Suzuki cross-coupling reactions between alkenylboronic acids and aryl bromides catalysed by a tetraphosphane-palladium catalyst

Article abstract of DOI:10.1002/ejoc.200300627

A range of alkenylboronic acids undergo Suzuki cross-coupling with aryl bromides in good yields in the presence of [PdCl(C₃H ₅)]₂/cis,cis,cis-1,2,3,4-tetrakis[(diphenylphosphanyl) methyl]cyclopentane as a catalyst. A wide variety of 1-arylprop-1-enes, 2-arylprop-1-enes, 2-arylbut-1-enes and 1,1-diarylethylene or styrene derivatives have been prepared. Moreover, the reaction tolerates several functions, such as acetyl, formyl, nitrile or nitro. Furthermore, this catalyst can be used at low loading, even for reactions of sterically hindered substrates. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.

Full text of DOI:10.1002/ejoc.200300627

FULL PAPER
Suzuki Cross-Coupling Reactions between Alkenylboronic Acids and Aryl
Bromides Catalysed by a Tetraphosphane-Palladium Catalyst
[a]
[a]
[a]
[a]
´
Eugenie Peyroux, Florian Berthiol, Henri Doucet,* and Maurice Santelli*
Keywords: Alkenes / Aryl halides / Catalysis / Cross-coupling / Palladium / Phosphanes
A range of alkenylboronic acids undergo Suzuki cross-coup-
pared. Moreover, the reaction tolerates several functions,
ling with aryl bromides in good yields in the presence of such as acetyl, formyl, nitrile or nitro. Furthermore, this cata-
[PdCl(C3H5)]2/cis,cis,cis-1,2,3,4-tetrakis[(diphenylphos-
phanyl)methyl]cyclopentane as a catalyst. A wide variety of
1-arylprop-1-enes, 2-arylprop-1-enes, 2-arylbut-1-enes and
lyst can be used at low loading, even for reactions of
sterically hindered substrates.
( Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
1,1-diarylethylene or styrene derivatives have been pre- Germany, 2004)
Introduction
cis,cis,cis-1,2,3,4-tetrakis[(diphenylphosphanyl)methyl]-
cyclopentane, or Tedicyp (Scheme 1),[35] in which the four
(diphenylphosphanyl)alkyl groups are stereospecifically
bound to the same face of the cyclopentane ring. We have
already reported the results obtained with Tedicyp as ligand
in allylic substitution,[35] in Heck reactions,[36] in Suzuki
cross-coupling[37Ϫ42] and in Sonogashira[43] reactions. As an
example, a TON of 98 000 000 had been obtained for the
coupling of 4-bromoacetophenone with benzeneboronic
acid. We have also recently reported the cross-coupling of
arylboronic acids with a range of vinyl bromides.[44] Here,
in order to establish further the requirements for a success-
ful Suzuki cross-coupling reaction, we wish to report on the
reactions between alkenylboronic acids and a variety of aryl
bromides in the presence of Tedicyp as the ligand.
The Suzuki cross-coupling reactions are among the most
widely used palladium-catalysed methodologies in organic
synthesis.[1Ϫ5] In recent years, the efficiencies of several
thermally stable palladium catalysts in reactions between
aryl halides and arylboronic acids have been studied in
detail.[6Ϫ13] On the other hand, these reactions in the pres-
ence of alkenylboronic acids have attracted less
attention,[14Ϫ33] although a few ligands have successfully
been employed. The most popular of is triphenylphos-
phane, but the catalyst formed by association of this ligand
with palladium complexes is not very efficient in terms of
substrate/catalyst ratio.[15Ϫ29] Recently, more efficient pal-
ladium catalysts have also been successfully employed for
Suzuki cross-coupling reactions with these alkenylboron
derivatives.[30Ϫ33] Molander et al., for example, have re-
ported that the PdCl2(dppf) complex is an efficient catalyst
for reactions between aryl bromides and alkenyltrifluoro-
borates.[31,32] Two palladium-supported catalyst have also
been used successfully.[30,33] To the best of our knowledge,
however, the efficiency of tetraphosphane ligands for the
cross-coupling of alkenylboronic acids has not been re-
ported.
Scheme 1
From previous results,[44] xylene was chosen as the sol-
vent and potassium carbonate as the base for this study.
The reactions were generally performed at 130 °C under
argon in the presence of a 1:2 [Pd(C3H5)Cl]2/Tedicyp ratio
as catalyst.
We first tried to prepare styrene derivatives by the Suzuki
reactions. Styrene derivatives have recently been prepared
by Suzuki cross-coupling between arylboronic acids and vi-
nyl bromide.[45] Here we describe the synthesis of these
compounds by cross-coupling between vinylboronic acid
and several aryl bromides (Scheme 2, Table 1). We have ob-
served that it is indeed possible to cross-couple vinylboronic
acid and aryl bromides efficiently, under conditions similar
to those employed for the corresponding arylboronic acids.
This reaction can be performed with as little as 0.01% cata-
Results and Discussion
In order to find stable and efficient palladium catalysts,
we have prepared the tetrapodal[34] phosphane ligand
[a]
`
´
´
Laboratoire de Synthese Organique associe au CNRS, Faculte
´ ˆ
des Sciences de Saint Jerome,
Avenue Escadrille Normandie-Niemen, 13397 Marseille Cedex
20, France
Fax: (internat.) ϩ33-4-91983865
E-mail: henri.doucet@univ.u-3mrs.fr
m.santelli@univ.u-3mrs.fr
Eur. J. Org. Chem. 2004, 1075Ϫ1082
DOI: 10.1002/ejoc.200300627
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1075

E. Peyroux, F. Berthiol, H. Doucet, M. Santelli
FULL PAPER
lyst. The [Pd(C3H5)Cl]2/Tedicyp catalyst system is also tol- gated the scope of the coupling reaction with substituted
erant of electronic variation in the aryl halide component. vinylboronic acids. We first studied the reactivity of isopro-
Vinylboronic acid reacts cleanly at 130 °C both with elec- penylboronic acid (Scheme 3, Table 2). The results, pre-
tron-poor and with electron-rich aryl bromides. A wide sented in Table 2, also reveal a strong aryl bromide substitu-
range of functions on the aryl bromide Ϫ such as methoxy, ent effect on the reaction rate. Electron-withdrawing groups
fluoro, trifluoromethyl, dimethylamino, nitro, nitrile, formyl in the aryl bromides support the Suzuki reaction, while elec-
or acetyl Ϫ was tolerated. A strong influence of these sub- tron-donating groups are unfavourable. For example, turn-
stituents on the reaction rate was observed. In the presence over numbers of 3 100Ϫ8 600 can be achieved with this
of para-substituted, electron-poor aryl bromides such as 4- catalyst for activated substrates such as 4-bromoaceto-
bromoacetophenone or 4-bromobenzaldehyde, TONs of 1 phenone, 4-bromobenzophenone, 4-bromobenzaldehyde
000Ϫ2 400 were obtained (Entries 3Ϫ8, Table 1). In the and 4-bromobenzonitrile (Entries 3Ϫ10, Table 2). With de-
presence of electron-rich aryl bromides, on the other hand, activated 4-dimethylaminobromobenzene, on the other
lower TONs of 89 and 250 were observed (Entries 1 and hand, we obtained a TON of 340 (Entries 11 and 12,
2, Table 1). Lower TONs were also observed with ortho- Table 2). We next studied the influence of ortho-substituents
substituted aryl bromides such as 2-bromobenzaldehyde or on the aryl bromide, and the results observed were better
2-bromobenzonitrile (Entries 11Ϫ15, Table 1).
than those seen in the couplings with vinylboronic acid
(Table 1). 2-Bromoacetophenone and 2-bromobenzonitrile
gave TONs similar to those for para-substituted aryl bro-
mides (Entries 15, 16 and 20, Table 2), and satisfactory
TONs were obtained even in the presence of highly con-
gested substrates such as 9-bromoanthracene or 1-bromo-
2,4,6-triisopropylbenzene (187 and 105; Entries 22Ϫ26,
Table 2). In summary, isopropenylboronic acid proved to be
a very efficient reagent for the introduction of an isoprop-
enyl group into aryl derivatives.
