Silica-supported bidentate arsine palladium(0) complex: A highly active and stereoselective catalyst for arylation of conjugated alkenes

Article abstract of DOI:10.1016/S0022-328X(03)00668-5

A silica-supported bidentate arsine palladium(0) complex has been prepared from 4-oxa-6,7-dichloroheptyltriethoxysilane via immobilization on fumed silica, followed by reacting with potassium diphenylarsenide and palladium chloride, and then the reduction with hydrazine hydrate. The complex has been characterized by X-ray photoelectron spectroscopy and it is a highly active and stereoselective catalyst for arylation of styrene and acrylic acid with aryl halides affording a variety of trans -stilbenes and substituted trans -cinnamic acids in high yields.

Full text of DOI:10.1016/S0022-328X(03)00668-5

Journal of Organometallic Chemistry 682 (2003) 20Á25
/
www.elsevier.com/locate/jorganchem
Silica-supported bidentate arsine palladium(0) complex: a highly
active and stereoselective catalyst for arylation of conjugated alkenes
a,
Mingzhong Cai *, Yizheng Huang , Hong Zhao , Caisheng Song
a
b
a
a
Department of Chemistry, Jiangxi Normal University, Nanchang 330027, China
b
Department of Chemistry, Shangrao Teachers’ College, Shangrao 334000, China
Received 28 May 2003; accepted 28 June 2003
Abstract
A silica-supported bidentate arsine palladium(0) complex has been prepared from 4-oxa-6,7-dichloroheptyltriethoxysilane via
immobilization on fumed silica, followed by reacting with potassium diphenylarsenide and palladium chloride, and then the
reduction with hydrazine hydrate. The complex has been characterized by X-ray photoelectron spectroscopy and it is a highly active
and stereoselective catalyst for arylation of styrene and acrylic acid with aryl halides affording a variety of trans-stilbenes and
substituted trans-cinnamic acids in high yields.
#
2003 Elsevier B.V. All rights reserved.
Keywords: Supported palladium catalyst; Bidentate arsine palladium(0) complex; Heck arylation; Stereoselective synthesis
1
. Introduction
supported palladium(0) catalyst and obtained 78%
stereoselectivity. Andersson et al. [6] have compared
polystyrene-supported phosphine palladium complex
with analogous homogeneous palladium complex, pal-
ladium salts, Pd/C in terms of catalyst activity and
selectivity and found that polymer-supported phosphine
palladium complex with P/Pd ratio of 1 is highly active,
but noticeable deactivation of catalyst during repeated
use was the main disadvantage. Zhang et al. [7]
described a polymer-supported phenanthroline palla-
dium(0)-catalyzed arylation of acrylamide, however
when tributylamine was used as the base, the activity
of the catalyst was remarkably lowered on recycling and
moreover the preparation of the catalyst is rather
complicated. Choudary et al. [8] also reported a clay
anchored phosphine palladium complex catalyzed ary-
lation of acrylates and cross coupling of phenylvinyl
acetate with aryl iodides, but no procedure to recover
the catalyst was detailed. Recently, we have found that
the silica-supported sulfur palladium(0) complex is an
efficient catalyst for Heck arylation of styrene and
acrylic acid with aryl iodides [9]. However, none of the
The palladium-catalyzed arylation of alkenes is an
important discovery in organopalladium chemistry
made by Heck et al. and has found wide application in
organic synthesis [1,2]. In this reaction, homogeneous
palladium complexes such as Pd(OAc) are usually used
2
as the catalysts and the amount of catalyst used is about
1
mol% of reactant. Although homogeneous palladium
catalysts have proven to be efficient, their activity and
stereoselectivity are moderate and use of homogeneous
palladium catalysts is still uneconomic for large scale
preparation. As Heck [3,4] has noted, practical applica-
tion of the reaction under such conditions is not feasible
due to its expensive cost. Easy recovery and reuse of the
catalytic species make the reaction very attractive
commercially.
Polymer-supported organotransition metal complexes
catalysts offer several significant advantages in synthetic
and industrial chemistry and are currently attracting
great interest. Terasawa et al. [5] have studied Heck
arylation of styrene with iodobenzene using polystyrene-
reported polymeric palladium catalysts [5Á9] shows
/
activity for the arylation of conjugated alkenes with
aryl bromides. Study of new types of polymer-bound
palladium catalysts which might be suitable for Heck
*
E-mail address: caimz618@sina.com (M. Cai).
