Palladium-tetraphosphine catalysed heck reaction with simple alkenes: Influence of reaction conditions on the migration of the double bond

Article abstract of DOI:10.1055/s-2007-966063

The Heck reaction of aryl halides with simple alk-1-enes is a powerful method for the synthesis of (E)-1-arylalk-1-ene derivatives. The major problem of this reaction is the palladium-catalysed migration of the carbon-carbon double bond along the alkyl ch

Full text of DOI:10.1055/s-2007-966063

PAPER
1683
Palladium-Tetraphosphine Catalysed Heck Reaction with Simple Alkenes:
Influence of Reaction Conditions on the Migration of the Double Bond
I
nfluence of React
a
ionConditi
c
ons onHec
o
k
R
eactionw
u
ithSimple
A
b
lkenes Fall,a Florian Berthiol,a Henri Doucet,*b Maurice Santelli*a
a
UMR 6180 CNRS and Université d’Aix-Marseille III: ‘Chirotechnologies: catalyse et biocatalyse’, Laboratoire de Synthèse Organique,
Faculté des Sciences de Saint Jérôme, Université d’Aix-Marseille III, Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex20,
France
Fax +33(4)91983865; E-mail: m.santelli@univ-cezanne.fr
Institut Sciences Chimiques de Rennes, UMR 6226 CNRS-Université de Rennes: ‘Catalyse et Organometalliques’, Campus de Beaulieu,
35042 Rennes, France
b
Fax +33(2)23236939; E-mail: henri.doucet@univ-rennes1.fr
Received 21 November 2006; revised 30 March 2007
Alkyl
[Pd]
Alkyl
Abstract: The Heck reaction of aryl halides with simple alk-1-enes
is a powerful method for the synthesis of (E)-1-arylalk-1-ene deriv-
atives. The major problem of this reaction is the palladium-cataly-
sed migration of the carbon–carbon double bond along the alkyl
chain. We observed that this migration could be partially controlled
using appropriate reaction conditions. The ramification of the alkyl
chain and the substituents on the aryl halide has also an important
influence on this migration. The cis,cis,cis-1,2,3,4-tetrakis(diphe-
nylphosphinomethyl)cyclopentane/[Pd(C3H5)Cl]2 system catalyses
efficiently the Heck reaction of a wide variety of aryl halides with
the linear alkenes oct-1-ene and dec-1-ene or the branched alkenes
4-methylhex-1-ene, 5-methylhex-1-ene, allylcyclopentane, or allyl-
cyclohexane. In most cases, selectivities of 70–80% were obtained.
In some cases, up to 97% in favour of (E)-1-arylalk-1-enes can be
+
+
R1MX
ArX
R1M
Ar
M = Zn, Sn or B
Scheme 1
alkenes have been reported so far.8,9 Moreover, in most
cases only one or two examples of such reactions have
been described and the selectivity is often not clearly re-
ported. In a few cases the crude mixture of regio- and ste-
reoisomers was hydrogenated to give the corresponding
mixture of 1- and 2-arylalkanes.8 Only a few catalysts
observed. Moreover several reactions can be performed using very have been used for the reaction with this class of alkenes.
low catalyst loadings.
For example, the system Pd(OAc)2/P(o-Tol)3 (10 mol%)
catalyses the coupling of pent-1-ene with an aryl bromide
in 59% yield and 69:31 selectivity of 1-arylpent-1-ene and
2-arylpent-1-ene.9a Fu et al. have reported the regioselec-
tive formation of an 1-arylhex-1-ene in 70% yield using 4-
chloroacetophenone and hex-1-ene, with Pd2(dba)3 (1.5
mol%) associated to P(t-Bu)3 (6 mol%) as catalyst. How-
ever, a mixture of E- and Z-isomers was obtained in 86:14
ratio.9c Milstein et al. have reported the palladium cou-
pling of pentafluorobromobenzene with hex-1-ene in 37%
yield as a mixture of isomers.9d The reaction of 4-bromo-
toluene with hex-1-ene using a Pd(OAc)2/diazabutadiene
catalyst (3 mol%) was described by Nolan et al. Using this
catalyst, the selectivity between terminal and internal iso-
mers was 75:25, and the stereoselectivity of (E)- and (Z)-
1-arylhex-1-enes was 95:5.9e A dendridic catalyst also led
to a mixture of isomers for the coupling of iodobenzene
and oct-1-ene.9g Finally, 3 mol% of PdCl2(PCy3)2 cataly-
ses the alkenylation of chlorobenzene. Using this catalyst,
the (E)-1-phenyloct-1-ene was obtained in 60% selectivi-
ty.9h
Key words: Heck reaction, palladium, alkenes, double bond migra-
tion
Palladium-catalysed Heck reaction is one of the most
powerful methods for the formation of C–C bonds. The
arylation of alkenes such as acrylates, styrenes, or, more
recently, enol ethers, catalysed by palladium has been ex-
tensively developed in the last thirty years.1–4 On the other
hand, the palladium-catalysed Heck alkenylation using
simple linear of branched alkenes remains open to study,
since migration of the carbon–carbon double bond along
the alkyl chain generally leads to mixtures of regio- and
stereoisomers. In fact, the classical method to prepare se-
lectively (E)-1-arylalk-1-ene is to employ an aryl halide
with an organometallic derivative of the alkene
2
3
[metal = ZnX,1 SnR3 B(OR)2 ] using a palladium catalyst
(Scheme 1). These reactions are very regio- and stereose-
lective in favour of the formation of (E)-1-arylalk-1-ene
derivatives.5–7 However, these reactions require the prep-
aration of the alkyl organometallic derivative and provide
an organometallic (MX) as a by-product.
In summary, very few regio- and stereoselective Heck re-
actions using non-functionalized linear or branched alk-1-
enes have been reported so far. To our knowledge, the in-
fluence of the reaction conditions and of the substituents
on the aryl halide or on the alkyl chain of the alk-1-ene has
not been explored in detail. Thus, an effective and selec-
tive method using low catalyst loadings for the prepara-
tion of (E)-1-arylalk-1-enes is still subject to significant
improvement.
To our knowledge, only a few examples of Heck reactions
in the presence of non-functionalised linear or branched
SYNTHESIS 2007, No. 11, pp 1683–1696
x
x.
x
x
.
2
0
0
7
Advanced online publication: 11.05.2007
DOI: 10.1055/s-2007-966063; Art ID: Z24006SS
© Georg Thieme Verlag Stuttgart · New York

1684
Y. Fall et al.
PAPER
In order to obtain a highly stable palladium catalyst, we the polar solvents NMP or DMA gave 1a in 51 and 53%
have prepared the tetraphosphine ligand, cis,cis,cis- selectivities with K2CO3 as base and 57% or 67% using
1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane
or Tedicyp.10 The idea of the design of this ligand was that
intermediate Pd(0) species have to be protected by inter-
nal ligation against possible decomposition pathways
through under-ligation and subsequent colloid formation.
We have already reported the results obtained in allylic
substitution,11 for Suzuki or Negishi cross-coupling,12 for
Sonogashira reaction13 and for coupling of furans and aryl
bromides via CH activation14 using Tedicyp as the ligand.
We have also described several results obtained for Heck
reaction.15,16 For example, we have reported the reaction
with n-butyl acrylate,15,16a styrene,16b acrolein ethylene ac-
etal,16c alkenols16d,e,h enolethers,16b,g vinylsilanes16f or
vinylsulfur16i with a variety of aryl bromides. We have
also reported preliminary results using simple alkenes
such as dec-1-ene, 3,3-dimethylbut-1-ene, or cycloalk-
enes.17 Using 3,3-dimethylbut-1-ene or cycloalkenes, re-
gioselective reactions had generally been obtained. On the
other hand, using dec-1-ene or oct-1-ene, the (E)-1-aryl-
alk-1-ene derivatives were obtained in 34–70% selectivi-
ties. Such selectivities are not good enough to give a
useful process compared to the coupling reactions using
organometallic derivatives of the alkene.5–7 Therefore, in
order to improve this selectivity of the arylation with such
alkenes, we decided to study the influence of several pa-
rameters on the regio- and stereocontrol of this reaction.
NaOAc (Table 1, entries 9–12).
The temperature has also an influence on this selectivity.
When using a lower temperature of 110 °C instead of
130 °C, the selectivity increased from 67% to 73%. Using
a higher substrate/catalyst ratio of 10000, a selectivity of
76% in 1a was obtained (Table 1, entry 15). Finally, in the
absence of ligand or with PPh3 the reaction did not pro-
ceed (Table 1, entries 16 and 17). It should be noted that a
reverse selectivity in favour of regioisomer 1b was ob-
tained using acetonitrile as solvent (Table 1, entries 18
and 19). However, in this solvent the reaction was much
slower than in DMA. Such internal arylations have al-
ready been reported in a few cases for example for the re-
action with unsaturated alcohols using ionic liquid as
solvent.18
After this optimisation of the reaction conditions, we per-
formed several arylations using dec-1-ene (Table 2), oct-
1-ene (Table 3), 4-methylhex-1-ene, 5-methylhex-1-ene,
allylcyclopentane or allylcyclohexane (Table 4) with a set
of aryl bromides.
First, we examined the influence of the substituents on the
aryl bromides on the yields, selectivities and reaction rates
for the arylation of dec-1-ene (Table 2). Higher reactions
rates and selectivities in favour of (E)-1-aryldec-1-ene
had been observed with electron-poor aryl bromides than
with electron-rich aryl bromides when the reactions were
conducted in DMF using K2CO3 as base.17 Using DMA
and NaOAc as base, quite different results were obtained.
Using electron-poor aryl bromides, such as 4-bromobenz-
aldehyde, 4-bromobenzophenone or 3,5-bistrifluorometh-
ylbromobenzene, selectivities of 66%, 64% and 70% have
been obtained using the DMF/K2CO3 procedure and 81%,
80% and 83% using the DMA/NaOAc procedure
(Table 2, entries 2–14). The presence of electron-donating
substituents on the aryl bromides generally decreases the
selectivity in favour of (E)-1-aryldec-1-ene. Using the
electron-rich aryl bromides, 4-bromoanisole or 2-bro-
mothiophene lower selectivities of 63% and 60% were ob-
tained using DMA/NaOAc conditions. Again, lower
selectivities of 51% and 34% had been obtained using
DMF/K2CO3 system (Table 2, entries 19–21, 26 and 27).