Scheme 2
We next tried to evaluate the differences in reaction rate
between mono- and di-ortho-substituted aryl bromides, and
we observed that even very hindered aryl bromides could
be coupled efficiently with vinylboronic acid. With 1-
bromo-2,4,6-trimethylbenzene and 1-bromo-2,4,6-triisopro-
pylbenzene, for example, high levels of conversion were ob-
tained in the presence of 0.4 and 5% catalyst, respectively
(Entries 16 and 17, Table 1). Moreover, the catalyst was also
active for the heteroaryl bromide 3-bromoquinoline (En-
tries 18 and 19, Table 1).
Scheme 3
Having demonstrated that vinylboronic acid can be an
With but-1-en-2-ylboronic acid the coupling products
efficient alkenylating agent for aryl bromides, we investi- were also obtained selectively and in good yields (Scheme 4,
Table 1. Suzuki reactions with H2CϭCHB(OH)2 (see also Scheme 2)
Entry[a]
ArBr
Substrate/catalyst ratio
Product
Yield, %
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
4-tBu-PhBr
4-NMe2-PhBr
4-MeCO-C6H4Br
4-MeCO-C6H4Br
4-HCO-C6H4Br
4-HCO-C6H4Br
4-CN-C6H4B
4-CN-C6H4Br
6-Methoxy-2-bromonaphthalene
6-Methoxy-2-bromonaphthalene
2-MeCO-C6H4Br
2-MeCO-C6H4Br
2-HCO-C6H4Br
2-CN-C6H4Br
2-CN-C6H4Br
2,4,6-Me3ϪC6H2Br
2,4,6-iPr3ϪC6H2Br
3-Bromoquinoline
3-Bromoquinoline
250
100
1000
10000
250
1000
250
1000
250
1000
250
1000
100
250
1000
250
1
2
87, 100[b][c]
89
3
85
3
24[b]
4
100[b]
78, 100[b]
100[b]
84, 100[b]
80, 100[b]
64[b]
4
5
5
6
6
7
100[b]
84, 100[b]
85
7
8
9
87
9
35[b]
10
11
12
12
88, 100[b]
22
20
250
1000
92
87[b]
[a]
[b]
Conditions: catalyst see ref.[35], aryl bromide (1 equiv.), H2CϭCHB(OH)2 (3 equiv.), K2CO3 (2 equiv.), xylenes, 130 °C, 20 h. Yield
[c]
determined by GC and NMR. Reaction time: 3 h.
1076
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Eur. J. Org. Chem. 2004, 1075Ϫ1082

Suzuki Cross-Coupling Reactions between Alkenylboronic Acids and Aryl Bromides
FULL PAPER
Table 2. Suzuki reactions with CH3(CϭCH2)B(OH)2 (Scheme 3)
Entry[a]
ArBr
Substrate/catalyst ratio
Product
Yield, %
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
4-tBu-PhBr
4-tBu-PhBr
250
1000
1000
10000
1000
10000
1000
10000
1000
10000
100
13
13
14
14
15
15
16
16
17
17
18
18
19
20
21
22
22
23
24
24
25
26
27
28
29
29
30
92, 100[b]
54[b]
4-MeCO-C6H4Br
4-MeCO-C6H4Br
4-PhCO-C6H4Br
4-PhCO-C6H4Br
4-HCO-C6H4Br
4-HCO-C6H4Br
4-CN-C6H4Br
96
31[b]
96
66[b]
83
86[b]
84, 100[b]
36[b]
4-CN-C6H4Br
4-Me2N-C6H4Br
4-Me2N-C6H4Br
6-Methoxy-2-bromonaphthalene
2-Ph-C6H4Br
2-MeO-C6H4Br
2-MeCO-C6H4Br
2-MeCO-C6H4Br
2-HCO-C6H4Br
2-NO2-C6H4Br
86, 100[b]
1000
10000
250
34[b]
95
87, 100[b]
78, 100[b]
79, 100[b]
55[b]
100
1000
10000
1000
250
1000
1000
1000
250
100
20
250
100
56
89
2-NO2-C6H4Br
2-CN-C6H4Br
84[b]
88
95
75
1-Bromonaphthalene
9-Bromoanthracene
2,4,6-Me3-C6H2Br
2,4,6-iPr3-C6H2Br
2,4,6-iPr3-C6H2Br
3-Bromoquinoline
86
89, 100[b]
42[b]
83
[a]
Conditions: catalyst see ref.[35], aryl bromide (1 equiv.), CH3(CϭCH2)B(OH)2 (2 equiv.), K2CO3 (2 equiv.), xylenes, 130 °C, 20 h.
GC and NMR yield.
[b]
Table 3). The reaction rates were very similar to those ob-
served in the presence of isopropenylboronic acid. The
highest TONs were obtained in the presence of ortho- and
para-substituted, electron-poor aryl bromides such as
bromoacetophenone, bromobenzaldehyde or bromo-
benzonitrile (Entries 5Ϫ10 and 12Ϫ17, Table 3). Bromo-
benzene was also efficiently coupled, although lower TONs
were observed (Entries 3 and 4, Table 3). No isomerisation
of the double bond was generally detected.
Table 3. Suzuki reactions with CH3CH2(CϭCH2)B(OH)2 (see
also Scheme 4)
Entry[a] ArBr
Substrate/catalyst ratio Product Yield, %
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
PhI
PhI
PhBr
PhBr
100
1000
100
31
31
31
31
32
32
33
33
34
34
35
36
36
37
37
38
38
78, 100[b]
33[b]
91[c]
250
86[b]
4-MeCO-C6H4Br 1000
4-MeCO-C6H4Br 10000
4-HCO-C6H4Br 1000
4-HCO-C6H4Br 10000
4-CN-C6H4Br
4-CN-C6H4Br
2-Me-C6H4Br
2-MeCO-C6H4Br 1000
2-MeCO-C6H4Br 10000
2-HCO-C6H4Br 1000
2-HCO-C6H4Br 10000
2-CN-C6H4Br
2-CN-C6H4Br
93
98[b] [d]
90
34[b]
1000
10000
250
94
65[b]
93
86, 100[b]
84[b]
89, 100[b]
75[b]
Scheme 4
1000
10000
84, 100[b]
80[b]
We also studied the synthesis of 1,1-biarylethylene deriva-
tives by Suzuki cross-coupling. We have already reported
the synthesis of these compounds through Suzuki cross-
coupling between α-bromostyrene and arylboronic acids.[44]
Here we report the synthesis of these compounds by cross-
coupling between 1-phenylvinylboronic acid and aryl bro-
[a]
Conditions: catalyst see ref.[35]
, aryl bromide (1 equiv.),
CH3CH2(CϭCH2)B(OH)2 (2 equiv.), K2CO3 (2 equiv.), xylenes,
[b]
[c]
[d]
130 °C, 20 h.
