.21 (d,
J = 16.0 Hz, 1 H), 5.52 (s, 1 H), 5.45 (s, 1 H), 3.76 (t, J = 7.5 Hz, 2
H), 2.59 (t, J = 7.5 Hz, 2 H), 2.52 (t, J = 7.5 Hz, 2 H), 1.61 (m, 2 H),
1.30 (m, 4 H), 0.88 (t, J = 7.5 Hz, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.86 (d, J = 15.5 Hz, 1 H), 5.77 (d,
J = 15.5 Hz, 1 H), 4.15 (t, J = 6.8 Hz, 2 H), 1.95 (s, 3 H), 1.86 (s, 3
H), 1.78 (s, 3 H), 1.65 (m, 2 H), 1.40 (m, 2 H), 0.94 (t, J = 7.3 Hz,
3 H).
13C NMR (75 MHz, CDCl3): d = 168.2, 143.4, 141.5, 125.9, 115.4,
64.0, 30.8, 22.5, 20.9, 19.2, 14.0, 13.7.
Anal. Calcd for C12H20O2: C, 73.43; H, 10.27. Found: C, 73.61; H,
10.04.
13C NMR (75 MHz, CDCl3): d = 201.1, 143.8, 141.4, 126.5, 125.7,
60.8, 40.7, 34.8, 31.4, 23.9, 22.4, 13.9.
[(E)-3,4-Dimethylpenta-1,3-dienyl]benzene (39) (Table 7, Entry
2)
The reaction of 2-bromo-3-methylbut-2-ene (0.149 g, 1 mmol), sty-
rene (0.208 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the pal-
ladium complex (0.004 mmol) at 100 °C afforded 39; yield: 0.152
g (88%).
1H NMR (300 MHz, CDCl3): d = 7.51 (m, 2 H), 7.48 (d, J = 15.9
Hz, 1 H), 7.25 (m, 3 H), 6.35 (d, J = 15.9 Hz, 1 H), 1.96 (s, 3 H),
1.88 (s, 6 H).
Anal. Calcd for C12H20O2: C, 73.43; H, 10.27. Found: C, 73.56; H,
10.31.
Butyl (E)-5-Methylhexa-2,4-dienoate (34) (Table 6, Entry 1)
The reaction of 1-bromo-2-methylprop-1-ene (0.135 g, 1 mmol), n-
butyl acrylate (0.256 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with
the palladium complex (0.004 mmol) at 100 °C afforded 34; yield:
0.162 g (89%).
1H NMR (300 MHz, CDCl3): d = 7.54 (dd, J = 11.7, 15.2 Hz, 1 H),
5.97 (d, J = 11.7 Hz, 1 H), 5.75 (d, J = 15.2 Hz, 1 H), 4.15 (t, J = 6.8
Hz, 2 H), 1.88 (s, 3 H), 1.86 (s, 3 H), 1.65 (m, 2 H), 1.40 (m, 2 H),
0.94 (t, J = 7.3 Hz, 3 H).
4-[(E)-3,4-Dimethylpenta-1,3-dienyl]pyridine (40) (Table 7,
Entry 3)
The reaction of 2-bromo-3-methylbut-2-ene (0.149 g, 1 mmol), 4-
vinylpyridine (0.210 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with
the palladium complex (0.004 mmol) at 100 °C afforded 40; yield:
0.159 g (92%).
1H NMR (300 MHz, CDCl3): d = 8.50 (d, J = 5.1 Hz, 2 H), 7.47 (d,
J = 15.9 Hz, 1 H), 7.25 (d, J = 5.1 Hz, 2 H), 6.35 (d, J = 15.9 Hz, 1
H), 1.95 (s, 3 H), 1.87 (s, 6 H).
[(E)-4-Methylpenta-1,3-dienyl]benzene (35) (Table 6, Entry 3)
The reaction of 1-bromo-2-methylprop-1-ene (0.135 g, 1 mmol),
styrene (0.208 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with the
palladium complex (0.004 mmol) at 100 °C afforded 35; yield:
0.123 g (78%).
1H NMR (300 MHz, CDCl3): d = 7.38 (d, J = 7.7 Hz, 2 H), 7.29 (t,
J = 7.2 Hz, 2 H), 7.17 (t, J = 7.2 Hz, 1 H), 6.99 (dd, J = 15.5, 11.0
Hz, 1 H), 6.41 (d, J = 15.5 Hz, 1 H), 5.99 (d, J = 11.0 Hz, 1 H), 1.86
(s, 3 H), 1.84 (s, 3 H).