With the ortho-substituted aryl bromide, 2-bromotoluene,
a good selectivity of 70% in favour of 11a was also ob-
served (36% in DMF/K2CO3) (Table 2, entries 22 and 23).
Since there are only a few examples of Heck alkenylation
using simple alk-1-enes in the literature, we began by ex-
ploring the reaction of dec-1-ene with 4-bromoacetophe-
none using various reaction conditions (Scheme 2,
Table 1). The first reactions were performed at 130 °C,
under argon, in the presence of a ratio 1:2 of
[Pd(C3H5)Cl]2/Tedicyp as catalyst.
After extensive screening of the reaction conditions, we
found that the most suitable base appears to be NaOAc.
Bases such as NaHCO3, Na2CO3 or KF using DMF as sol-
vent led to the (E)-1-aryldec-1-ene 1a only in 29–38% se-
lectivity (Table 1, entries 1–3). The best selectivities
using DMF as solvent were obtained using K2CO3 or
NaOAc as base in 64% and 54% yield, respectively
(Table 1, entries 4 and 5). Then, we examined the influ-
ence of a few solvents. The nonpolar solvent xylene using
K2CO3 as base gave extremely low selectivities in 1a of
9% and 10% (Table 1, entries 6 and 7). On the other hand,
Ph2P
PPh2
n-C8H17
Ph2P
PPh2
+
Tedicyp
R
n-C8H17
R
[Pd(C3H5)Cl]2
1a–14a
1b–14b
n-C8H17
X
+
DMA, NaOAc 110 °C
R
migration of the double
bond along the chain, up
to 30 isomers can be
obtained
n-C8H17
+
+
R = MeCO, PhCO, HCO, CN, NO2, CF3, F, MeO, Me, H
R
1c–14c
Scheme 2
Synthesis 2007, No. 11, 1683–1696 © Thieme Stuttgart · New York

PAPER
Influence of Reaction Conditions on Heck Reaction with Simple Alkenes
1685
Table 1 Influence of the Conditions on the Selectivity of Palladium-Catalysed Coupling of 4-Bromoacetophenone with Dec-1-ene;
(Scheme 2)a
Entry
Base
Solvent
Temp ( °C)
Substrate/catalyst Selectivity in favour
Yield (%)
ratio
of isomer 1a (%)
1
2
KF
DMF
130
130
130
130
130
130
100
110
130
130
130
130
130
110
110
110
110
100
100
250
29
32
38
64
54
49
10
9
100
100
35
NaHCO3
Na2CO3
K2CO3
NaOAc
NaOAc
K2CO3
K2CO3
K2CO3
K2CO3
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
NaOAc
K2CO3
NaOAc
DMF
250
250
3
DMF
4
DMF
10000
250
80
5
DMF
94
6
DMF
250
39b
100
93
7
xylene
xylene
NMP
100
8
250
9
250
51
53
57
67
46
73
76
–
100
100
100
100
100
100
99 (96)c
0d
10
11
12
13
14
15
16
17
18
19
DMA
NMP
250
250
DMA
pentan-1-ol
DMA
DMA
DMA
DMA
MeCN
MeCN
1000
250
1000
10000
10000
10000
100
–
0e
82f
84f
36
100
53
a Conditions: [Pd(C3H5)Cl]2/Tedicyp = 1:2, 4-bromoacetophenone: 1 mmol, dec-1-ene: 2 mmol, base: 2 mmol, 20 h, argon. GC and NMR
yields.
b Two mmol of Bu4NI was added.
c Isolated yield.
d Reaction performed without ligand.
e Reaction performed with [Pd(C3H5)Cl]2/PPh3 = 1:4 as catalyst.
f Selectivity in favour of isomer 1b.
On the other hand, in the presence of di-ortho-substituted alkene-palladium complex from which the aryl is trans-
aryl bromides such as bromomesitylene or 9-bromo- ferred to the terminal position to give complex C. Then,
anthracene, mixtures of isomers were obtained (Table 2, the 1-arylalk-1-enes would be formed after irreversible
entries 24 and 25).
elimination of a PdH species.
The heteroaromatics, 3-bromopyridine and 3-bromoquin- We have further investigated this reaction in the presence
oline also led to isomers 13a and 14a in similar selectivi- of oct-1-ene (Scheme 4, Table 3). The length of the alkyl
ties of 70% and 75% (Table 2, entries 25–27).
chain on the alkene has a minor influence on the selectiv-
ity. Similar or slightly higher selectivities in favour of (E)-
1-arylalk-1-enes were obtained with oct-1-ene than with
dec-1-ene. For example selectivities of 84% and 75% in
favour of products 16a and 21a were obtained for the cou-
pling of oct-1-ene with 4-bromobenzaldehyde or 4-fluo-
robromobenzene instead of 81% and 70% with dec-1-ene
(Table 3, entries 3 and 12). With this alkene we also ex-
amined the selectivity of the reaction using a several other
aryl bromides. For example, with methyl 4-bromoben-
In summary, in all cases the DMA/NaOAc conditions
gave higher selectivities than the DMF/K2CO3 conditions.
The migration of the double bond of the alkene occurs af-
ter ordinary Heck arylation on the terminal (or internal)
carbon (Scheme 3). Then, an elimination-readdition of
HPdBr to give intermediate B would occur. We assumed
that using the DMA/NaOAc conditions, a sodium acetate
mediated abstraction of bromide from the arylpalladium
bromide takes place. This intermediate would form a p
Synthesis 2007, No. 11, 1683–1696 © Thieme Stuttgart · New York

1686
Y. Fall et al.
PAPER
Table 2 Palladium-Catalysed Coupling of Aryl Halides with Dec-1-ene (Scheme 2)a
Entry
Aryl halide
Solvent
Base
Substrate/catalyst Product number Ratio of isomers Yield (%)
ratio
Isomer a
a:b:other isomers
(%)
1
2
4-bromoacetophenone
4-bromobenzaldehyde
4-bromobenzaldehyde
4-bromobenzaldehyde
4-bromobenzophenone
4-bromobenzophenone
4-bromobenzophenone
4-trifluoromethylbromobenzene
4-trifluoromethylbromobenzene
4-bromobenzonitrile
DMAc
DMAc
DMA
DMF
DMA
DMA
DMF
DMA
DMF
DMA
DMF
DMA
NaOAc
NaOAc
NaOAc
K2CO3
NaOAc
NaOAc
K2CO3
NaOAc
K2CO3
NaOAc
K2CO3
NaOAc
NaOAc
K2CO3
NaOAc
NaOAc
K2CO3
NaOAc
NaOAc
NaOAc
K2CO3
NaOAc
K2CO3
NaOAc
NaOAc
NaOAc
K2CO3
NaOAc
K2CO3
NaOAc
10000
1000
1a
2a
76:10:14
82:9:9
99 (96)
100 (97)
92
3
10000
10000
1000
2a
81:10:9
66:14:20
76:10:14
80:7:13
64:14:22
73:9:18
59:11:30
76:10:14
52:20:28
80:10:10
83:8:9
4
2a
100b
5
3a
98 (96)
33
6
10000
10000
10000
10000
10000
10000
10000
10000
10000
1000
3a
7
3a
80b
8
4a
100 (97)
95b
9
4a
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
5a
99 (95)
92b
4-bromobenzonitrile
5a
4-bromonitrobenzene
6a
95 (93)
100 (95)
82b
3,5-bistrifluoromethylbromobenzene DMA
3,5-bistrifluoromethylbromobenzene DMF
7a
7a
70:15:15
69:12:19
68:9:23
43:25:32
64:14:22
63:15:22
62:15:23
51:21:28
70:3:27
36:8:56
nd
4-fluorobromobenzene
iodobenzene
DMA
DMA
DMF
DMA
DMA
DMA
DMF
DMA
DMF
DMA
DMA
DMA
DMF
DMA
DMF
DMA
8a
100 (95)
100 (94)
88b
10000
10000
1000
9a
iodobenzene
9a
bromobenzene
9a
93 (82)
100 (96)
22
4-bromoanisole
4-bromoanisole
4-bromoanisole
2-bromotoluene
2-bromotoluene
bromomesitylene
9-bromoanthracene
2-bromothiophene
2-bromothiophene
3-bromopyridine
3-bromopyridine
3-bromoquinoline
1000
10a
10a
10a
11a
11a
–
10000
100
58
10000
1000
96 (93)
70b
1000
ndc
1000
–
nd
ndc
1000
12a
12a
13a
13a
14a
60:28:12
34:24:42
70:12:18
50:18:32
75:15:10
100 (94)
82b
1000
10000
1000
100 (94)
100b
10000
92 (90)
a Conditions: [Pd(C3H5)Cl]2/Tedicyp = 1:2, aryl halide: 1 mmol, dec-1-ene: 2 mmol, base: 2 mmol, 20 h, 110 °C, argon. GC and NMR yields,
yields in parenthesis are isolated mixtures of all the isomers.
b Reaction performed at 130 °C.
c Unidentified mixture of isomers.
Synthesis 2007, No. 11, 1683–1696 © Thieme Stuttgart · New York

PAPER
Influence of Reaction Conditions on Heck Reaction with Simple Alkenes
1687
Ar
Br
Ar
Br
H
Br
[Pd]
(CH2)nCH3
Pd
Pd
ArBr
Pd
+
Ar
(CH2)nCH3
(CH2)n–1CH3
(CH2)nCH3
A
NaOAc
DMA
Br
(CH2)nCH3
Pd
a
Ar
Ar
(CH2)n–1CH3
B
+
(CH2)n–1CH3
+
AcO–
(CH2)n–2CH3
Pd
AcO–
Pd
Ar
(CH2)nCH3
Ar
Ar
(CH2)nCH3
Ar
C
+ NaBr
Scheme 3
zoate, bromobenzene or 3-bromonitrobenzene, products good yields. With these alkenes, mixtures of isomers are
20a, 22a and 27a were obtained in 74%, 79%, and 73% generally obtained due to the partial migration of the alk-
selectivity, respectively (Table 3, entries 11,13 and 18).
ene carbon–carbon double bond. The selectivity of the re-
action depends on the substituents of the aryl halide, on
the steric hindrance of the alkene and also on the reaction
conditions such as the base, solvent and temperature. In
all cases, the major isomer is the (E)-1-arylalk-1-ene, and
up to 97% of this isomer have been obtained using a
branched alkene. However, in most cases selectivities of
70–80% were obtained. Both the para-substituted elec-
tron-excessive and the electron-deficient aryl bromides
were reacted successfully using 0.1–0.01 mol% catalyst.