Yield determined by GC and NMR. 80 °C.
The formation of 7% of 2-arylbut-2-ene was observed.
mides. The Suzuki reaction between this vinylboronic acid lene derivatives (Scheme 5, Table 4). We observed that this
and functionalized aryl bromides should be a powerful pro- reaction can be performed with as little as 0.01% catalyst
cedure for the preparation of functionalized 1,1-biarylethy- and tolerates a wide range of functions Ϫ such as methoxy,
Eur. J. Org. Chem. 2004, 1075Ϫ1082
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E. Peyroux, F. Berthiol, H. Doucet, M. Santelli
FULL PAPER
fluoro, acetyl, formyl, nitrile or benzoyl Ϫ on the aryl bro- we also prepared them by the Suzuki reaction (Scheme 6,
mide. Higher reaction rates were observed in the presence Table 5). Quite similar reaction rates were observed for both
of para-substituted aryl bromides (Entries 1Ϫ7, Table 4) Heck and Suzuki reactions, and the reaction performed in
than with ortho-substituted aryl bromides (Entries 8Ϫ10, the presence of (E)-prop-1-en-1-ylboronic acid also gave
Table 4). No evidence of stilbene derivatives from a compet- mixtures of regio- and stereoisomers. This substrate seems
ing Heck reaction was observed in any case.
to react both through a Heck reaction and subsequent de-
boronation (isomer geminal G) and through a Suzuki reac-
tion [isomers (Z) and (E)].[47] In the presence of 4-bromo-
benzophenone, 4-bromobenzaldehyde and 4-bromobenzon-
itrile, mixtures of the three isomers were obtained and the
best selectivity in favour of (E)-1-arylprop-1-enes was 83%
(Entries 1Ϫ6, Table 5). A reaction performed at a lower
temperature gave higher selectivity in favour of the (E) iso-
mer (Entry 7, Table 5). In the presence of ortho-substituted
aryl bromides the selectivity in favour of the linear isomers
was also higher, up to 95% of the (E) isomer being obtained
(Entries 8 and 9, Table 5). These results indicate that the
Heck reaction seems to be the most economical procedure
for the preparation of these vinylarenes. However, the Su-
zuki cross-coupling procedure reported here is very simple
and overcomes the inconvenience of using gas under press-
ure.
Scheme 5
Table 4. Suzuki reactions with Ph(CϭCH2)B(OH)2 (see also
Scheme 5)
Entry[a] ArBr
Substrate/catalyst ratio Product Yield, %
1
4-MeO-C6H4Br 11000
39
40
40
41
42
43
44
45
46
46
88, 100[b]
91
12
13
14
15
16
17
18
19
10
4-F-C6H4Br
4-F-C6H4Br
11250
11000
100[b]
80
4-MeCO-C6H4Br 15000
4-HCO-C6H4Br 11000
80, 100[b]
78
4-CN-C6H4Br
15000
4-PhCO-C6H4Br 10000
2-MeCO-C6H4Br 11000
83, 99[b]
51
2-CN-C6H4Br
2-CN-C6H4Br
11250
11000
81, 100[b]
100[b]
[a]
Conditions: catalyst see ref.[35], aryl bromide (1 equiv.), Ph(Cϭ
Scheme 6
[b]
CH2)B(OH)2 (2 equiv.), K2CO3 (2 equiv.), xylenes, 130 °C, 20 h.
GC and NMR yield.
Conclusion
We lastly studied the synthesis of (E)-1-arylprop-1-enes
by cross-coupling between (E)-prop-1-en-1-ylboronic acid
In summary, we have established that the Tedicyp/pal-
and aryl bromides. We have already reported the prep- ladium system is not limited to Suzuki reactions of aryl-
aration of similar compounds with [Pd(C3H5)Cl]2/Tedicyp boronic acids; alkenylboronic acids are also efficiently cou-
as catalyst in Heck reactions between aryl bromides and pled. In the presence of this catalyst, Suzuki cross-couplings
alk-1-enes. In all cases, we had obtained mixtures of regio- of vinylboronic acid, isopropenylboronic acid, but-1-en-2-
and stereoisomers and the best selectivity in favour of (E)- ylboronic acid, 1-phenylvinylboronic acid or (E)-prop-1-en-
1-arylalk-1-enes was 70%.[46] Here, to determine the most 1-ylboronic acid can be performed with as little as 0.01%
efficient procedure for the preparation of such compounds, catalyst. In view of the high price of palladium, the practi-
Table 5. Suzuki reactions with (E)-MeCHϭCHB(OH)2 (Scheme 6)
Entry[a]
ArBr
Substrate/catalyst ratio
Product
Ratio G/Z/E
Yield
1
2
3
4
5
6
7
8
9
4-MeCO-C6H4Br
4-MeCO-C6H4Br
4-HCO-C6H4Br
4-HCO-C6H4Br
4-CN-C6H4Br
4-CN-C6H4Br
4-CN-C6H4Br
250
1000
250
1000
250
1000
250
250
47
47
48
48
49
49
49
50
51
6:11:83
6:12:82
17:11:72
18:18:64
17:6:77
15:8:77
7:12:81
0:5:95
90
63[b]
89, 100[b]
80[b]
100[b]
74
100[b] [c]
79
74
2-MeCO-C6H4Br
2-CN-C6H4Br
250
2:5:93
[a]
Conditions: catalyst see ref.[35], aryl bromide (1 equiv.), (E)-MeCHϭCHB(OH)2 (2 equiv.), K2CO3 (2 equiv.), xylenes, 130 °C, 20 h.
[b]
[c]
Yield determined by GC and NMR. 70 °C.
1078
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Suzuki Cross-Coupling Reactions between Alkenylboronic Acids and Aryl Bromides
FULL PAPER
6.75 (dd, J ϭ 17.6, 11.7 Hz, 1 H, ϭCH), 7.46 (d, J ϭ 8.3 Hz, 2 H,
Ar), 7.90 (d, J ϭ 8.3 Hz, 2 H, Ar) ppm.
cal advantage of such low catalyst loading reactions may
become increasingly important for industrial processes. This
efficiency probably comes from the presence of the four (di-
phenylphosphanyl)alkyl groups stereospecifically bound to
the same face of the cyclopentane ring, which probably in-
creases the coordination of the ligand to the metal and pre-
vent precipitation of the catalyst. The cross-coupling of alk-
enylboronic acids with aryl bromides is generally slower
than the cross-coupling of alkenyl bromides with aryl-
boronic acids,[44] but the functional group tolerance is re-
markable, substituents such as fluoro, methyl, methoxy, ace-
tyl, formyl, benzoyl, nitro and nitrile on the aryl bromide
having been used successfully. As would be expected, both
the steric hindrance and the electronic properties of the aryl
bromide have an effect on the reaction rates, but even the
o,o-disubstituted aryl bromide partners provide the desired
products.