(E)-6,7-Dimethylocta-4,6-dien-3-one (41) (Table 7, Entry 4)
The reaction of 2-bromo-3-methylbut-2-ene (0.149 g, 1 mmol),
pent-1-en-3-one (0.164 g, 2 mmol), hydroquinone (0.009 g, 0.08
mmol) and NaOAc (0.164 g, 2 mmol) with the palladium complex
(0.001 mmol) at 110 °C afforded 41; yield: 0.087 g (57%).
1H NMR (300 MHz, CDCl3): d = 7.77 (d, J = 15.9 Hz, 1 H), 6.11 (d,
J = 15.9 Hz, 1 H), 2.60 (q, J = 7.4 Hz, 2 H), 1.97 (s, 3 H), 1.88 (s, 3
H), 1.79 (s, 3 H), 1.12 (t, J = 7.4 Hz, 3 H).
4-[(E)-4-Methylpenta-1,3-dienyl]benzonitrile (36) (Table 6,
Entry 4)
The reaction of 1-bromo-2-methylprop-1-ene (0.135 g, 1 mmol), 4-
cyanostyrene (0.260 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with
the palladium complex (0.004 mmol) at 100 °C afforded 36; yield:
0.138 g (75%).
1H NMR (300 MHz, CDCl3): d = 7.55 (d, J = 7.5 Hz, 2 H), 7.42 (d,
J = 7.5 Hz, 2 H), 7.08 (dd, J = 15.5, 10.9 Hz, 1 H), 6.38 (d, J = 15.5
Hz, 1 H), 6.01 (d, J = 10.9 Hz, 1 H), 1.87 (s, 3 H), 1.86 (s, 3 H).
13C NMR (75 MHz, CDCl3): d = 201.8, 142.6, 141.1, 126.2, 123.8,
34.1, 22.7, 20.9, 14.1, 8.5.
Anal. Calcd for C10H16O: C, 78.90; H, 10.59. Found: C, 78.69; H,
10.41.
13C NMR (75 MHz, CDCl3): d = 142.7, 140.0, 132.3, 129.2, 127.5,
(E)-2,3-Dimethylundeca-2,4-dien-6-one (42) (Table 7, Entry 5)
The reaction of 2-bromo-3-methylbut-2-ene (0.149 g, 1 mmol), oct-
1-en-3-one (0.206 g, 2 mmol), hydroquinone (0.009 g, 0.08 mmol)
and NaOAc (0.164 g, 2 mmol) with the palladium complex (0.001
mmol) at 110 °C afforded 42; yield: 0.120 g (62%).
126.3, 125.1, 119.2, 109.7, 26.4, 18.7.
Anal. Calcd for C13H13N: C, 85.21; H, 7.15. Found: C, 85.35; H,
7.01.
4-[(E)-4-Methylpenta-1,3-dienyl]pyridine (37) (Table 6, Entry
5)
The reaction of 1-bromo-2-methylprop-1-ene (0.135 g, 1 mmol), 4-
vinylpyridine (0.210 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with
the palladium complex (0.004 mmol) at 100 °C afforded 37; yield:
0.135 g (85%).
1H NMR (300 MHz, CDCl3): d = 8.51 (m, 2 H), 7.17 (dd, J = 11.0,
15.5 Hz, 1 H), 7.15 (m, 2 H), 6.32 (d, J = 15.5 Hz, 1 H), 6.02 (d,
J = 11.0 Hz, 1 H), 1.88 (s, 3 H), 1.87 (s, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.75 (d, J = 15.9 Hz, 1 H), 6.09 (d,
J = 15.9 Hz, 1 H), 2.54 (t, J = 7.4 Hz, 2 H), 1.96 (s, 3 H), 1.87 (s, 3
H), 1.78 (s, 3 H), 1.62 (m, 2 H), 1.30 (m, 4 H), 0.88 (t, J = 7.4 Hz,
3 H).
13C NMR (75 MHz, CDCl3): d = 201.5, 142.7, 141.1, 126.2, 124.0,
41.1, 31.5, 24.3, 22.7, 22.5, 21.0, 14.1, 13.9.
Anal. Calcd for C13H22O: C, 80.35; H, 11.41. Found: C, 80.17; H,
11.29.
Butyl (E)-4,5-Dimethylhexa-2,4-dienoate (38) (Table 7, Entry 1)
The reaction of 2-bromo-3-methylbut-2-ene (0.149 g, 1 mmol), n-
butyl acrylate (0.256 g, 2 mmol) and K2CO3 (0.280 g, 2 mmol) with
Acknowledgment
We thank CNRS for financial support.
Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York

1152
M. Lemhadri et al.
PAPER
(5) (a) Williams, D. R.; Kammler, D. C.; Donnell, A. F.;
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Synthesis 2008, No. 7, 1142–1152 © Thieme Stuttgart · New York