These results indicate that the oxidative addition of the
aryl bromide to palladium is probably not the rate-limiting
step of the catalytic cycle with such alkenes using this cat-
alyst. For this reason, this method is applicable to both
electron-deficient and electron-rich aryl bromides. Even
ortho-substituted aryl bromides have been used success-
fully and led to satisfactory regio- and stereoselectivities
in favour of isomers a. On the other hand, the di-ortho-
substituted aryl bromides gave mixtures of isomers. We
believe that this system compares favourably with other
catalyst systems that have been reported for the reactions
using simple alk-1-enes. These results represent econom-
ically attractive and environmentally friendly procedures.
Moreover, several alk-1-enes are commercially available.
This is a practical advantage of this reaction compared to
the Suzuki, Negishi or Stille coupling procedures using
organometallic derivatives of these alkenes.
Finally, we have investigated this reaction in the presence
of four branched alk-1-enes, 4-methylhex-1-ene, 5-meth-
ylhex-1-ene, allylcyclopentane, and allylcyclohexane
(Scheme 5, Table 4). The best results were obtained using
4-methylhex-1-ene (Table 4, entries 1–13). With this alk-
ene, the migration of the double bond was generally not
observed and only 3–9% of the isomers 31b–37b was de-
tected. Therefore, with this alkene, very high selectivities
of 91–97% in favour of 31a–37a were obtained. Again,
this selectivity does not seem to be largely influenced by
electronic factors on the aryl bromide. For example, 4-
bromoanisole or 4-bromobenzaldehyde led to similar re-
gio- and stereoselectivities (Table 4, entries 2, 3, 12 and
13). With the other branched alkenes, 5-methylhex-1-ene,
allylcyclopentane and allylcyclohexane, selectivities of
74–78% in isomers 38a–47a which are very similar to
those obtained using the linear alkenes have been mea-
sured (Table 4, entries 14–33). This difference of selectiv-
ity between 4-methylhex-1-ene and the other linear of
branched alkene probably comes from steric factors.
These steric factors seem to have an influence on the elim-
ination–readdition process of HPdBr to give intermediate
B in Scheme 3.
In summary, in the presence of the Tedicyp/palladium
complex, the Heck alkenylation of several aryl halides
with linear and branched alk-1-enes can be performed in
Ph2P
PPh2
PPh2
Ph2P
n-C6H13
[Pd(C3H5)Cl]2
DMA, NaOAc, 110 °C
n-C6H13
X
+
+
R
R
n-C6H13
15b–30b
+ other isomers
R
15a–30a
R = MeCO, HCO, CO2Me, CN, NO2, CF3, F, MeO, OH, Me, CH2OH, H
Scheme 4
Synthesis 2007, No. 11, 1683–1696 © Thieme Stuttgart · New York

1688
Y. Fall et al.
PAPER
Table 3 Palladium-Catalysed Coupling of Aryl Halides with Oct-1-ene (Scheme 4)a
Entry
Aryl bromide
Substrate/catalyst
ratio
Product number
Isomer a
Ratio of isomers
a:b:other isomers (%)
Yield (%)
1
2
4-bromoacetophenone
4-bromoacetophenone
4-bromobenzaldehyde
4-bromobenzaldehyde
4-trifluoromethylbromobenzene
4-trifluoromethylbromobenzene
4-bromobenzonitrile
4-bromobenzonitrile
4-bromonitrobenzene
4-bromonitrobenzene
methyl 4-bromobenzoate
4-fuorobromobenzene
bromobenzene
250
1000
1000
10000
1000
10000
250
15a
15a
16a
16a
17a
17a
18a
18a
19a
19a
20a
21a
22a
23a
24a
25a
26a
27a
28a
29a
29a
30a
78:10:12
79:9:12
86 (84)
52
3
84:4:12
98 (94)
12
4
76:10:14
75:10:15
78:6:26
5
100 (92)
77
6
7
76:9:15
95 (90)
61
8
1000
1000
10000
1000
1000
1000
1000
250
76:9:15
9
80:9:11
100 (93)
60
10
11
12
13
14
15
16
17
18
19
20
21
22
74:9:17
74:10:16
75:8:17
95 (90)
94 (89)
85 (82)
100 (94)
93 (90)
40 (36)
95 (91)
85 (80)
28 (25)
100 (90)
20
79:6:15
4-bromotoluene
77:9:14
4-bromoanisole
62:13:25
70:10:20
70:15:15
73:13:14
57:nd:43b
70:nd:30b
48:nd:52b
74:nd:26b
4-bromophenol
1000
1000
250
3-bromobenzaldehyde
3-bromonitrobenzene
2-bromoacetophenone
2-bromobenzyl alcohol
2-bromobenzyl alcohol
2-bromotoluene
250
250
1000
1000
100 (93)
a Conditions: [Pd(C3H5)Cl]2/Tedicyp = 1:2, aryl bromide: 1 mmol, oct-1-ene: 2 mmol, NaOAc: 2 mmol, DMA, 20 h, 110 °C, argon. GC and
NMR yields, yields in parenthesis are isolated mixtures of all the isomers.
b nd = not determined.
Ar
+
Ph2P
Ph2P
Ar
PPh2
PPh2
31a–37a
38a, 39a
31b–37b
38b, 39b
or
or
[Pd(C3H5)Cl]2
DMA, NaOAc, 110 °C
+
+
ArBr +
+ other isomers
Ar
Ar
Ar
Ar
(CH2)n
(CH2)n
(CH2)n
n = 1: 40a–43a
n = 2: 44a–47a
40b–43b
44b–47b
Scheme 5
Synthesis 2007, No. 11, 1683–1696 © Thieme Stuttgart · New York

PAPER
Influence of Reaction Conditions on Heck Reaction with Simple Alkenes
1689
Table 4 Palladium-Catalysed Coupling of Aryl Halides with 4-Methylhex-1-ene, 5-Methylhex-1-ene, Allylcyclopentane, or Allylcyclo-
hexane (Scheme 5)a
Entry
Aryl bromide
Alkene
Substrate/catalyst Product number Ratio of isomers
Yield (%)
ratio
Isomer a
31a
31a
32a
33a
33a
34a
34a
35a
35a
36a
36a
37a
37a
38a
38a
39a
39a
40a
40a
41a
41a
42a
42a
43a
43a
44a
44a
45a
45a
46a
46a
47a
47a
a:b:other isomers (%)
1
2
4-bromoacetophenone
4-bromoacetophenone
4-bromobenzaldehyde
4-bromobenzophenone
4-bromobenzophenone
4-trifluoromethylbromobenzene
4-trifluoromethylbromobenzene
4-bromobenzonitrile
4-bromobenzonitrile
4-bromonitrobenzene
4-bromonitrobenzene
4-bromoanisole
4-methylhex-1-ene
1000
92:8:0
100 (95)
60
4-methylhex-1-ene 10000
92:8:0
3
4-methylhex-1-ene
4-methylhex-1-ene
1000
250
92:8:0
100 (94)
100 (95)
15
4
91:9:0
5
4-methylhex-1-ene 10000
91:9:0
6
4-methylhex-1-ene
4-methylhex-1-ene
4-methylhex-1-ene
4-methylhex-1-ene
4-methylhex-1-ene
4-methylhex-1-ene
4-methylhex-1-ene
4-methylhex-1-ene
5-methylhex-1-ene
250
1000
250
97:3:0
100 (94)
90
7
97:3:0
8
95:5:0
100 (95)
35
9
1000
250
97:3:0
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
96:4:0
92 (87)
38
1000
250
96:4:0
92:8:0
98 (94)
79
4-bromoanisole
1000
1000
90:8:2
4-bromoacetophenone
4-bromoacetophenone
4-bromobenzophenone
4-bromobenzophenone
4-bromoacetophenone
4-bromoacetophenone
4-bromobenzophenone
4-bromobenzophenone
4-bromonitrobenzene
4-bromonitrobenzene
3-bromopyridine
76:10:14
78:8:14
74:12:14
75:11:14
76:11:13
75:11:14
77:12:11
77:11:12
75:11:14
74:12:14
78:8:14
78:8:14
76:9:15
78:8:14
76:7:17
78:7:15
77:13:10
77:12:11
77:13:10
78:13:9
100 (96)
18
5-methylhex-1-ene 10000
5-methylhex-1-ene
5-methylhex-1-ene
allylcyclopentane
allylcyclopentane
allylcyclopentane
allylcyclopentane
allylcyclopentane
allylcyclopentane
allylcyclopentane
allylcyclopentane
allylcyclohexane
allylcyclohexane
allylcyclohexane
allylcyclohexane
allylcyclohexane
allylcyclohexane
allylcyclohexane
allylcyclohexane
250
1000
250
100 (94)
45
92 (87)
83
1000
250
83 (80)
38
1000
250
100 (93)
52
1000
250
100 (91)
50
3-bromopyridine
1000
1000
10000
250
4-bromoacetophenone
4-bromoacetophenone
4-bromonitrobenzene
4-bromonitrobenzene
3-bromotoluene
97 (94)
37
100 (92)
52
1000
250
100 (91)
70
3-bromotoluene
1000
1000
10000
3-bromopyridine
100 (94)
13
3-bromopyridine
a Conditions: [Pd(C3H5)Cl]2/Tedicyp = 1:2, aryl bromide: 1 mmol, alk-1-ene: 2 mmol, NaOAc: 2 mmol, DMA, 20 h, 110 °C, argon. GC and
NMR yields, yields in parenthesis are isolated mixtures of all the isomers.
Synthesis 2007, No. 11, 1683–1696 © Thieme Stuttgart · New York

1690
Y. Fall et al.
PAPER
DMA (N,N-dimethylacetamide) analytical grade (99%) was not dis-
tilled before use. NaOAc 99% was used. Aryl halides and alkenes
were used without purification. All reactions were run under argon
using vacuum lines in Schlenk tubes in oven-dried glassware. The
reactions were followed by GC and NMR. Conversions were deter-
7.42 (d, J = 8.3 Hz, 2 H), 6.45 (d, J = 15.7 Hz, 1 H), 6.39 (dt,
J = 15.7, 7.0 Hz, 1 H), 2.27–2.18 (m, 2 H), 1.53–1.40 (m, 2 H),
1.40–1.18 (m, 10 H), 0.87 (t, J = 7.0 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 207.3, 142.6, 137.0, 134.9, 132.5,
131.9, 131.0, 130.3, 129.3, 128.6, 126.0, 33.6, 32.2, 31.3, 29.8,
29.6, 29.5, 23.0, 14.5.