4-Vinylbenzaldehyde (4): 1H NMR: δ ϭ 5.42 (d, J ϭ 11.9 Hz, 1
H, ϭCHH), 5.90 (d, J ϭ 17.6 Hz, 1 H, ϭCHH), 6.76 (dd, J ϭ
17.6, 11.9 Hz, 1 H, ϭCH), 7.53 (d, J ϭ 8.3 Hz, 2 H, Ar), 7.83 (d,
J ϭ 8.3 Hz, 2 H, Ar), 9.97 (s, 1 H, CHO) ppm.
4-Vinylbenzonitrile (5): 1H NMR: δ ϭ 5.43 (d, J ϭ 11.9 Hz, 1 H, ϭ
CHH), 5.86 (d, J ϭ 17.6 Hz, 1 H, ϭCHH), 6.72 (dd, J ϭ 17.6,
11.9 Hz, 1 H, ϭCH), 7.47 (d, J ϭ 8.5 Hz, 2 H, Ar), 7.60 (d, J ϭ
8.5 Hz, 2 H, Ar) ppm.
6-Methoxy-2-vinylnaphthalene (6): 1H NMR: δ ϭ 3.92 (s, 3 H,
OMe), 5.29 (d, J ϭ 11.0 Hz, 1 H, ϭCHH), 5.83 (d, J ϭ 17.5 Hz,
1 H, ϭCHH), 6.86 (dd, J ϭ 17.5, 11.0 Hz, 1 H, ϭCH), 7.10Ϫ7.20
(m, 2 H, Ar), 7.58Ϫ7.72 (m, 4 H, Ar) ppm.
1
2-Vinylacetophenone (7): H NMR: δ ϭ 2.57 (s, 3 H, Me), 5.33 (d,
J ϭ 10.9 Hz, 1 H, ϭCHH), 5.63 (d, J ϭ 17.6 Hz, 1 H, ϭCHH),
7.19 (dd, J ϭ 17.6, 10.9 Hz, 1 H, ϭCH), 7.32 (t, J ϭ 7.5 Hz, 1 H,
Ar), 7.44 (t, J ϭ 7.5 Hz, 1 H, Ar),), 7.55 (d, J ϭ 7.5 Hz, 1 H, Ar).
7.62 (d, J ϭ 7.5 Hz, 1 H, Ar) ppm.
Experimental Section
2-Vinylbenzaldehyde (8): 1H NMR: δ ϭ 5.51 (d, J ϭ 10.9 Hz, 1
H, ϭCHH), 5.69 (d, J ϭ 17.4 Hz, 1 H, ϭCHH), 7.39Ϫ7.59 (m, 4
H, ϭCH and Ar), 7.82 (d, J ϭ 7.6 Hz, 1 H, Ar), 10.29 (s, 1 H,
CHO) ppm.
General Remarks: All reactions were run under argon in Schlenk
tubes with the use of vacuum lines. Analytical grade xylene was
not distilled before use. Some of the aryl halides were distilled be-
fore use. Potassium carbonate (99ϩ) was used without drying. Alk-
enylboronic acid were prepared by a reported procedure,[48] by ad-
dition of 2 equiv. of B(OMe)3 to alkenylmagnesium bromide solu-
tions in THF at Ϫ90 °C, the solution then being warmed to room
temperature, poured onto ice, extracted with diethyl ether and dried
(MgSO4), and the solvents being evaporated. Vinylboronic acid is
not very stable and was prepared just before use. Isopropenyl-
boronic acid, but-1-en-2-ylboronic acid, 1-phenylvinylboronic acid
and (E)-prop-1-en-1-ylboronic acid were stored at Ϫ20 °C. The re-
actions were followed by GC and NMR for high boiling point sub-
strates and by GC for low boiling point substrates. GC/MS were
recorded with a Varian Saturn 2100T spectrometer. 1H and 13C
NMR spectrum were recorded with a Bruker 300 MHz spec-
trometer in CDCl3 solutions. Chemical shifts are reported in ppm
relative to CDCl3 (7.25). Flash chromatography was performed on
silica gel (230Ϫ400 mesh) GC and NMR yields in the tables are
conversions of the aryl halides into the products calculated from
2-Vinylbenzonitrile (9): 1H NMR: δ ϭ 5.53 (d, J ϭ 10.9 Hz, 1 H, ϭ
CHH), 5.94 (d, J ϭ 17.6 Hz, 1 H, ϭCHH), 7.07 (dd, J ϭ 17.6,
10.9 Hz, 1 H, ϭCH), 7.33 (t, J ϭ 7.5 Hz, 1 H, Ar), 7.54 (t, J ϭ
7.5 Hz, 1 H, Ar),), 7.62 (d, J ϭ 7.5 Hz, 1 H, Ar). 7.66 (d, J ϭ
7.5 Hz, 1 H, Ar) ppm.
1
2,4,6-Trimethylstyrene (10): H NMR: δ ϭ 2.26 (s, 9 H, Me), 5.22
(dd, J ϭ 18.0, 2.0 Hz, 1 H, ϭCHH), 5.49 (dd, J ϭ 11.3, 2.0 Hz, 1
H, ϭCHH), 6.66 (dd, J ϭ 18.0, 11.3 Hz,1 H, ϭCH), 6.85 (s, 2 H,
Ar) ppm.
1
2,4,6-Triisopropylstyrene (11): H NMR: δ ϭ 1.18 (d, J ϭ 6.8 Hz,
6 H, Me), 1.25 (d, J ϭ 6.8 Hz, 12 H, Me), 2.85 (sept., J ϭ 6.8 Hz,
1 H, CH), 3.24 (sept., J ϭ 6.8 Hz, 2 H, CH), 5.17 (dd, J ϭ 17.8,
2.3 Hz, 1 H, ϭCHH), 5.50 (dd, J ϭ 11.3, 2.3 Hz, 1 H, ϭCHH),
6.76 (dd, J ϭ 17.8, 11.3 Hz, 1 H, ϭCH), 6.99 (s, 2 H, Ar) ppm.
1
GC and H NMR spectra of the crude mixtures.
1
3-Vinylquinoline (12): H NMR: δ ϭ 5.44 (d, J ϭ 11.1 Hz, 1 H, ϭ
General Procedure for the Coupling of Alkenylboronic Acids with
Aryl Bromides: Treatment of the aryl bromide (10 mmol), K2CO3
(2.76 g, 20 mmol) and the alkenylboronic acid (20 or 30 mmol, see
Tables 1Ϫ5) at the appropriate temperature (see Tables 1Ϫ5) under
argon in xylene (10 mL) in the presence of the Tedicyp/palladium
complex for 20 h afforded the corresponding coupling product after
addition of water, extraction with dichloromethane or diethyl ether,
separation, drying (MgSO4), evaporation and filtration through sil-
ica gel.