Corresponding author. Fax: ꢀ86-791-851-7500.
/
0022-328X/03/$ - see front matter # 2003 Elsevier B.V. All rights reserved.
doi:10.1016/S0022-328X(03)00668-5

M. Cai et al. / Journal of Organometallic Chemistry 682 (2003) 20Á
/25
21
arylation of conjugated alkenes has theoretical and
practical significance. To our knowledge, little attention
has so far been given to organoarsenium transition
metal complexes [10,11] and no Heck arylation of
conjugated alkenes with aryl halides catalyzed by a
organoarsenium palladium complex has been reported.
In this paper, we wish to report the synthesis of silica-
supported bidentate arsine palladium(0) complex (ab-
Table 1
XPS data for ‘Si’Á
in eV)
/
2AsÁ
/
Pd(0), ‘Si’Á
/
2AsÁ
/
Pd(II), ‘Si’Á2As and PdCl
2
/
(
Sample
Pd3d5/2
As3d
Si2p
O
1s
Cl2p
‘
‘
‘
Si’Á
Si’Á
Si’Á
/
2AsÁ
/
Pd(0)
335.7
336.8
42.7
42.6
41.7
103.1
103.2
103.1
532.4
532.4
532.3
/
2AsÁ
/
Pd(II)
199.0
199.2
/
2As
PdCl
2
338.3
breviation: ‘Si’Á
in the arylation of conjugated alkenes with aryl halides.
/
2AsÁPd(0)) and its catalytic properties
/
The binding energies are referenced to C1s (284.6 eV), and the energy
differences were determined with an accuracy of 90.2 eV.
/
binding energies of Si2p and O1s of ‘Si’Á
similar to those of ‘Si’Á2As, and the binding energy of
Cl2p of ‘Si’Á2AsÁPd(II) is similar to that of PdCl2.
However the difference of As3d binding energies between
Si’Á2AsÁPd(II) and ‘Si’Á2As is 0.9 eV. The difference
of Pd3d5/2 binding energies between ‘Si’Á2AsÁPd(II) and
/
2AsÁ
/
Pd(II) are
2
. Results and discussion
/
/
/
It is well known that zero-valent palladium complexes
show unique reactivity in various organic reactions.
However, it is very difficult to use the Pd(0) complexes
as practical catalysts because of their instability to air
and moisture. A silica-supported bidentate arsine palla-
dium(0) complex, the first polymeric organoarsenium
palladium(0) complex, was conveniently prepared from
‘
/
/
/
/
/
PdCl is 1.5 eV. These results show that a coordination
2
bond between As and Pd is formed. The binding energy
(
335.7 eV) of Pd3d5/2 of ‘Si’Á
/
2AsÁ/Pd(0) is lower than the
binding energy (336.8 eV) of Pd3d5/2 of ‘Si’Á
/
2AsÁPd(II).
/
4
-oxa-6,7-dichloroheptyltriethoxysilane via immobiliza-
The Pd3d5/2 binding energy depends strongly on the
nature of the ligands. Consequently, it is impossible to
identify the reduced complex as a zero-valent one on the
basis of its Pd3d5/2 binding energy only. However, the
tion on fumed silica, followed by reacting with potas-
sium diphenylarsenide in THF and palladium chloride
in acetone, and then the reduction with hydrazine
hydrate in ethanol (Scheme 1).
The polymer-bound palladium(0) complexes catalysts
are very stable to air and moisture as a result of the
isolation of the reactive species by the polymer matrix.
As a result, the present catalyst can be stored for a long
period and is very convenient to use. The X-ray
photoelectron spectroscopy (XPS) has been used to
characterize this polymeric palladium catalyst. Table 1
binding energy of Cl2p in the ‘Si’Á
/
2AsÁPd(0) can not be
/
detected, the shift (lower) of Pd3d5/2 binding energy,
together with the black color suggest that the reduction
of the starting palladium(II) complex to the lower valent
state has taken place.