1
mined using H NMR and the GC analysis of the crude mixture
1
without internal standard. H NMR (300 MHz) and 13C NMR (75
Anal. Calcd for C23H28O: C, 86.20; H, 8.81. Found: C, 86.14; H,
8.97.
MHz) spectra were recorded in CDCl3 solutions. Chemical shifts (d)
are reported in ppm relative to CDCl3. Flash chromatography was
performed on silica gel (230–400 mesh). The isolated yields given
are for mixtures of all the isomers. The NMR analyses were per-
formed on the cleanest purified fraction.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.36 (s, 1 H), 5.17 (s, 1 H).
(E)-1-(Dec-1-enyl)-4-trifluoromethylbenzene (4a) (Table 2,
Entry 8)5b
The reaction of 4-trifluoromethylbromobenzene (0.225 g, 1 mmol)
and dec-1-ene (0.280 g, 2 mmol) afforded 4a in 73% selectivity and
in 97% (0.276 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.53 (d, J = 8.4 Hz, 2 H), 7.41 (d,
J = 8.4 Hz, 2 H), 6.40 (d, J = 15.7 Hz, 1 H), 6.32 (dt, J = 15.7, 7.0
Hz, 1 H), 2.27–2.18 (m, 2 H), 1.53–1.40 (m, 2 H), 1.40–1.18 (m, 10
H), 0.88 (t, J = 7.0 Hz, 3 H).
Pd-Tedicyp Catalyst10
An oven-dried 40-mL Schlenk tube equipped with a magnetic stir-
ring bar under argon, was charged with [Pd(h3-C3H5)Cl]2 (4.2 mg,
11.6 mmol) and Tedicyp (20 mg, 23.2 mmol). Anhyd DMF (2.5 mL)
was added, and the solution was stirred at r.t. for 10 min.
Heck Reaction of Alk-1-enes with Aryl Halides; General Proce-
dure
A mixture of aryl halide (1 mmol), alk-1-ene (2 mmol) and NaOAc
(0.164 g, 2 mmol) in DMA (3 mL) was heated at 110 °C for 20 h in
the presence of cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinometh-
yl)cyclopentane/[Pd(C3H5)Cl]2 complex (1:2, prepared as above)
under argon. The corresponding products or mixture of products
were obtained after addition of H2O (20 mL), extraction with
CH2Cl2 (20 mL), separation, drying (MgSO4), evaporation and pu-
rification by chromatography on silica gel (pentane–Et2O).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.31 (s, 1 H), 5.12 (s, 1 H).
(E)-4-(Dec-1-enyl)benzonitrile (5a) (Table 2, Entry 10)5b
The reaction of 4-bromobenzonitrile (0.182 g, 1 mmol) and dec-1-
ene (0.280 g, 2 mmol) afforded 5a in 76% selectivity and in 95%
(0.229 g) yield.
(E)-1-Acetyl-4-(dec-1-enyl)benzene (1a) (Table 2, Entry 1)5b
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and dec-
1-ene (0.280 g, 2 mmol) afforded 1a in 76% selectivity and in 96%
(0.248 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.87 (d, J = 8.7 Hz, 2 H), 7.39 (d,
J = 8.7 Hz, 2 H), 6.41 (d, J = 15.9 Hz, 1 H), 6.34 (m, 1 H), 2.57 (s,
3 H), 2.25–2.10 (m, 2 H), 1.50–1.35 (m, 2 H), 1.35–1.15 (m, 10 H),
0.87 (m, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.55 (d, J = 8.4 Hz, 2 H), 7.39 (d,
J = 8.4 Hz, 2 H), 6.37 (m, 2 H), 2.27–2.18 (m, 2 H), 1.53–1.40 (m,
2 H), 1.40–1.18 (m, 10 H), 0.87 (t, J = 7.0 Hz, 3 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.31 (s, 1 H), 5.16 (s, 1 H).
(E)-1-(Dec-1-enyl)-4-nitrobenzene (6a) (Table 2, Entry 12)5b
The reaction of 4-bromonitrobenzene (0.202 g, 1 mmol) and dec-1-
ene (0.280 g, 2 mmol) afforded 6a in 80% selectivity and in 93%
(0.243 g) yield.
1H NMR (300 MHz, CDCl3): d = 8.12 (d, J = 7.9 Hz, 2 H), 7.43 (d,
J = 7.9 Hz, 2 H), 6.46–6.34 (m, 2 H), 2.30–2.15 (m, 2 H), 1.50–1.40
(m, 2 H), 1.40–1.10 (m, 10 H), 0.90–0.75 (m, 3 H).
(E)-1-Acetyl-4-(dec-1-en-2-yl)benzene (1b)
1H NMR (300 MHz, CDCl3): d = 7.91 (d, J = 8.7 Hz, 2 H), 7.48 (d,
J = 8.7 Hz, 2 H), 5.35 (s, 1 H), 5.15 (s, 1 H), 2.59 (s, 3 H), 2.50–2.40
(m, 2 H), 1.50–1.10 (m, 12 H), 0.86 (t, J = 7.7 Hz, 3 H).
(E)-4-(Dec-1-enyl)benzaldehyde (2a) (Table 2, Entry 2)
The reaction of 4-bromobenzaldehyde (0.185 g, 1 mmol) and dec-
1-ene (0.280 g, 2 mmol) afforded 2a in 82% selectivity and in 97%
(0.237 g) yield.
1H NMR (300 MHz, CDCl3): d = 9.94 (s, 1 H), 7.78 (d, J = 8.3 Hz,
2 H), 7.46 (d, J = 8.3 Hz, 2 H), 6.41 (m, 2 H), 2.30–2.20 (m, 2 H),
1.50–1.23 (m, 12 H), 0.93–0.53 (m, 3 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.37 (s, 1 H), 5.21 (s, 1 H).
(E)-1-(Dec-1-enyl)-3,5-bis(trifluoromethyl)benzene (7a) (Table
2, Entry 13)
The reaction of 3,5-bis(trifluoromethyl)bromobenzene (0.293 g, 1
mmol) and dec-1-ene (0.280 g, 2 mmol) afforded 7a in 83% selec-
tivity and in 95% (0.335 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.71 (s, 2 H), 7.65 (s, 1 H), 6.43
(d, J = 15.9 Hz, 1 H), 6.35 (m, 1 H), 2.30–2.17 (m, 2 H), 1.52–1.15
(m, 12 H), 0.90–0.80 (m, 3 H).
13C NMR (75 MHz, CDCl3): d = 191.7, 144.1, 135.5, 134.8, 130.1,
128.9, 126.3, 33.2, 31.8, 30.9, 29.4, 29.2, 29.0, 22.6, 14.0.
Anal. Calcd for C17H24O: C, 83.55; H, 9.90. Found: C, 83.29; H,
9.91.
13C NMR (75 MHz, CDCl3): d = 139.5, 135.2, 131.3 (q, J = 32.3
Hz), 126.8, 125.2 (m), 123.1 (q, J = 273.1 Hz), 119.7 (m), 33.0,
31.8, 30.9, 29.4, 29.2, 29.0, 22.6, 14.1.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.37 (s, 1 H), 5.18 (s, 1 H).
Anal. Calcd for C18H22F6: C, 61.36; H, 6.29. Found: C, 61.49; H,
6.40.
(E)-1-Benzoyl-4-(dec-1-enyl)benzene (3a) (Table 2, Entry 5)
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol) and dec-
1-ene (0.280 g, 2 mmol) afforded 3a in 76% selectivity and in 96%
(0.307 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.77 (d, J = 8.3 Hz, 2 H), 7.73 (d,
J = 8.3 Hz, 2 H), 7.56 (t, J = 7.6 Hz, 1 H), 7.45 (t, J = 7.6 Hz, 2 H),
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.36 (s, 1 H), 5.22 (s, 1 H).
Synthesis 2007, No. 11, 1683–1696 © Thieme Stuttgart · New York

PAPER
Influence of Reaction Conditions on Heck Reaction with Simple Alkenes
1691
(E)-1-Fluoro-4-(dec-1-enyl)benzene (8a) (Table 2, Entry 15)5b
The reaction of 4-fluorobromobenzene (0.175 g, 1 mmol) and dec-
1-ene (0.280 g, 2 mmol) afforded 8a in 69% selectivity and in 95%
(0.223 g) yield.
(E)-3-(Dec-1-enyl)pyridine (13a) (Table 2, Entry 28)5b
The reaction of 3-bromopyridine (0.158 g, 1 mmol) and dec-1-ene
(0.280 g, 2 mmol) afforded 13a in 70% selectivity and in 94%
(0.204 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.27 (dd, J = 8.6, 5.5 Hz, 2 H),
6.96 (t, J = 8.6 Hz, 2 H), 6.32 (d, J = 15.7 Hz, 1 H), 6.12 (dt,
J = 15.7, 7.0 Hz, 1 H), 2.25–2.10 (m, 2 H), 1.50–1.40 (m, 2 H),
1.40–1.10 (m, 10 H), 0.87 (t, J = 7.0 Hz, 3 H).
1H NMR (300 MHz, CDCl3): d = 8.54 (s, 1 H), 8.40 (d, J = 4.7 Hz,
1 H), 7.65 (d, J = 7.5 Hz, 1 H), 7.21 (dd, J = 7.5, 4.7 Hz, 1 H), 6.35
(d, J = 15.8 Hz, 1 H), 6.29 (dt, J = 15.8, 7.1 Hz, 1 H), 2.25–2.15 (m,
2 H), 1.50–1.40 (m, 2 H), 1.40–1.10 (m, 10 H), 0.88 (t, J = 7.0 Hz,
3 H).
Traces of branched isomer were also observed.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.30 (s, 1 H), 5.14 (s, 1 H).
1H NMR (300 MHz, CDCl3): d = 5.19 (s, 1 H), 5.02 (s, 1 H).
(E)-1-Phenyldec-1-ene (9a) (Table 2, Entry 16)19
The reaction of iodobenzene (0.204 g, 1 mmol) and dec-1-ene
(0.280 g, 2 mmol) afforded 9a in 68% selectivity and in 94% (0.203
g) yield.
1H NMR (300 MHz, CDCl3): d = 7.35–7.10 (m, 5 H), 6.37 (d,
J = 15.8 Hz, 1 H), 6.22 (dt, J = 15.8, 6.8 Hz, 1 H), 2.25–2.10 (m, 2
H), 1.55–1.10 (m, 12 H), 0.87 (t, J = 7.0 Hz, 3 H).