CHH), 5.96 (d, J ϭ 17.8 Hz, 1 H, ϭCHH), 6.85 (dd, J ϭ 17.8,
11.1 Hz, 1 H, ϭCH), 7.51 (t, J ϭ 7.2 Hz, 1 H, Ar), 7.66 (t, J ϭ
7.2 Hz, 1 H, Ar), 7.78 (d, J ϭ 8.1 Hz, 1 H, Ar), 8.02Ϫ8.10 (m, 2
H, Ar), 9.01 (d, J ϭ 1.9 Hz, 1 H, Ar) ppm.
2-(4-tert-Butylphenyl)propene (13): 1H NMR: δ ϭ 1.30 (s, 9 H, tBu),
2.14 (s, 3 H, Me), 5.03 (s, 1 H, ϭCHH), 5.35 (s, 1 H, ϭCHH), 7.35
(d, J ϭ 8.7 Hz, 2 H, Ar), 7.42 (d, J ϭ 8.7 Hz, 2 H, Ar) ppm.
2-(4-Acetylphenyl)propene (14): 1H NMR: δ ϭ 2.07 (s, 3 H, Me),
2.56 (s, 3 H, COMe), 5.17 (s, 1 H, ϭCHH), 5.47 (s, 1 H, ϭCHH),
7.49 (d, J ϭ 7.5 Hz, 2 H, Ar), 7.91 (d, J ϭ 7.5 Hz, 2 H, Ar) ppm.
1
4-tert-Butylstyrene (1): H NMR: δ ϭ 1.31 (s, 9 H, Me), 5.18 (d,
J ϭ 10.9 Hz, 1 H, ϭCHH), 5.70 (d, J ϭ 17.6 Hz, 1 H, ϭCHH),
6.69 (dd, J ϭ 17.6, 10.9 Hz, 1 H, ϭCH), 7.34 (m, 4 H, Ar) ppm.
1
N,N-dimethyl-4-vinylaniline (2): 1H NMR: δ ϭ 2.95 (s, 6 H, Me),
5.01 (d, J ϭ 10.8 Hz, 1 H, ϭCHH), 5.53 (d, J ϭ 17.5 Hz, 1 H, ϭ
CHH), 6.60 (dd, J ϭ 17.5, 10.8 Hz, 1 H, ϭCH), 6.69 (d, J ϭ
9.0 Hz, 2 H, Ar), 7.30 (d, J ϭ 9.0 Hz, 2 H, Ar) ppm.
2-(4-Benzoylphenyl)propene (15): H NMR: δ ϭ 2.07 (s, 3 H, Me),
5.07 (s, 1 H, ϭCHH), 5.43 (s, 1 H, ϭCHH), 7.30Ϫ7.50 (m, 5 H,
Ar), 7.30Ϫ7.50 (m, 4 H, Ar) ppm.
1
2-(4-Formylphenyl)propene (16): H NMR: δ ϭ 2.11 (s, 3 H, Me),
1
4-Vinylacetophenone (3): H NMR: δ ϭ 2.58 (s, 3 H, Me), 5.39 (d,
5.20 (s, 1 H, ϭCHH), 5.48 (s, 1 H, ϭCHH), 7.54 (d, J ϭ 8.5 Hz,
J ϭ 11.7 Hz, 1 H, ϭCHH), 5.86 (d, J ϭ 17.6 Hz, 1 H, ϭCHH), 2 H, Ar), 7.86 (d, J ϭ 8.5 Hz, 2 H, Ar), 9.96 (s, 1 H, CHO) ppm.
Eur. J. Org. Chem. 2004, 1075Ϫ1082
www.eurjoc.org  2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1079

E. Peyroux, F. Berthiol, H. Doucet, M. Santelli
FULL PAPER
2-(4-Cyanophenyl)propene (17): 1H NMR: δ ϭ 2.08 (s, 3 H, Me),
2-Phenylbut-1-ene (31): 1H NMR: δ ϭ 1.08 (t, J ϭ 7.4 Hz, 3 H,
5.20 (s, 1 H, ϭCHH), 5.46 (s, 1 H, ϭCHH), 7.50 (d, J ϭ 8.7 Hz, Me), 2.48 (q, J ϭ 7.4 Hz, 2 H, CH2), 5.05 (s, 1 H, ϭCHH), 5.26
2 H, Ar), 7.59 (d, J ϭ 8.7 Hz, 2 H, Ar) ppm.
(s, 1 H, ϭCHH), 7.20Ϫ7.45 (m, 5 H, Ph) ppm.
2-(4-Dimethylaminophenyl)propene (18): 1H NMR: δ ϭ 2.14 (s, 3
H, Me), 2.97 (s, 6 H, Me), 4.93 (s, 1 H, ϭCHH), 5.28 (s, 1 H, ϭ
CHH), 6.71 (d, J ϭ 9.0 Hz, 2 H, Ar), 7.41 (d, J ϭ 9.0 Hz, 2 H,
Ar) ppm.
2-(4-Acetylphenyl)but-1-ene (32): 1H NMR: δ ϭ 1.10 (t, J ϭ 7.4 Hz,
3 H, Me), 2.58 (s, 3 H, Me), 2.49 (q, J ϭ 7.4 Hz, 2 H, CH2), 5.14
(s, 1 H, ϭCHH), 5.37 (s, 1 H, ϭCHH), 7.46 (d, J ϭ 8.2 Hz, 2 H,
Ar), 7.91 (d, J ϭ 8.2 Hz, 2 H, Ar) ppm.
2-(6-Methoxy-2-naphthyl)propene (19): 1H NMR: δ ϭ 2.24 (s, 3 H,
Me), 3.92 (s, 3 H, OMe), 5.12 (s, 1 H, ϭCHH), 5.49 (s, 1 H, ϭ
CHH), 7.15 (m, 2 H, Ar), 7.65Ϫ7.80 (m, 3 H, Ar), 7.82 (s, 1 H,
Ar) ppm.
2-(4-Formylphenyl)but-1-ene (33): 1H NMR: δ ϭ 1.05 (t, J ϭ
7.4 Hz, 3 H, Me), 2.49 (q, J ϭ 7.4 Hz, 2 H, CH2), 5.18 (s, 1 H, ϭ
CHH), 5.37 (s, 1 H, ϭCHH), 7.54 (d, J ϭ 7.5 Hz, 2 H, Ar), 7.82
(d, J ϭ 7.5 Hz, 2 H, Ar), 9.95 (s, 1 H, CHO) ppm. C11H12O (160.2):
calcd. C 82.46, H 7.55; found C 82.25, H 7.27. MS (EI, 70 eV): m/
z (%) ϭ 160 (100) [Mϩ].
1
2-(2-Phenylphenyl)propene (20): H NMR: δ ϭ 2.00 (s, 3 H, Me),
5.34 (s, 1 H, ϭCHH), 5.42 (s, 1 H, ϭCHH), 7.50Ϫ7.80 (m, 9 H,
Ar) ppm.