In order to test the catalytic activity of the novel
polymer-supported palladium(0) catalyst (‘Si’Á
/
2AsÁ
/
shows the XPS data for ‘Si’Á
/
2AsÁ
/
Pd(0), ‘Si’Á
/
2AsÁ
/
Pd(0)), the arylation reactions of styrene and acrylic
acid with aryl halides were studied (Scheme 2). The
Pd(II), ‘Si’Á2As and PdCl . It can be seen that the
/
2
Scheme 1.

22
M. Cai et al. / Journal of Organometallic Chemistry 682 (2003) 20Á
/25
Scheme 2.
reactions were carried out under conditions similar to
those used in the corresponding homogeneous reactions.
The results are summarized in Table 2.
presence of PPh3 in the arylation of styrene with
bromobenzene, only 1.5% trans-stilbene was found
[14]. Terasawa et al. [5] tried to react bromobenzene
with styrene using a polymer-bound tetrakis(triphenyl-
phosphine)palladium analogue as catalyst, only traces of
trans-stilbene was found in that study. In present study,
the substituent effects in the aryl iodides appeared to be
less significant than in the aryl bromides and the
reactivity of aryl bromides with electron-withdrawing
substituents was higher than that of aryl bromides with
electron-donating substituents. Probably because the
oxidative addition reaction of aryl bromides with this
polymeric palladium(0) complex is slow, the electron-
withdrawing substituents on benzene ring can facilitate
Synthesis of trans-stilbenes assumes importance be-
cause of their large molecular hyperpolarizable property
suited for the construction of non-linear optics [12] and
their uses as organic intermediates [13]. Synthesis of
trans-stilbenes usually involves a tedious multistep
synthetic procedure and the yields are poor to moderate.
An arylation of alkenes attempted by Heck using
palladium salts as catalyst afforded moderate yields on
longer reaction time [4]. Andersson et al. [6] indicated
that polymeric palladium catalysts tend to be more
efficient in the Heck reaction. As seen from Table 2, the
arylation reaction of styrene with aryl iodides proceeded
the oxidative addition of CÃ
Pd(0). This polymeric catalyst can be easily recovered
by simple filtration. When ‘Si’Á2AsÁPd(0) was used in
/
Br bond with ‘Si’Á
/
2AsÁ
/
smoothly at 100 8C using ‘Si’Á
/
2AsÁPd(0) as catalyst to
/
give the desired trans-stilbenes in high yields. The trans-
selectivity was always near quantitative and no cis-
product was observed. In the presence of a catalytic
/
/
four consecutive runs for the arylation reaction of
styrene with iodobenzene, trans-stilbene was formed in
91, 90, 88 and 89% yield, respectively. This result
suggests that the bidentate arsine ligand can efficiently
prevent palladium leaching from the polymer support.
b-Arylacrylic acids are important chemical substances
and organic intermediates and usually prepared by
amounts of ‘Si’Á
/
2AsÁPd(0) and triphenylphosphine, the
/
arylation reaction of styrene with aryl bromides could
also proceed smoothly at 140 8C to afford the desired
trans-products in moderate to good yields. When
palladium acetate was used as the catalyst in the
Table 2
trans-Stilbenes 3aÁ/g and cinnamic acids 3hÁ/n prepared
a
Yield (%)
Entry
ArX
Y
Temperature (8C)
Time (h)
Product
1
2
3
4
5
6
7
8
9
PhI
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
100
140
100
140
100
100
140
100
140
100
140
100
100
140
100
100
100
140
100
140
6
12
6
3a
3a
3b
3b
3c
3d
3d
3e
3e
3f
91
52
92
64
92
88
43
87
74
90
67
92
95
55
91
90
93
78
87
86
PhBr
4-ClC
4-ClC
6
6
H
H
4
I
Br
4
12
6
4-CH
4-CH
4-CH
3 6 4
OC H I
3
C
C
6
6
H
H
4
I
Br
6
3
4
12
6
4-O
4-O
3-O
2
2
2
NC
NC
NC
6
6
6
H
H
H
4
I
4
4
Br
I
12
6
10
11
12
13
14
15
16
17
18
19
20
4-CH
PhI
3
OCOC
6
H
4
Br
12
6
3g
3h
3i
CO
CO
CO
CO
CO
CO
CO
CO
CO
2
2
2
2
2
2
2
2
2
H
H
H
H
H
H
H
H
H
4-ClC
4-ClC
6
H
H
4
I
Br
6
6
4
12
6
3i
4-CH
4-CH
3
OC
6
H
4
I
3j
3
C
6
H
4
I
6
3k
3l
4-O
4-O
3-O
2
2
2
NC
NC
NC
6
6
6
H
4
H
4
H
4
I
6
Br
I
12
6
3l
3m
3n
4-CH OCOC
3
6
H
4
Br
12
3
Reactions were carried out with 5 mmol of aryl halide, 5.5 mmol of styrene or acrylic acid, 0.03 mmol of palladium catalyst, 6 mmol of Bu N in 0.5
ml of p-xylene. When aryl bromide was used as the arylating agent, 0.05 mmol of PPh
a
Yield of isolated product 3 based on the aryl halide.