(E)-3-(Dec-1-enyl)quinoline (14a) (Table 2, Entry 30)
The reaction of 3-bromoquinoline (0.208 g, 1 mmol) and dec-1-ene
(0.280 g, 2 mmol) afforded 14a in 75% selectivity and in 90%
(0.240 g) yield.
1H NMR (300 MHz, CDCl3): d = 8.95 (d, J = 2.2 Hz, 1 H), 8.04 (d,
J = 8.1 Hz, 1 H), 7.94 (d, J = 2.2 Hz, 1 H), 7.73 (d, J = 8.1 Hz, 1
H), 7.61 (t, J = 7.5 Hz, 1 H), 7.48 (t, J = 7.5 Hz, 1 H), 6.51 (d,
J = 15.8 Hz, 1 H), 6.43 (dt, J = 15.8, 7.1 Hz, 1 H), 2.30–2.20 (m, 2
H), 1.55–1.45 (m, 2 H), 1.40–1.10 (m, 10 H), 0.87 (t, J = 7.0 Hz, 3
H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.24 (s, 1 H), 5.01 (s, 1 H).
(E)-1-(Dec-1-enyl)-4-methoxybenzene (10a) (Table 2, Entry
19)5b
The reaction of 4-bromoanisole (0.187 g, 1 mmol) and dec-1-ene
(0.280 g, 2 mmol) afforded 10a in 63% selectivity and in 96%
(0.236 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.26 (d, J = 8.7 Hz, 2 H), 6.82 (d,
J = 8.7 Hz, 2 H), 6.30 (d, J = 15.8 Hz, 1 H), 6.05 (dt, J = 15.8, 7.1
Hz, 1 H), 3.80 (s, 3 H), 2.20–2.10 (m, 2 H), 1.50–1.40 (m, 2 H),
1.40–1.10 (m, 10 H), 0.88 (t, J = 7.0 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 149.3, 147.1, 134.0, 131.4, 130.8,
129.1, 128.7, 128.1, 127.6, 126.7, 126.5, 33.3, 31.8, 29.4, 29.3,
29.2, 29.1, 22.6, 14.1.
Anal. Calcd for C19H25N: C, 85.34; H, 9.42. Found: C, 85.30; H,
9.27.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.45 (s, 1 H), 5.24 (s, 1 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.18 (s, 1 H), 4.96 (s, 1 H).
(E)-1-Acetyl-4-(oct-1-enyl)benzene (15a) (Table 3, Entry 1)21
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and oct-1-
ene (0.224 g, 2 mmol) afforded 15a in 78% selectivity and in 84%
(0.193 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.87 (d, J = 8.5 Hz, 2 H), 7.39 (d,
J = 8.5 Hz, 2 H), 6.41 (d, J = 15.9 Hz, 1 H), 6.33 (m, 1 H), 2.56 (s,
3 H), 2.30–2.15 (m, 2 H), 1.65–1.10 (m, 8 H), 0.90–0.65 (m, 3 H).
(E)-1-(Dec-1-enyl)-2-methylbenzene (11a) (Table 2, Entry 22)
The reaction of 2-bromotoluene (0.171 g, 1 mmol) and dec-1-ene
(0.280 g, 2 mmol) afforded 11a in 70% selectivity and in 93%
(0.214 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.40 (d, J = 7.2 Hz, 1 H), 7.15–
7.05 (m, 3 H), 6.55 (d, J = 15.7 Hz, 1 H), 6.07 (dt, J = 15.7, 7.0 Hz,
1 H), 2.31 (s, 3 H), 2.27–2.07 (m, 2 H), 1.50–1.40 (m, 2 H), 1.40–
1.15 (m, 10 H), 0.87 (t, J = 7.0 Hz, 3 H).
13C NMR (75 MHz, CDCl3): d = 137.8, 135.6, 133.3, 130.8, 128.3,
127.4, 126.7, 126.2, 34.1, 32.6, 30.3, 30.2, 30.0, 29.9, 23.4, 20.5,
14.8.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.34 (s, 1 H), 5.14 (s, 1 H).
(E)-4-(Oct-1-enyl)benzaldehyde (16a) (Table 3, Entry 3)5a
The reaction of 4-bromobenzaldehyde (0.185 g, 1 mmol) and oct-1-
ene (0.224 g, 2 mmol) afforded 16a in 84% selectivity and in 94%
(0.203 g) yield.
Anal. Calcd for C17H26: C, 88.63; H, 11.37. Found: C, 88.50; H,
11.17.
1H NMR (300 MHz, CDCl3): d = 9.95 (s, 1 H), 7.80 (d, J = 8.1 Hz,
2 H), 7.47 (d, J = 8.1 Hz, 2 H), 6.44 (d, J = 15.9 Hz, 1 H), 6.40–6.30
(m, 1 H), 2.30–2.10 (m, 2 H), 1.60–1.10 (m, 8 H), 0.88 (t, J = 7.0
Hz, 3 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.15 (s, 1 H), 4.81 (s, 1 H).
Traces of branched isomer were also observed.
(E)-2-(Dec-1-enyl)thiophene (12a) (Table 2, Entry 26)20
The reaction of 2-bromothiophene (0.163 g, 1 mmol) and dec-1-ene
(0.280 g, 2 mmol) afforded 12a in 60% selectivity and in 94%
(0.209 g) yield.
1H NMR (300 MHz, CDCl3): d = 5.35 (s, 1 H), 5.14 (s, 1 H).
(E)-1-(Oct-1-enyl)-4-(trifluoromethyl)benzene (17a) (Table 3,
Entry 5)22
The reaction of 4-trifluoromethylbromobenzene (0.225 g, 1 mmol)
and oct-1-ene (0.224 g, 2 mmol) afforded 17a in 75% selectivity
and in 92% (0.236 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.51 (d, J = 8.3 Hz, 2 H), 7.39 (d,
J = 8.3 Hz, 2 H), 6.39 (d, J = 15.9 Hz, 1 H), 6.30 (m, 1 H), 2.25–
2.15 (m, 2 H), 1.60–1.10 (m, 8 H), 0.95–0.65 (m, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.05 (m, 1 H), 6.92 (m, 1 H), 6.85
(m, 1 H), 6.48 (d, J = 15.8 Hz, 1 H), 6.06 (dt, J = 15.8, 7.1 Hz, 1 H),
2.20–2.10 (m, 2 H), 1.50–1.40 (m, 2 H), 1.40–1.10 (m, 10 H), 0.88
(t, J = 7.0 Hz, 3 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.37 (s, 1 H), 4.93 (s, 1 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.29 (s, 1 H), 5.13 (s, 1 H).
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(E)-4-(Oct-1-enyl)benzonitrile (18a) (Table 3, Entry 7)23
The reaction of 4-bromobenzonitrile (0.182 g, 1 mmol) and oct-1-
ene (0.224 g, 2 mmol) afforded 18a in 76% selectivity and in 90%
(0.192 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.28 (d, J = 8.3 Hz, 2 H), 7.12 (d,
J = 8.3 Hz, 2 H), 6.38 (d, J = 15.8 Hz, 1 H), 6.20 (dt, J = 15.8, 6.8
Hz, 1 H), 2.35 (s, 3 H), 2.25–2.10 (m, 2 H), 1.55–1.10 (m, 8 H),
1.00–0.75 (m, 3 H).
1H NMR (300 MHz, CDCl3): d = 7.56 (d, J = 8.5 Hz, 2 H), 7.39 (d,
J = 8.5 Hz, 2 H), 6.40 (d, J = 15.9 Hz, 1 H), 6.35 (m, 1 H), 2.30–
2.10 (m, 2 H), 1.65–1.10 (m, 8 H), 0.95–0.65 (m, 3 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.25 (s, 1 H), 5.02 (s, 1 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.33 (s, 1 H), 5.19 (s, 1 H).
(E)-1-Methoxy-4-(oct-1-enyl)benzene (24a) (Table 3, Entry
15)22
The reaction of 4-bromoanisole (0.187 g, 1 mmol) and oct-1-ene
(0.224 g, 2 mmol) afforded 24a in 62% selectivity and in 90%
(0.196 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.26 (d, J = 8.5 Hz, 2 H), 6.82 (d,
J = 8.5 Hz, 2 H), 6.30 (d, J = 15.8 Hz, 1 H), 6.07 (dt, J = 15.8, 7.0
Hz, 1 H), 3.80 (s, 3 H), 2.20–2.08 (m, 2 H), 1.55–1.10 (m, 8 H),
0.90–0.75 (m, 3 H).
(E)-1-Nitro-4-(oct-1-enyl)benzene (19a) (Table 3, Entry 9)23
The reaction of 4-bromonitrobenzene (0.202 g, 1 mmol) and oct-1-
ene (0.224 g, 2 mmol) afforded 19a in 80% selectivity and in 93%
(0.217 g) yield.
1H NMR (300 MHz, CDCl3): d = 8.11 (d, J = 8.8 Hz, 2 H), 7.42 (d,
J = 8.8 Hz, 2 H), 6.41 (d, J = 15.9 Hz, 1 H), 6.37 (m, 1 H), 2.30–
2.15 (m, 2 H), 1.55–1.10 (m, 8 H), 0.88 (t, J = 7.0 Hz, 3 H).
Traces of branched isomer were also observed.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.17 (s, 1 H), 4.95 (s, 1 H).
1H NMR (300 MHz, CDCl3): d = 5.36 (s, 1 H), 5.21 (s, 1 H).
(E)-4-(Oct-1-enyl)phenol (25a) (Table 3, Entry 16)26
The reaction of 4-bromophenol (0.173 g, 1 mmol) and oct-1-ene
(0.224 g, 2 mmol) afforded 25a in 70% selectivity and in 36%
(0.074 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.24 (d, J = 8.5 Hz, 2 H), 6.76 (d,
J = 8.5 Hz, 2 H), 6.28 (d, J = 15.8 Hz, 1 H), 6.03 (dt, J = 15.8, 7.0
Hz, 1 H), 2.20–2.05 (m, 2 H), 1.55–1.10 (m, 8 H), 0.90–0.75 (m, 3
H).