2-(4-Cyanophenyl)but-1-ene (34): 1H NMR: δ ϭ 1.10 (t, J ϭ 7.4 Hz,
3 H, Me), 2.47 (q, J ϭ 7.4 Hz, 2 H, CH2), 5.19 (s, 1 H, ϭCHH),
5.35 (s, 1 H, ϭCHH), 7.47 (d, J ϭ 8.3 Hz, 2 H, Ar), 7.60 (d, J ϭ
8.3 Hz, 2 H, Ar) ppm. C11H11N (157.2): calcd. C 84.04, H 7.05;
found C 83.87, H 7.00. MS (EI, 70 eV): m/z (%) ϭ 157 (81) [Mϩ].
2-(2-Methoxyphenyl)propene (21): 1H NMR: δ ϭ 2.11 (s, 3 H, Me),
3.83 (s, 3 H, OMe), 5.04 (s, 1 H, ϭCHH), 5.16 (s, 1 H, ϭCHH),
6.85Ϫ7.35 (m, 4 H, Ar) ppm.
2-(2-Acetylphenyl)propene (22): 1H NMR: δ ϭ 2.10 (s, 3 H, Me),
2.48 (s, 3 H, Me), 4.87 (s, 1 H, ϭCHH), 5.19 (s, 1 H, ϭCHH), 7.26
(d, J ϭ 7.5 Hz, 1 H, Ar), 7.31 (td, J ϭ 7.5, 1.5 Hz, 1 H, Ar), 7.41
(td, J ϭ 7.5, 1.5 Hz, 1 H, Ar), 7.47 (dd, J ϭ 7.5, 1.5 Hz, 1 H, Ar)
ppm. C11H12O (160.2): calcd. C 82.46, H 7.55; found C 82.68, H
7.38. MS (EI, 70 eV): m/z (%) ϭ 160 (21) [Mϩ].
2-(2-Methylphenyl)but-1-ene (35): 1H NMR: δ ϭ 1H NMR: δ ϭ
1.02 (t, J ϭ 7.4 Hz, 3 H, Me), 2.31 (q, J ϭ 7.4 Hz, 2 H, CH2), 2.27
(s, 3 H, Me), 4.83 (s, 1 H, ϭCHH), 5.15 (s, 1 H, ϭCHH), 7.00Ϫ7.30
(m, 4 H, Ar) ppm.
1
2-(2-Formylphenyl)propene (23): H NMR: δ ϭ 2.15 (s, 3 H, Me),
2-(2-Acetylphenyl)but-1-ene (36): 1H NMR: δ ϭ 1.05 (t, J ϭ 7.4 Hz,
3 H, Me), 2.42 (q, J ϭ 7.4 Hz, 2 H, CH2), 2.48 (s, 3 H, Me), 4.91
(s, 1 H, ϭCHH), 5.18 (s, 1 H, ϭCHH), 7.22 (d, J ϭ 7.8 Hz, 1 H,
Ar), 7.30 (t, J ϭ 7.8 Hz, 1 H, Ar), 7.38 (t, J ϭ 7.8 Hz, 1 H, Ar),
7.48 (d, J ϭ 7.8 Hz, 1 H, Ar) ppm. C12H14O (174.2): calcd. C 82.72,
H 8.10; found C 82.48, H 7.91. MS (EI, 70 eV): m/z (%) ϭ 174
(45) [Mϩ].
4.87 (s, 1 H, ϭCHH), 5.43 (s, 1 H, ϭCHH), 7.32 (d, J ϭ 7.5 Hz,
1 H, Ar), 7.37 (t, J ϭ 7.5 Hz, 1 H, Ar), 7.52 (td, J ϭ 7.5, 1.3 Hz,
1 H, Ar), 7.88 (dd, J ϭ 7.5, 1.3 Hz, 1 H, Ar), 10.19 (s, 1 H,
CHO) ppm.
2-(2-Nitrophenyl)propene (24): 1H NMR: δ ϭ 2.07 (s, 3 H, Me),
4.92 (s, 1 H, ϭCHH), 5.15 (s, 1 H, ϭCHH), 7.31 (d, J ϭ 7.5 Hz,
1 H, Ar), 7.38 (t, J ϭ 7.5 Hz, 1 H, Ar), 7.53 (t, J ϭ 7.5 Hz, 1 H,
Ar), 7.83 (d, J ϭ 7.5 Hz, 1 H, Ar) ppm.
2-(2-Formylphenyl)but-1-ene (37): 1H NMR: δ ϭ 1.00 (t, J ϭ
7.4 Hz, 3 H, Me), 2.45 (q, J ϭ 7.4 Hz, 2 H, CH2), 4.91 (s, 1 H, ϭ
CHH), 5.37 (s, 1 H, ϭCHH), 7.27 (d, J ϭ 7.8 Hz, 1 H, Ar), 7.37
(t, J ϭ 7.8 Hz, 1 H, Ar), 7.52 (t, J ϭ 7.8 Hz, 1 H, Ar), 7.92 (d, J ϭ
7.8 Hz, 1 H, Ar), 10.15 (s, 1 H, CHO) ppm. C11H12O (160.2): calcd.
C 82.46, H 7.55; found C 82.29, H 7.24. MS (EI, 70 eV): m/z (%) ϭ
160 (13) [Mϩ].
2-(2-Cyanophenyl)propene (25): 1H NMR: δ ϭ 2.20 (s, 3 H, Me),
5.23 (s, 1 H, ϭCHH), 5.35 (s, 1 H, ϭCHH), 7.34 (m, 2 H, Ar),
7.51 (td, J ϭ 8.0, 1.3 Hz, 1 H, Ar), 7.63 (dd, J ϭ 8.0, 1.3 Hz, 1 H,
Ar) ppm.
1
2-(1-Naphthyl)propene (26): H NMR: δ ϭ 2.16 (s, 3 H, Me), 5.05
(s, 1 H, ϭCHH), 5.40 (s, 1 H, ϭCHH), 7.10Ϫ8.00 (m, 7 H, Ar)
ppm.
2-(2-Cyanophenyl)but-1-ene (38): 1H NMR: δ ϭ 1.05 (t, J ϭ 7.4 Hz,
3 H, Me), 2.49 (q, J ϭ 7.4 Hz, 2 H, CH2), 5.15 (s, 1 H, ϭCHH),
5.34 (s, 1 H, ϭCHH), 7.32 (d, J ϭ 7.5 Hz, 1 H, Ar), 7.34 (t, J ϭ
7.5 Hz, 1 H, Ar), 7.52 (t, J ϭ 7.5 Hz, 1 H, Ar), 7.64 (d, J ϭ 7.5 Hz,
1 H, Ar) ppm. C11H11N (157.2): calcd. C 84.04, H 7.05; found C
83.75, H 6.97. MS (EI, 70 eV): m/z (%) ϭ 157 (55) [Mϩ].
9-Isopropenylanthracene (27): 1H NMR: δ ϭ 2.27 (s, 3 H, Me), 5.16
(s, 1 H, ϭCHH), 5.77 (s, 1 H, ϭCHH), 7.47 (m, 4 H, Ar), 8.00 (m,
2 H, Ar), 8.17 (m, 2 H, Ar), 8.40 (m, 1 H, Ar) ppm.
1
2-(2,4,6-Trimethylphenyl)propene (28): H NMR: δ ϭ 1.93 (s, 3 H,
1
Me), 2.21 (s, 6 H, Me), 2.26 (s, 3 H, Me), 4.73 (s, 1 H, ϭCHH),
5.23 (s, 1 H, ϭCHH), 6.85 (s, 2 H, Ar) ppm.