3
was added.

M. Cai et al. / Journal of Organometallic Chemistry 682 (2003) 20Á
/25
23
Perkin reaction, however, the yields and stereoselectivity
are poor to moderate [15]. In the presence of ‘Si’Á2AsÁ
h and then refluxed for 24 h. The reaction mixture was
cooled to room temperature and treated with t-BuCl (2
ml) for 2 h. The mixture was filtered and washed with
/
/
Pd(0) and tributylamine, a variety of substituted trans-
cinnamic acids were prepared from acrylic acid and aryl
iodides in high yields and high stereoselectivity. When
aryl bromides with electron-withdrawing substituents
were used as the arylating agents in the present study,
the arylation reaction of acrylic acid in the presence of
95% ethanol (4ꢁ
acetone (3ꢁ40 ml) and then dried under vacuum to give
4.97 g of silica-supported bidentate arsine ligand (‘Si’Á
/
40 ml), distilled water (5ꢁ
/
40 ml),
/
/
ꢂ1
2As). The arsenium content was 1.52 mmol g
.
PPh also proceeded smoothly at 140 8C and the desired
3
3.2. Preparation of silica-supported bidentate arsine
palladium(0) complex (‘Si’Á2AsÁPd(0))
trans-products were obtained in moderate to good yields
on longer time. In all reactions only 0.6 mol% catalyst
based on the aryl halides was used. As for the arylation
reaction of styrene with iodobenzene, the mole turnover
numbers of 152 are much larger than those of 75 in the
corresponding homogeneous reaction reported by Heck
et al. [16]. Even after the catalyst had been exposed to
air for 7 days, its activity did not remarkably decrease,
this stability should result from polymer effects.
/
/
To a solution of PdCl (0.156 g) in acetone (40 ml)
2
was added ‘Si’Á
under nitrogen for 48 h. The brown solid product was
filtered, washed with distilled water (3ꢁ30 ml) and
acetone (3ꢁ20 ml), then stirred with hydrazine hydrate
1.5 g) and EtOH (20 ml) at 30 8C under nitrogen for 2
h. The resulting product was filtered, washed with EtOH
4ꢁ30 ml) and Et O (2ꢁ30 ml) and dried under
vacuum to give 1.94 g of the black polymeric palla-
dium(0) complex (‘Si’Á2AsÁPd(0)). The arsenium con-
tent was 1.39 mmol g and the palladium content was
/2As (2.01 g). The mixture was refluxed
/
/
(
(
/
/
2
3
. Experimental
/
/
ꢂ1
ꢂ1
Melting points were taken with a Yanaco micro
melting point apparatus and are uncorrected. IR spectra
0.42 mmol g
.
were obtained using a PerkinÁ
H-NMR spectra were recorded on a JEOL FX-90Q (90
MHz) or a Bruker AC-P300 (300 MHz) spectrometer
/
Elmer 683 instrument.
3.3. Typical procedure for arylation of styrene with aryl
halides
1
with TMS as an internal standard in CDCl or DMSO-
3
A mixture of styrene (0.57 g, 5.5 mmol), iodobenzene
1.02 g, 5 mmol), Bu N (1.11 g, 6 mmol), p-xylene (0.5
d6 as solvent. Microanalyses were obtained using a
(
3
PerkinÁ/Elmer 240 elemental analyzer.
ml) and the ‘Si’Á
/
2AsÁPd(0) complex (75 mg, 0.03 mmol
/
4
by a literature method [17]. p-Xylene, Bu N and styrene
-Oxa-6,7-dichloroheptyltriethoxysilane was prepared
of Pd) was stirred under N in an oil bath at 100 8C for 6
2
3
h. The mixture was cooled and dissolved in Et O (50
2
were distilled before use, other reagents were used as
received without further purification.