(E)-Methyl 4-(oct-1-enyl)benzoate (20a) (Table 3, Entry 11)24
The reaction of methyl 4-bromobenzoate (0.215 g, 1 mmol) and oct-
1-ene (0.224 g, 2 mmol) afforded 20a in 74% selectivity and in 90%
(0.222 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.95 (d, J = 8.5 Hz, 2 H), 7.37 (d,
J = 8.5 Hz, 2 H), 6.40 (d, J = 15.9 Hz, 1 H), 6.31 (m, 1 H), 3.86 (m,
3 H), 2.30–2.10 (m, 2 H), 1.60–1.10 (m, 8 H), 0.90–0.70 (m, 3 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.15 (s, 1 H), 4.92 (s, 1 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.28 (s, 1 H), 5.11 (s, 1 H).
(E)-3-(Oct-1-enyl)benzaldehyde (26a) (Table 3, Entry 17)27
The reaction of 3-bromobenzaldehyde (0.185 g, 1 mmol) and oct-1-
ene (0.224 g, 2 mmol) afforded 26a in 70% selectivity and in 91%
(0.197 g) yield.
1H NMR (300 MHz, CDCl3): d = 9.99 (s, 1 H), 7.83 (s, 1 H), 7.69
(d, J = 6.4 Hz, 1 H), 7.57 (d, J = 7.7 Hz, 1 H), 7.43 (t, J = 7.4 Hz, 1
H), 6.42 (d, J = 15.7 Hz, 1 H), 6.34 (dt, J = 15.7, 7.0 Hz, 1 H), 2.25–
2.10 (m, 2 H), 1.55–1.10 (m, 8 H), 0.90–0.75 (m, 3 H).
(E)-1-Fluoro-4-(oct-1-enyl)benzene (21a) (Table 3, Entry 12)
The reaction of 4-fluorobromobenzene (0.175 g, 1 mmol) and oct-
1-ene (0.224 g, 2 mmol) afforded 21a in 75% selectivity and in 89%
(0.183 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.27 (dd, J = 8.6, 5.5 Hz, 2 H),
6.97 (t, J = 8.6 Hz, 2 H), 6.33 (d, J = 15.7 Hz, 1 H), 6.12 (dt,
J = 15.7, 7.0 Hz, 1 H), 2.25–2.15 (m, 2 H), 1.55–1.10 (m, 8 H), 0.88
(t, J = 7.0 Hz, 3 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.30 (s, 1 H), 5.14 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 161.4 (d, J = 245.4 Hz), 133.7 (m),
130.5, 128.1, 126.8 (d, J = 7.7 Hz), 114.8 (d, J = 21.4 Hz), 32.5,
31.3, 28.9, 28.5, 22.2, 13.7.
(E)-1-Nitro-3-(oct-1-enyl)benzene (27a) (Table 3, Entry 18)28
The reaction of 3-nitrobromobenzene (0.202 g, 1 mmol) and oct-1-
ene (0.224 g, 2 mmol) afforded 27a in 73% selectivity and in 80%
(0.186 g) yield.
1H NMR (300 MHz, CDCl3): d = 8.17 (s, 1 H), 8.01 (d, J = 7.9 Hz,
1 H), 7.60 (d, J = 7.6 Hz, 1 H), 7.42 (t, J = 8.2 Hz, 1 H), 6.43 (d,
J = 15.7 Hz, 1 H), 6.35 (dt, J = 15.7, 7.0 Hz, 1 H), 2.30–2.15 (m, 2
H), 1.55–1.10 (m, 8 H), 0.90–0.70 (m, 3 H).
Anal. Calcd for C14H19F: C, 81.51; H, 9.28. Found: C, 81.67; H,
9.20.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.19 (s, 1 H), 5.03 (s, 1 H).
(E)-1-Phenyloct-1-ene (22a) (Table 3, Entry 13)25
The reaction of bromobenzene (0.157 g, 1 mmol) and oct-1-ene
(0.224 g, 2 mmol) afforded 22a in 79% selectivity and in 82%
(0.154 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.40–7.10 (m, 5 H), 6.35 (d,
J = 15.9 Hz, 1 H), 6.20 (dt, J = 15.9, 6.6 Hz, 1 H), 2.25–2.05 (s, 2
H), 1.60–1.10 (m, 12 H), 0.95–0.70 (m, 3 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.36 (s, 1 H), 5.19 (s, 1 H).
(E)-1-Acetyl-2-(oct-1-enyl)benzene (28a) (Table 3, Entry 19)29
The reaction of 2-bromoacetophenone (0.199 g, 1 mmol) and oct-1-
ene (0.224 g, 2 mmol) afforded 28a in 57% selectivity and in 25%
(0.061 g) yield.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.22 (s, 1 H), 5.01 (s, 1 H).
1H NMR (300 MHz, CDCl3): d = 7.60–7.47 (m, 2 H), 7.38–7.22 (m,
2 H), 6.82 (d, J = 16.1 Hz, 1 H), 6.09 (dt, J = 16.1, 6.8 Hz, 1 H),
2.57 (s, 3 H), 2.25–2.15 (m, 2 H), 1.50–1.15 (m, 8 H), 0.90 (t,
J = 7.0 Hz, 3 H).
(E)-1-Methyl-4-(oct-1-enyl)benzene (23a) (Table 3, Entry 14)9e
The reaction of 4-bromotoluene (0.171 g, 1 mmol) and oct-1-ene
(0.224 g, 2 mmol) afforded 23a in 77% selectivity and in 94%
(0.190 g) yield.
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Influence of Reaction Conditions on Heck Reaction with Simple Alkenes
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(E)-[(2-Oct-1-enyl)phenyl]methanol (29a) (Table 3, Entry 20)30
The reaction of 2-bromobenzyl alcohol (0.187 g, 1 mmol) and oct-
1-ene (0.224 g, 2 mmol) afforded 29a in 70% selectivity and in 90%
(0.196 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.48 (d, J = 7.2 Hz, 1 H), 7.35–
7.15 (m, 3 H), 6.70 (d, J = 15.7 Hz, 1 H), 6.17 (dt, J = 15.7, 6.8 Hz,
1 H), 4.72 (s, 2 H), 2.29–2.20 (m, 2 H), 1.60–1.15 (m, 8 H), 0.90 (t,
J = 7.0 Hz, 3 H).
Anal. Calcd for C20H22O: C, 86.29; H, 7.97. Found: C, 86.54; H,
8.14.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.37 (s, 1 H), 5.14 (s, 1 H).
(E)-1-(4-Methylhex-1-enyl)-4-(trifluoromethyl)benzene (34a)
(Table 4, Entry 6)
The reaction of 4-trifluoromethylbromobenzene (0.225 g, 1 mmol)
and 4-methylhex-1-ene (0.196 g, 2 mmol) afforded 34a in 97% se-
lectivity and in 94% (0.228 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.53 (d, J = 8.3 Hz, 2 H), 7.41 (d,
J = 8.3 Hz, 2 H), 6.39 (d, J = 15.8 Hz, 1 H), 6.33 (dt, J = 15.8, 7.1
Hz, 1 H), 2.30–1.95 (m, 2 H), 1.55–1.10 (m, 3 H), 0.95–0.80 (m, 6
H).
13C NMR (75 MHz, CDCl3): d = 132.8, 129.6 (m), 127.5, 126.0,
125.4 (q, J = 3.8 Hz), 40.2, 34.8, 29.2, 19.1, 11.4.
(E)-1-Methyl-2-(oct-1-enyl)benzene (30a) (Table 3, Entry 22)23
The reaction of 2-bromotoluene (0.171 g, 1 mmol) and oct-1-ene
(0.224 g, 2 mmol) afforded 30a in 74% selectivity and in 93%
(0.188 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.40 (d, J = 6.4 Hz, 1 H), 7.19–
7.06 (m, 3 H), 6.55 (d, J = 15.7 Hz, 1 H), 6.07 (dt, J = 15.7, 7.0 Hz,
1 H), 2.29 (s, 3 H), 2.28–2.10 (m, 2 H), 1.70–1.05 (m, 8 H), 0.95–
0.60 (m, 3 H).
Anal. Calcd for C14H17F3: C, 69.40; H, 7.07. Found: C, 69.51; H,
6.91.
(E)-1-Acetyl-4-(4-methylhex-1-enyl)benzene (31a) (Table 4,
Entry 1)
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and
4-methylhex-1-ene (0.196 g, 2 mmol) afforded 31a in 92% selectiv-
ity and in 95% (0.205 g) yield.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.31 (s, 1 H), 5.11 (s, 1 H).
(E)-4-(4-Methylhex-1-enyl)benzonitrile (35a) (Table 4, Entry 8)
The reaction of 4-bromobenzonitrile (0.182 g, 1 mmol) and 4-meth-
ylhex-1-ene (0.196 g, 2 mmol) afforded 35a in 95% selectivity and
in 95% (0.189 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.56 (d, J = 7.4 Hz, 2 H), 7.40 (d,
J = 7.4 Hz, 2 H), 6.39 (d, J = 15.9 Hz, 1 H), 6.32 (dt, J = 15.9, 7.4
Hz, 1 H), 2.30–1.95 (m, 2 H), 1.55–1.10 (m, 3 H), 0.95–0.80 (m, 6
H).
1H NMR (300 MHz, CDCl3): d = 7.87 (d, J = 8.5 Hz, 2 H), 7.40 (d,
J = 8.5 Hz, 2 H), 6.41 (d, J = 15.8 Hz, 1 H), 6.36 (dt, J = 15.8, 7.1
Hz, 1 H), 2.57 (s, 3 H), 2.30–2.00 (m, 2 H), 1.60–1.10 (m, 3 H),
0.90–0.65 (m, 6 H).
13C NMR (75 MHz, CDCl3): d = 197.1, 142.2, 134.9, 132.8, 129.6,
128.3, 125.5, 39.8, 34.4, 28.8, 26.1, 18.7, 11.0.
Anal. Calcd for C15H20O: C, 83.28; H, 9.32. Found: C, 83.40; H,
9.17.
13C NMR (75 MHz, CDCl3): d = 142.4, 134.3, 132.3, 129.5, 126.3,
119.1, 109.9, 40.2, 34.8, 29.2, 19.1, 11.4.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.34 (s, 1 H), 5.12 (s, 1 H).
Anal. Calcd for C14H17N: C, 84.37; H, 8.60. Found: C, 84.02; H,
8.89.
(E)-4-(4-Methylhex-1-enyl)benzaldehyde (32a) (Table 4,
Entry 3)
The reaction of 4-bromobenzaldehyde (0.185 g, 1 mmol) and
4-methylhex-1-ene (0.196 g, 2 mmol) afforded 32a in 92% selectiv-
ity and in 94% (0.190 g) yield.