1-(4-Methoxyphenyl)-1-phenylethylene (39): H NMR: δ ϭ 3.82 (s,
3 H, Me), 5.35 (d, J ϭ 1.3 Hz, 1 H, ϭCHH), 5.39 (d, J ϭ 1.3 Hz,
1 H, ϭCHH), 6.86 (d, J ϭ 9.0 Hz, 2 H, Ar), 7.27 (d, J ϭ 9.0 Hz,
2 H, Ar), 7.33 (m, 5 H, Ph) ppm.
2-(2,4,6-Triisopropylphenyl)propene (29): 1H NMR: δ ϭ 1.18 (d,
J ϭ 6.8 Hz, 6 H, Me), 1.28 (d, J ϭ 6.8 Hz, 12 H, Me), 1.95 (s, 3
H, Me), 2.85 (sept., J ϭ 6.8 Hz, 1 H, CH), 3.05 (sept., J ϭ 6.8 Hz,
2 H, CH), 4.76 (s, 1 H, ϭCHH), 5.24 (s, 1 H, ϭCHH), 6.96 (s, 2
H, Ar) ppm. C18H28 (244.4): calcd. C 88.45, H 11.55; found C
88.18, H 11.29. MS (EI, 70 eV): m/z (%) ϭ 244 (51) [Mϩ].
1-(4-Fluorophenyl)-1-phenylethylene (40): 1H NMR: δ ϭ 5.34 (d,
J ϭ 1.1 Hz, 1 H, ϭCHH), 5.36 (d, J ϭ 1.1 Hz, 1 H, ϭCHH), 6.93
(t, J ϭ 8.8 Hz, 2 H, Ar), 7.23 (dd, J ϭ 5.4, 8.8 Hz, 2 H, Ar), 7.26
(m, 5 H, Ph) ppm.
1
3-Isopropenylquinoline (30): H NMR: δ ϭ 2.20 (s, 3 H, Me), 5.25
1
(s, 1 H, ϭCHH), 5.54 (s, 1 H, ϭCHH), 7.51 (td, J ϭ 8.1, 1.2 Hz, 1-(4-Acetylphenyl)-1-phenylethylene (41): H NMR: δ ϭ 2.50 (s, 3
1 H, Ar), 7.63 (td, J ϭ 8.1, 1.2 Hz, 1 H, Ar), 7.77 (dd, J ϭ 8.1, H, COMe), 5.43 (s, 1 H, ϭCHH), 5.44 (s, 1 H, ϭCHH), 7.25 (m,
1.2 Hz, 1 H, Ar), 8.06 (m, 2 H, Ar), 9.09 (d, J ϭ 1.9 Hz, 1 H, 5 H, Ph), 7.32 (d, J ϭ 7.9 Hz, 2 H, Ar), 7.26 (d, J ϭ 7.9 Hz, 2 H,
Ar) ppm.
Ar) ppm.
1080
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1075Ϫ1082

Suzuki Cross-Coupling Reactions between Alkenylboronic Acids and Aryl Bromides
FULL PAPER
1
1-(4-Formylphenyl)-1-phenylethylene (42): H NMR: δ ϭ 5.53 (s, 1
H, ϭCHH), 5.54 (s, 1 H, ϭCHH), 7.27 (m, 5 H, Ph), 7.47 (d, J ϭ
[1]
´
J. Hassan, M. Sevignon, C. Gozzi, E. Schulz, M. Lemaire,
8.2 Hz, 2 H, Ar), 7.83 (d, J ϭ 8.2 Hz, 2 H, Ar), 10.00 (s, 1 H,
CHO) ppm.
Chem. Rev. 2002, 102, 1359Ϫ1470.
S. Kotha, K. Lahiri, D. Kashinath, Tetrahedron 2002, 58,
9633Ϫ9695.
[2]
1
1-(4-Cyanophenyl)-1-phenylethylene (43): H NMR: δ ϭ 5.51 (s, 1
[3]
[4]
A. Suzuki, J. Organomet. Chem. 2002, 653, 83Ϫ90.
A. Suzuki, Metal-catalysed cross-coupling reaction (Eds.: F. Di-
ederich, P. J. Stang), John Wiley & Sons, New York, 1998.
N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457Ϫ2483.
M. Beller, H. Fischer, W. A. Herrmann, K. Öfele, C. Brossmer,
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D. A. Albisson, R. B. Bedford, S. E. Lawrence, P. N. Scully,
Chem. Commun. 1998, 2095Ϫ2096.
H. Weissman, D. Milstein, Chem. Commun. 1999, 1901Ϫ1902.
J. P. Wolfe, S. L. Buchwald, Angew. Chem. Int. Ed. 1999, 38,
2413Ϫ2416.
R. B. Bedford, C. S. J. Cazin, Chem. Commun. 2001,
1540Ϫ1541.
H, ϭCHH), 5.56 (s, 1 H, ϭCHH), 7.27 (m, 2 H, Ph), 7.54 (m, 3
H, Ph), 7.42 (d, J ϭ 8.5 Hz, 2 H, Ar), 7.62 (d, J ϭ 8.5 Hz, 2 H,
Ar) ppm.
[5]
[6]
1-(4-Benzoylphenyl)-1-phenylethylene (44): 1H NMR: δ ϭ 5.61 (s, 2
H, ϭCHH), 7.34 (m, 5 H, Ar), 7.42 (d, J ϭ 8.2 Hz, 2 H, Ar), 7.46
(t, J ϭ 7.7 Hz, 2 H, Ar), 7.58 (t, J ϭ 7.5 Hz, 1 H, Ar), 7.77 (d, J ϭ
8.3 Hz, 2 H, Ar), 7.82 (d, J ϭ 7.5 Hz, 2 H, Ar) ppm. C21H16O
(284.3): calcd. C 88.70, H 5.67; found C 88.54, H 5.47. MS (EI,
70 eV): m/z (%) ϭ 284 (100) [Mϩ].
[7]
[8]
[9]
[10]
1
1-(2-Acetylphenyl)-1-phenylethylene (45): H NMR: δ ϭ 2.62 (s, 3
H, Me), 5.25 (d, J ϭ 1.3 Hz, 1 H, ϭCHH), 5.75 (d, J ϭ 1.3 Hz, 1
H, ϭCHH), 7.25Ϫ7.62 (m, 7 H, Ar), 8.02 (d, J ϭ 8.5 Hz, 2 H,
Ar) ppm.
[11]
[12]
[13]
A. Zapf, M. Beller, Chem. Eur. J. 2000, 6, 1830Ϫ1833.
R. B. Bedford, S. Welch, Chem. Commun. 2001, 129Ϫ130.
J. P. Wolfe, R. A. Singer, B. H. Yang, S. L. Buchwald, J. Am.
Chem. Soc. 1999, 121, 9550Ϫ9561.