ml). The ‘Si’Á
the mixture by filtration, washed with distilled water
2ꢁ10 ml), EtOH (3ꢁ10 ml) and Et O (3ꢁ10 ml) and
reused in the next run. The ethereal solution was washed
with 5 N HCl (2ꢁ10 ml), brine (4ꢁ10 ml) and dried
MgSO ) and filtered. The solid product formed after
/
2AsÁ
/
Pd(0) complex was separated from
(
/
/
/
2
3
.1. Preparation of silica-supported bidentate arsine
ligand (‘Si’Á2As)
/
/
/
(
4
A mixture of fumed silica (10.0 g) and 4-oxa-6,7-
dichloroheptyltriethoxysilane (7.0 g) in toluene (160 ml)
was stirred at 120 8C for 24 h. Distilled water (30 ml)
was added and the mixture was refluxed for another 48
h. After being cooled to room temperature, the mixture
concentration of the ethereal solution was recrystallized
EtOH) to give (E)-1,2-diphenylethene (3a) (0.818 g,
(
91%).
3.3.1. (E)-1,2-Diphenylethene (3a)
was filtered, washed with distilled water (4ꢁ
dried at 200 8C in vacuo for 5 h. The resulting white
powder was washed with acetone (3ꢁ50 ml), followed
by drying under vacuum to give 10.8 g of silica-
supported poly-4-oxa-6,7-dichloroheptylsiloxane (‘Si’Á
/50 ml) and
M.p. 123Á124 8C, Ref. [18]. M.p. 124 8C. IR (KBr): n
/
ꢂ1
1
(
cm ) 3021, 1598, 1500, 760, 690. H-NMR: d 7.70Á
/
/
7.11 (m, 10H), 7.09 (s, 2H).
/
ꢂ1
3.3.2. (E)-1-(4-Chlorophenyl)-2-phenylethene (3b)
2
Cl). The chlorine content was 1.97 mmol g
A mixture of AsPh3 (3.62 g, 11.83 mmol) and
.
M.p. 128Á129 8C, Ref. [19]. M.p. 129 8C. IR (KBr): n
/
ꢂ1
1
cm ) 3058, 1592, 1496, 940, 815, 700. H-NMR: d
(
potassium (0.93 g, 23.66 mmol) in THF (60 ml) was
stirred under nitrogen at 60 8C for 16 h. After being
cooled to room temperature, the mixture was treated
with t-BuCl (1.10 g, 11.83 mmol) for 1 h to give a brown
7
.47Á7.26 (m, 9H), 7.09 (s, 2H).
/
3.3.3. (E)-1-(4-Methoxyphenyl)-2-phenylethene (3c)
M.p. 135Á136 8C, Ref. [20]. M.p. 136 8C. IR (KBr): n
(cm ) 3052, 1600, 1498, 1250, 1171, 820, 754. H-
solution. The resulting solution was added ‘Si’Á
/
2Cl (5.0
g) and the mixture was stirred at room temperature for 2
/
ꢂ1
1

24
M. Cai et al. / Journal of Organometallic Chemistry 682 (2003) 20Á25
/
1
NMR: d 7.58Á
/
7.20 (m, 7H), 7.02 (s, 2H), 6.87 (d, Jꢃ
/9.0
H-NMR: d 7.86Á
/
7.40 (m, 5H), 6.57 (d, Jꢃ 16.0 Hz,
/
Hz, 2H), 3.83 (s, 3H).
1H).
3
.3.4. (E)-1-(4-Methylphenyl)-2-phenylethene (3d)
M.p. 119Á120 8C, Ref. [21]. M.p. 120 8C. IR (KBr): n
cm ) 3028, 1597, 1492, 941, 825, 715. H-NMR: d
3
.4.3. (E)-3-(4-Methoxyphenyl)acrylic acid (3j)
M.p. 172Á173 8C, Ref. [25]. M.p. 174 8C. IR (KBr): n
cm ) 2920, 1681, 1632, 1600, 1499, 1250, 1170, 830.