1H NMR (300 MHz, CDCl3): d = 9.95 (s, 1 H), 7.79 (d, J = 8.5 Hz,
2 H), 7.47 (d, J = 8.3 Hz, 2 H), 6.43 (d, J = 15.9 Hz, 1 H), 6.38 (m,
1 H), 2.30–2.00 (m, 2 H), 1.50–1.10 (m, 3 H), 0.90–0.65 (m, 6 H).
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.33 (s, 1 H), 5.14 (s, 1 H).
(E)-1-(4-Methylhex-1-enyl)-4-nitrobenzene (36a) (Table 4,
Entry 10)
The reaction of 4-bromonitrobenzene (0.202 g, 1 mmol) and
4-methylhex-1-ene (0.196 g, 2 mmol) afforded 36a in 96% selectiv-
ity and in 87% (0.191 g) yield.
1H NMR (300 MHz, CDCl3): d = 8.15 (d, J = 8.9 Hz, 2 H), 7.45 (d,
J = 8.9 Hz, 2 H), 6.51 (d, J = 15.9 Hz, 1 H), 6.47 (dt, J = 15.9, 7.4
Hz, 1 H), 2.35–2.10 (m, 2 H), 1.65–1.10 (m, 3 H), 0.90–0.75 (m, 6
H).
13C NMR (75 MHz, CDCl3): d = 192.1, 144.4, 135.0, 134.6, 130.6,
130.5, 126.8, 40.8, 35.3, 29.6, 19.6, 11.9.
Anal. Calcd for C14H18O: C, 83.12; H, 8.97. Found: C, 83.00; H,
9.07.
13C NMR (75 MHz, CDCl3): d = 146.8, 144.8, 135.8, 129.6, 126.7,
124.3, 40.7, 35.2, 29.6, 19.6, 11.8.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.36 (s, 1 H), 5.15 (s, 1 H).
Anal. Calcd for C13H17NO2: C, 71.21; H, 7.81. Found: C, 71.29; H,
7.68.
(E)-1-Benzoyl-4-(4-methylhex-1-enyl)benzene (33a) (Table 4,
Entry 4)
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol) and 4-
methylhex-1-ene (0.196 g, 2 mmol) afforded 33a in 91% selectivity
and in 95% (0.264 g) yield.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.36 (s, 1 H), 5.20 (s, 1 H).
(E)-1-Methoxy-4-(4-methylhex-1-enyl)benzene (37a) (Table 4,
Entry 12)
The reaction of 4-bromoanisole (0.187 g, 1 mmol) and 4-methyl-
hex-1-ene (0.196 g, 2 mmol) afforded 37a in 92% selectivity and in
94% (0.192 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.28 (d, J = 8.3 Hz, 2 H), 6.82 (d,
J = 8.3 Hz, 2 H), 6.30 (d, J = 15.9 Hz, 1 H), 6.05 (dt, J = 15.9, 7.4
1H NMR (300 MHz, CDCl3): d = 7.78 (d, J = 8.4 Hz, 2 H), 7.75 (d,
J = 8.4 Hz, 2 H), 7.58 (t, J = 7.5 Hz, 1 H), 7.48 (t, J = 7.5 Hz, 2 H),
7.42 (d, J = 8.4 Hz, 2 H), 6.44 (d, J = 15.8 Hz, 1 H), 6.37 (dt,
J = 15.8, 7.1 Hz, 1 H), 2.30–2.00 (m, 2 H), 1.60–1.10 (m, 3 H),
0.90–0.80 (m, 6 H).
13C NMR (75 MHz, CDCl3): d = 196.6, 142.5, 138.3, 136.0, 133.5,
132.5, 131.0, 130.5, 130.3, 128.6, 126.1, 40.7, 35.3, 29.6, 19.6,
11.9.
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Y. Fall et al.
PAPER
1-Benzoyl-4-(3-cyclopentylpropenyl)benzene (41a) (Table 4,
Hz, 1 H), 3.80 (s, 3 H), 2.25–1.95 (m, 2 H), 1.60–1.10 (m, 3 H),
0.90–0.70 (m, 6 H).
Entry 20)
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol) and allyl-
cyclopentane (0.220 g, 2 mmol) afforded 41a in 77% selectivity and
in 80% (0.232 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.79 (d, J = 8.5 Hz, 2 H), 7.75 (d,
J = 8.5 Hz, 2 H), 7.57 (t, J = 7.5 Hz, 1 H), 7.49 (t, J = 7.5 Hz, 2 H),
7.42 (d, J = 8.5 Hz, 2 H), 6.45 (d, J = 15.8 Hz, 1 H), 6.35 (dt,
J = 15.8, 7.1 Hz, 1 H), 2.24 (m, 2 H), 1.95–1.10 (m, 9 H).
13C NMR (75 MHz, CDCl3): d = 158.6, 130.8, 130.1, 127.7, 126.9,
113.9, 55.3, 40.1, 35.0, 29.1, 19.1, 11.5.
Anal. Calcd for C14H20O: C, 82.30; H, 9.87. Found: C, 82.37; H,
10.08.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.17 (s, 1 H), 4.92 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 196.6, 142.5, 138.3, 136.0, 132.5,
132.0, 131.9, 131.0, 130.3, 128.6, 126.0, 40.2, 39.9, 32.7, 25.5.
1-Acetyl-4-(5-methylhex-1-enyl)benzene (38a) (Table 4,
Entry 14)
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and
5-methylhex-1-ene (0.196 g, 2 mmol) afforded 38a in 76% selectiv-
ity and in 96% (0.207 g) yield.
Anal. Calcd for C21H22O: C, 86.85; H, 7.64. Found: C, 86.99; H,
7.82.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 7.87 (d, J = 8.5 Hz, 2 H), 7.39 (d,
J = 8.5 Hz, 2 H), 6.42 (d, J = 15.8 Hz, 1 H), 6.34 (dt, J = 15.8, 7.1
Hz, 1 H), 2.57 (s, 3 H), 2.26 (m, 2 H), 1.65 (m, 1 H), 1.39 (m, 2 H),
0.92 (d, J = 7.8 Hz, 6 H).
1H NMR (300 MHz, CDCl3): d = 5.34 (s, 1 H), 5.16 (s, 1 H).
1-(3-Cyclopentylpropenyl)-4-nitrobenzene (42a) (Table 4,
Entry 22)
The reaction of 4-bromonitrobenzene (0.202 g, 1 mmol) and allyl-
cyclopentane (0.220 g, 2 mmol) afforded 42a in 75% selectivity and
in 93% (0.215 g) yield.
1H NMR (300 MHz, CDCl3): d = 8.13 (d, J = 8.5 Hz, 2 H), 7.43 (d,
J = 8.5 Hz, 2 H), 6.45 (d, J = 15.8 Hz, 1 H), 6.41 (dt, J = 15.8, 7.1
Hz, 1 H), 2.25 (m, 2 H), 1.95–1.10 (m, 9 H).
13C NMR (75 MHz, CDCl3): d = 198.0, 143.1, 135.8, 135.1, 129.2,
129.1, 126.3, 38.6, 31.4, 27.9, 26.9, 22.8.
Anal. Calcd for C15H20O: C, 83.28; H, 9.32. Found: C, 83.48; H,
9.12.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.34 (s, 1 H), 5.16 (s, 1 H).
13C NMR (75 MHz, CDCl3): d = 144.9, 136.4, 128.9, 126.7, 124.4,
124.0, 40.1, 39.9, 32.8, 25.5.
1-Benzoyl-4-(5-methylhex-1-enyl)benzene (39a) (Table 4,
Entry 16)
The reaction of 4-bromobenzophenone (0.261 g, 1 mmol) and 5-
methylhex-1-ene (0.196 g, 2 mmol) afforded 39a in 74% selectivity
and in 94% (0.261 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.79 (d, J = 8.5 Hz, 2 H), 7.75 (d,
J = 8.5 Hz, 2 H), 7.57 (t, J = 7.5 Hz, 1 H), 7.49 (t, J = 7.5 Hz, 2 H),
7.42 (d, J = 8.5 Hz, 2 H), 6.45 (d, J = 15.8 Hz, 1 H), 6.38 (dt,
J = 15.8, 7.1 Hz, 1 H), 2.26 (m, 2 H), 1.65 (m, 1 H), 1.39 (m, 2 H),
0.92 (d, J = 7.8 Hz, 6 H).
Anal. Calcd for C14H17NO2: C, 72.70; H, 7.41. Found: C, 72.89; H,
7.50.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.34 (s, 1 H), 5.22 (s, 1 H).
3-(3-Cyclohexylpropenyl)pyridine (43a) (Table 4, Entry 24)
The reaction of 3-bromopyridine (0.158 g, 1 mmol) and allylcyclo-
pentane (0.220 g, 2 mmol) afforded 43a in 78% selectivity and in
91% (0.170 g) yield.
13C NMR (75 MHz, CDCl3): d = 196.6, 142.6, 138.4, 136.0, 135.0,
1H NMR (300 MHz, CDCl3): d = 8.53 (s, 1 H), 8.39 (d, J = 4.7 Hz,
1 H), 7.64 (d, J = 7.5 Hz, 1 H), 7.20 (dd, J = 7.5, 4.7 Hz, 1 H), 6.32
(d, J = 15.8 Hz, 1 H), 6.26 (dt, J = 15.8, 7.1 Hz, 1 H), 2.25 (m, 2 H),
1.95–1.10 (m, 9 H).
13C NMR (75 MHz, CDCl3): d = 147.8, 147.7, 133.5, 133.1, 132.4,
126.6, 123.3, 39.8, 39.5, 32.3, 25.1.
132.7, 131.0, 130.3, 129.2, 128.6, 126.0, 38.7, 31.4, 28.0, 22.9.
Anal. Calcd for C20H22O: C, 86.29; H, 7.97. Found: C, 86.07; H,
8.04.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.34 (s, 1 H), 5.15 (s, 1 H).
Anal. Calcd for C13H17N: C, 83.37; H, 9.15. Found: C, 83.37; H,
9.21.
1-Acetyl-4-(3-cyclopentylpropenyl)benzene (40a) (Table 4,
Entry 18)
Traces of branched isomer were also observed.