1
1-(2-Cyanophenyl)-1-phenylethylene (46): H NMR: δ ϭ 5.46 (s, 1
[14]
[15]
[16]
[17]
[18]
H, ϭCHH), 5.84 (s, 1 H, ϭCHH), 7.22Ϫ7.34 (m, 6 H, Ar), 7.40
(t, J ϭ 7.5 Hz, 1 H, Ar), 7.54 (d, J ϭ 7.5 Hz, 1 H, Ar), 7.68 (d,
J ϭ 7.5 Hz, 1 H, Ar) ppm.
D. Badone, M. Baroni, R. Cardamone, A. Ielmini, U. Guzzi,
J. Org. Chem. 1997, 62, 7170Ϫ7173.
N. Miyaura, K. Maeda, H. Suginome, A. Suzuki, J. Org. Chem.
1982, 47, 2117Ϫ2120.
I. Rivera, J. A. Soderquist, Tetrahedron Lett. 1991, 32,
2311Ϫ2314.
1
(E)-1-(4-Acetylphenyl)prop-1-ene (47): H NMR: δ ϭ 1.90 (d, J ϭ
5.3 Hz, 3 H, Me), 2.59 (s, 3 H, COMe), 6.40 (m, 1 H, ϭCH), 6.43
(d, J ϭ 15.9 Hz, 1 H, ϭCH), 7.36 (d, J ϭ 8.0 Hz, 2 H, Ar), 7.86
(d, J ϭ 8.0 Hz, 2 H, Ar) ppm.
Y. Wada, J. Ichikawa, T. Katsume, T. Nohiro, T. Okauchi, T.
Minami, Bull. Chem. Soc. Jpn. 2001, 74, 971Ϫ977.
J. Ichikawa, Y. Wada, M. Fujiwara, K. Sakoda, Synthesis
2002, 1917Ϫ1936.
J. Ichikawa, K. Sakoda, Y. Wada, Chem. Lett. 2002, 282Ϫ283.
S. Satoh, N. Miyaura, A. Suzuki, Chem. Lett. 1986,
1329Ϫ1332.
N. Miyaura, M. Satoh, A. Suzuki, Tetrahedron Lett. 1986, 27,
3745Ϫ3748.
M. Satoh, N. Miyaura, A. Suzuki, Synthesis 1987, 373Ϫ377.
S. Hyuga, N. Yamashina, S. Hara, A. Suzuki, Chem. Lett.
1988, 809Ϫ812.
S. W. Wright, D. L. Hageman, L. D. McClure, J. Org. Chem.
1994, 59, 6095Ϫ6097.
A. Torrado, S. Lopez, R. Alvarez, A. R. de Lera, Synthesis
1995, 285Ϫ293.
H. Müller, C. Tschiercke, J. Chem. Soc., Chem. Commun.
1
(E)-1-(4-Formylphenyl)prop-1-ene (48): H NMR: δ ϭ 1.91 (d, J ϭ
5.1 Hz,, 3 H, Me), 6.43 (m, 1 H, ϭCH), 6.45 (d, J ϭ 15.3 Hz, 1
H, ϭCH), 7.45 (d, J ϭ 8.3 Hz, 2 H, Ar), 7.81 (d, J ϭ 8.3 Hz, 2 H,
Ar), 9.95 (s, 1 H, CHO) ppm.
[19]
[20]
[21]
1
(E)-1-(4-Cyanophenyl)prop-1-ene (49): H NMR: δ ϭ 1.90 (d, J ϭ
5.3 Hz, 3 H, Me), 6.39 (m, 2 H, CHϭCH), 7.36 (d, J ϭ 7.8 Hz, 2
H, Ar), 7.55 (d, J ϭ 7.8 Hz, 2 H, Ar) ppm.
[22]
[23]
1
(E)-1-(2-Acetylphenyl)prop-1-ene (50): H NMR: δ ϭ 1.88 (d, J ϭ
[24]
[25]
[26]
[27]
[28]
5.3 Hz, 3 H, Me), 2.54 (s, 3 H, OMe), 6.10 (dq, J ϭ 15.5, 5.3 Hz,
1 H, ϭCH), 6.85 (d, J ϭ 15.5 Hz, 1 H, ϭCH), 7.20Ϫ7.50 (m, 3 H,
Ar), 7.55 (d, J ϭ 7.7 Hz, 1 H, Ar) ppm.
(E)-1-(2-Cyanophenyl)prop-1-ene (51): 1H NMR: δ ϭ 1.97 (dd, J ϭ
6.6, 1.7 Hz, 3 H, Me), 6.44 (dq, J ϭ 15.7, 6.6 Hz, 1 H, ϭCH), 6.74
(dd, J ϭ 15.7, 1.7 Hz, 1 H, ϭCH), 7.20Ϫ7.70 (m, 4 H, Ar) ppm.
C10H9N (143.2): calcd. C 83.88, H 6.34; found C 83.60, H 6.15.
MS (EI, 70 eV): m/z (%) ϭ 143 (100) [Mϩ].
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Chemical Abstract Registry No.: 1, 1746Ϫ23Ϫ2; 2, 2039Ϫ80Ϫ7; 3,
10537Ϫ63Ϫ0; 4, 1791Ϫ26Ϫ0; 5, 3435Ϫ51Ϫ6; 6, 63444Ϫ51Ϫ9; 7,
52095Ϫ40Ϫ6; 8, 28272Ϫ96Ϫ0; 9, 34560Ϫ28Ϫ6; 10, 769Ϫ25Ϫ5; 11,
2039Ϫ92Ϫ1; 12, 67752Ϫ31Ϫ2; 13, 25163Ϫ88Ϫ6; 14, 5359Ϫ04Ϫ6;
15, 103384Ϫ71Ϫ0; 16, 10133Ϫ50Ϫ3; 17, 19956Ϫ03Ϫ7; 18,
25108Ϫ56Ϫ9; 19, 34352Ϫ92Ϫ6; 20, 22364Ϫ43Ϫ8; 21,
10278Ϫ02Ϫ1; 23, 23417Ϫ79Ϫ0; 24, 60249Ϫ97Ϫ0; 25,
23877Ϫ63Ϫ6; 26, 1855Ϫ47Ϫ6; 27, 58873Ϫ48Ϫ6; 28, 14679Ϫ13Ϫ1;
30, 104967Ϫ60Ϫ4; 31, 2039Ϫ93Ϫ2; 32, 42427Ϫ52Ϫ1; 35,
82902Ϫ62Ϫ3; 39, 4333Ϫ75Ϫ9; 40, 395Ϫ21Ϫ1; 41, 87324Ϫ13Ϫ8;
42, 389582Ϫ37Ϫ0; 43, 81329Ϫ28Ϫ4; 45, 50431Ϫ52Ϫ2; 46,
92757Ϫ92Ϫ1; 47, 109586Ϫ46Ϫ1; 48, 169030Ϫ21Ϫ1; 49,
74254Ϫ13Ϫ0; 50, 91388Ϫ33Ϫ9.
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`
Acknowledgments
We thank the CNRS and the ‘‘Conseil General des Bouches-du-
´ ´
ˆ
Rhone, Fr’’ for providing financial support.
Eur. J. Org. Chem. 2004, 1075Ϫ1082
www.eurjoc.org
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1081

E. Peyroux, F. Berthiol, H. Doucet, M. Santelli
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Received October 6, 2003
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1082
 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
Eur. J. Org. Chem. 2004, 1075Ϫ1082