/
ꢂ1
1
/
(
7
ꢂ1
(
.65Á7.03 (m, 9H), 7.02 (s, 2H), 2.32 (s, 3H).
/
1
H-NMR: d 7.66 (d, Jꢃ
/
16.0 Hz, 1H), 7.50 (d, Jꢃ
/9.0
Hz, 2H), 6.90 (d, Jꢃ9.0 Hz, 2H), 6.32 (d, Jꢃ
/
/
16.0 Hz,
3
.3.5. (E)-1-(4-Nitrophenyl)-2-phenylethene (3e)
M.p. 156Á157 8C, Ref. [21]. M.p. 157 8C. IR (KBr): n
cm ) 3046, 1591, 1526, 1500, 1340, 840, 760, 690. H-
1H), 3.86 (s, 3H).
/
ꢂ1
1
(
NMR: d 8.44Á8.12 (m, 2H), 7.80Á7.20 (m, 7H), 7.18 (s,
/
/
3
.4.4. (E)-3-(4-Methylphenyl)acrylic acid (3k)
2
H).
M.p. 200Á201 8C, Ref. [24]. M.p. 198Á199 8C. IR
/
/
ꢂ1
1
(
KBr): n (cm ) 2924, 1687, 1630, 1598, 1496, 835. H-
NMR: d 7.81Á7.40 (m, 3H), 7.24 (d, Jꢃ9.0 Hz, 2H),
.41 (d, Jꢃ 16.0 Hz, 1H), 2.33 (s, 3H).
3
.3.6. (E)-1-(3-Nitrophenyl)-2-phenylethene (3f)
/
/
ꢂ1
M.p. 105Á
571, 1520, 1495, 1350, 968, 808, 756, 695. H-NMR: d
.38 (s, 1H), 8.10 (d, Jꢃ8.2 Hz, 1H), 7.80 (d, Jꢃ8.0
7.26 (m, 6H), 7.22 (s, 1H), 7.16 (s, 1H).
Anal. Found: C, 74.41; H, 4.73; N, 6.01. C H NO
/
106 8C. IR (KBr): n (cm ) 3081, 3026,
6
/
1
1
8
/
/
Hz, 1H), 7.56Á
/
3.4.5. (E)-3-(4-Nitrophenyl)acrylic acid (3l)
M.p. 286Á287 8C, Ref. [24]. M.p. 288 8C. IR (KBr): n
(cm ) 2950, 1685, 1632, 1598, 1525, 1345, 845. H-
NMR: d 8.22 (d, Jꢃ9.0 Hz, 2H), 7.96 (d, Jꢃ9.0 Hz,
2H), 7.67 (d, Jꢃ 16.0 Hz, 1H), 6.75 (d, Jꢃ16.0 Hz,
1H).
1
4
11
2
/
ꢂ1
1
Calc.: C, 74.67; H, 4.89; N, 6.22%.
/
/
3
.3.7. (E)-1-(4-Methoxycarbonylphenyl)-2-
phenylethene (3g)
M.p. 157Á158 8C, Ref. [22]. M.p. 159Á
KBr): n (cmꢂ1) 3025, 1715, 1600, 1180, 835, 770, 699.
/
/
/
/
160 8C. IR
(
1
3
.4.6. (E)-3-(3-Nitrophenyl)acrylic acid (3m)
H-NMR: d 8.03 (d, Jꢃ
/
9.0 Hz, 2H), 7.63Á/7.20 (m,
M.p. 195Á
/
196 8C. IR (KBr): n (cmꢂ1) 2963, 1699,
635, 1577, 1524, 1359, 979, 715. H-NMR: d 8.41 (s,
7
H), 7.15 (s, 2H), 3.94 (s, 3H).
1
1
1
H), 8.27 (d, Jꢃ
16.0 Hz, 1H). Anal. Found: C, 55.69; H, 3.42; N,
.02. C H NO Calc.: C, 55.96; H, 3.63; N, 7.25%.