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and allyl-
cyclopentane (0.220 g, 2 mmol) afforded 40a in 76% selectivity and
in 87% (0.198 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.88 (d, J = 8.5 Hz, 2 H), 7.39 (d,
J = 8.5 Hz, 2 H), 6.43 (d, J = 15.8 Hz, 1 H), 6.34 (dt, J = 15.8, 7.1
Hz, 1 H), 2.58 (s, 3 H), 2.23 (m, 2 H), 1.95–1.10 (m, 9 H).
1H NMR (300 MHz, CDCl3): d = 5.26 (s, 1 H), 5.12 (s, 1 H).
1-Acetyl-4-(3-Cyclohexylpropenyl)benzene (44a) (Table 4,
Entry 26)
The reaction of 4-bromoacetophenone (0.199 g, 1 mmol) and allyl-
cyclohexane (0.248 g, 2 mmol) afforded 44a in 76% selectivity and
in 94% (0.228 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.86 (d, J = 8.5 Hz, 2 H), 7.38 (d,
J = 8.5 Hz, 2 H), 6.39 (d, J = 15.9 Hz, 1 H), 6.35 (m 1 H), 2.55 (s, 3
H), 2.20 (m, 2 H), 1.95–0.85 (m, 11 H).
13C NMR (75 MHz, CDCl3): d = 197.5, 142.7, 135.4, 133.9, 129.3,
128.7, 125.9, 39.8, 39.5, 32.2, 26.5, 25.1.
Anal. Calcd for C16H20O: C, 84.16; H, 8.83. Found: C, 84.40; H,
8.73.
13C NMR (75 MHz, CDCl3): d = 198.2, 143.2, 135.9, 133.7, 130.5,
129.3, 126.5, 41.7, 38.6, 33.8, 27.1, 26.9, 26.8.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.31 (s, 1 H), 5.14 (s, 1 H).
Anal. Calcd for C17H22O: C, 84.25; H, 9.15. Found: C, 84.04; H,
9.27.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.31 (s, 1 H), 5.14 (s, 1 H).
Synthesis 2007, No. 11, 1683–1696 © Thieme Stuttgart · New York

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Influence of Reaction Conditions on Heck Reaction with Simple Alkenes
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1-(3-Cyclohexylpropenyl)-4-nitrobenzene (45a) (Table 4,
Entry 28)
The reaction of 4-bromonitrobenzene (0.202 g, 1 mmol) and allyl-
cyclohexane (0.248 g, 2 mmol) afforded 45a in 76% selectivity and
in 92% (0.225g) yield.
(6) For couplings of alk-1-enyl stannanes with aryl bromides via
Stille reaction, see: (a) Falcou, A.; Marsacq, D.;
Hourquebie, P.; Duchêne, A. Tetrahedron 2000, 56, 225.
(b) Wang, X.; Parlow, J. J.; Porco, J. A. Jr. Org. Lett. 2000,
2, 3509.
(7) For couplings of alk-1-enyl zinc with aryl halides via
Negishi reaction, see: Betzemeier, B.; Knochel, P. Angew.
Chem., Int. Ed. Engl. 1997, 36, 2623.
(8) (a) Mabic, S.; Vaysse, L.; Benezra, C.; Lepoittevin, J.-P.
Synthesis 1999, 1127. (b) Kline, T.; Bowman, J.; Iglewski,
B. H.; de Kievit, T.; Kakai, Y.; Passador, L. Bioorg. Med.
Chem. Lett. 1999, 9, 3447. (c) Cho, S. Y.; Ahn, J. H.; Ha, J.
D.; Kang, S. K.; Baek, J. Y.; Han, S. S.; Shin, E. Y.; Kim, S.
S.; Kim, K. R.; Cheong, H. G.; Choi, J.-K. Bull. Korean
Chem. Soc. 2003, 24, 1455.
(9) For examples of Heck reaction using aryl halides and alk-1-
enes: (a) Mabic, S.; Lepoittevin, J.-P. Tetrahedron Lett.
1995, 36, 1705. (b) Bräse, S.; Rümper, J.; Voigt, K.; Albecq,
S.; Thurau, G.; Villard, R.; Waegell, B.; de Meijere, A. Eur.
J. Org. Chem. 1998, 671. (c) Littke, A.; Fu, G. J. Am. Chem.
Soc. 2001, 123, 6989. (d) Albéniz, A. C.; Espinet, P.;
Martin-Ruiz, B.; Milstein, D. J. Am. Chem. Soc. 2001, 123,
11504. (e) Grasa, G. A.; Singh, R.; Stevens, E. D.; Nolan, S.
P. J. Organomet. Chem. 2003, 687, 269. (f) Xu, L.; Mo, J.;
Baillie, C.; Xiao, J. J. Organomet. Chem. 2003, 687, 301.
(g) Smith, G. S.; Mapolie, S. F. J. Mol. Catal. A: Chem.
2004, 213, 187. (h) Yi, C.; Hua, R. Tetrahedron Lett. 2006,
47, 2573.
1H NMR (300 MHz, CDCl3): d = 8.13 (d, J = 8.5 Hz, 2 H), 7.43 (d,
J = 8.5 Hz, 2 H), 6.48 (d, J = 15.8 Hz, 1 H), 6.38 (dt, J = 15.8, 7.1
Hz, 1 H), 2.20 (m, 2 H), 1.95–0.85 (m, 11 H).
13C NMR (75 MHz, CDCl3): d = 144.8, 135.7, 129.4, 126.7, 125.4,
124.4, 41.2, 37.9, 33.2, 26.4, 26.3.
Anal. Calcd for C15H19NO2: C, 73.44; H, 7.81. Found: C, 73.28; H,
7.89.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.39 (s, 1 H), 5.18 (s, 1 H).
1-(3-Cyclohexylpropenyl)-3-methylbenzene (46a) (Table 4,
Entry 30)
The reaction of 3-bromotoluene (0.171 g, 1 mmol) and allylcyclo-
hexane (0.248 g, 2 mmol) afforded 46a in 77% selectivity and in
91% (0.195 g) yield.
1H NMR (300 MHz, CDCl3): d = 7.20–6.94 (m, 4 H), 6.33 (d,
J = 15.8 Hz, 1 H), 6.20 (dt, J = 15.8, 7.1 Hz, 1 H), 2.32 (s, 3 H), 2.20
(m, 2 H), 1.85–0.85 (m, 11 H).
13C NMR (75 MHz, CDCl3): d = 137.3, 137.2, 130.0, 128.9, 127.7,
126.9, 125.9, 122.4, 40.4, 37.6, 32.5, 25.9, 25.7.
(10) Laurenti, D.; Feuerstein, M.; Pèpe, G.; Doucet, H.; Santelli,
M. J. Org. Chem. 2001, 66, 1633.
Anal. Calcd for C16H22: C, 89.65; H, 10.35. Found: C, 89.90; H,
10.41.
(11) Doucet, H.; Santelli, M. Synlett 2006, 2001.
(12) (a) Feuerstein, M.; Laurenti, D.; Bougeant, C.; Doucet, H.;
Santelli, M. Chem. Commun. 2001, 325. (b) Kondolff, I.;
Doucet, H.; Santelli, M. Organometallics 2006, 25, 5219.
(13) Feuerstein, M.; Berthiol, F.; Doucet, H.; Santelli, M. Org.
Biomol. Chem. 2003, 1, 2235.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.23 (s, 1 H), 4.98 (s, 1 H).
3-(3-Cyclohexylpropenyl)pyridine (47a) (Table 4, Entry 32)
The reaction of 3-bromopyridine (0.158 g, 1 mmol) and allylcyclo-
hexane (0.248 g, 2 mmol) afforded 47a in 77% selectivity and in
94% (0.189 g) yield.
(14) Kondolff, I.; Doucet, H.; Santelli, M. Organometallics 2007,
26, 472.
1H NMR (300 MHz, CDCl3): d = 8.53 (s, 1 H), 8.39 (d, J = 4.7 Hz,
1 H), 7.65 (d, J = 7.5 Hz, 1 H), 7.20 (dd, J = 7.5, 4.7 Hz, 1 H), 6.32
(d, J = 15.8 Hz, 1 H), 6.27 (dt, J = 15.8, 7.1 Hz, 1 H), 2.08 (m, 2 H),
1.85–0.85 (m, 11 H).
13C NMR (75 MHz, CDCl3): d = 147.7, 147.6, 133.5, 132.5, 132.4,
127.1, 123.3, 41.1, 38.0, 33.1, 26.4, 26.3.
(15) Feuerstein, M.; Doucet, H.; Santelli, M. J. Org. Chem. 2001,
66, 5923.
(16) (a) Feuerstein, M.; Doucet, H.; Santelli, M. Synlett 2001,
1980. (b) Feuerstein, M.; Doucet, H.; Santelli, M.
Tetrahedron Lett. 2002, 43, 2191. (c) Lemhadri, M.;
Doucet, H.; Santelli, M. Tetrahedron 2004, 50, 11533.
(d) Berthiol, F.; Doucet, H.; Santelli, M. Tetrahedron Lett.
2004, 45, 5633. (e) Berthiol, F.; Doucet, H.; Santelli, M.
Synthesis 2005, 3589. (f) Battace, A.; Zair, T.; Doucet, H.;
Santelli, M. J. Organomet. Chem. 2005, 690, 3790.
(g) Kondolff, I.; Doucet, H.; Santelli, M. Eur. J. Org. Chem.
2006, 765. (h) Berthiol, F.; Doucet, H.; Santelli, M. Appl.
Organomet. Chem. 2006, 20, 855. (i) Battace, A.; Zair, T.;
Doucet, H.; Santelli, M. Synthesis 2006, 3495.
(17) Berthiol, F.; Doucet, H.; Santelli, M. Tetrahedron Lett.
2003, 44, 1221.
(18) Mo, J.; Xu, L.; Ruan, J.; Liu, S.; Xiao, J. Chem. Commun.
2006, 3591.
(19) Miyaura, N.; Ishiyama, T.; Sasaki, H.; Ishikawa, M.; Sato,
M.; Suzuki, A. J. Am. Chem.Soc. 1989, 111, 314.
(20) Hatanaka, Y.; Fukushima, S.; Hiyama, T. Heterocycles
1990, 30, 303.
Anal. Calcd for C14H19N: C, 83.53; H, 9.51. Found: C, 83.40; H,
9.47.
Traces of branched isomer were also observed.
1H NMR (300 MHz, CDCl3): d = 5.28 (s, 1 H), 5.08 (s, 1 H).
References
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Synthesis 2007, No. 11, 1683–1696 © Thieme Stuttgart · New York