/
8.0 Hz, 1H), 7.89Á7.55 (m, 3H), 6.58
/
3.4. Typical procedure for arylation of acrylic acid with
aryl halides
(d, Jꢃ
/
7
9
7
4
A mixture of acrylic acid (0.40 g, 5.5 mmol),
iodobenzene (1.02 g, 5 mmol), Bu N (2.04 g, 11
3
3
(
.4.7. (E)-3-(4-Methoxycarbonylphenyl)acrylic acid
3n)
mmol), p-xylene (0.5 ml) and the ‘Si’Á
/
2AsÁPd(0)
/
complex (75 mg, 0.03 mmol of Pd) was stirred under
N in an oil bath at 100 8C for 6 h. After the reaction
M.p. 240Á
/
241 8C, Ref. [9]. M.p. 241Á
/
242 8C. IR
KBr): n (cm ) 2915, 1714, 1687, 1630, 1600, 1100,
2
ꢂ1
(
mixture was cooled, H O (20 ml) and NaHCO (1.10 g)
2
1
3
852, 770. H-NMR: d 8.04 (d, Jꢃ
/
9.0 Hz, 2H), 7.76Á
/
were added. After stirring for 10 min, the ‘Si’Á
/
2AsÁ
/
7.50 (m, 3H), 6.46 (d, Jꢃ16.0 Hz, 1H), 3.90 (s, 3H).
/
Pd(0) complex was separated from the mixture by
filtration. The aqueous phase was separated and acid-
ified with 5 N HCl (1.8 ml). After cooling to 0 8C, the
solid precipitate was filtered, washed with H O (5ꢁ
/
20
ml) and air dried to give (E)-3-phenylacrylic acid (3h)
0.682 g, 92%).
2
4
. Conclusions
(
We have described a new polymer-bound bidentate
arsine palladium(0) complex whose preparation is
simple and convenient. This complex has not only
high activity and stereoselectivity for arylation of
conjugated alkenes with aryl halides, but also offers
practical advantages such as easy handling, separation
from the product and reuse. The arylation of styrene
and acrylic acid with aryl iodides or bromides catalyzed
3
.4.1. (E)-3-Phenylacrylic acid (3h)
M.p. 130Á131 8C, Ref. [23]. M.p. 132Á
KBr): n (cm ) 2915, 1690, 1625, 1498, 1419, 760, 700.
/
/
133 8C. IR
ꢂ1
(
1
H-NMR: d 7.83 (d, Jꢃ
/
16.0 Hz, 1H), 7.69Á/7.21 (m,
5
H), 6.45 (d, Jꢃ
/
16.0 Hz, 1H).
3
.4.2. (E)-3-(4-Chlorophenyl)acrylic acid (3i)
M.p. 248Á249 8C, Ref. [24]. M.p. 249Á250 8C. IR
KBr): n (cm ) 2930, 1688, 1636, 1590, 1496, 954, 825.
by ‘Si’Á
/
2AsÁPd(0) provides a better and practical
/
/
/
procedure for the synthesis of unsymmetrical trans-
stilbenes and substituted trans-cinnamic acids.
ꢂ1
(

M. Cai et al. / Journal of Organometallic Chemistry 682 (2003) 20Á
/25
25
[
[
[
10] J. Tsuji, M. Hara, K. Ohno, Ger. Offen. 1, 942, 798; C.A., 73,
5497y (1970).
11] (a) Y.Y. Chen, X.R. Lu, Z.Y. Wang, Chin. J. Catal. 11 (1990) 75;
b) L. Ripa, A. Hallberg, J. Org. Chem. 62 (1997) 595.
Acknowledgements
1
This work was supported by the Natural Science
Foundation of Jiangxi Province in China.
(
12] A. Ulmann, C. Willand, W.K. Douglas, R. Rebello, D.J.
Williams, L. Handley, J. Am. Chem. Soc. 112 (1990) 7083.
13] B.J. Bridson, P. Nair, Tetrahedron 37 (1981) 173.
14] Z.Y. Zhang, H.W. Hu, T.Y. Kao, React. Polym. Ion Exch.
Sorbents 9 (1988) 249.
[
[
References
[
[
[
15] J.R. Johnson, Org. React. 1 (1942) 210.
16] R.F. Heck, J.P. Nolley, J. Org. Chem. 37 (1972) 2320.
17] X.R. Lu, Z.L. Zhong, Y.Y. Chen, Chem. J. Chin. Univ. 11 (1990)
[
1] (a) R.F. Heck, Org. React. 27 (1982) 345;
b) R.A. Abramovitch, D.H.R. Barton, J.P. Finet, Tetrahedron
4 (1988) 3039.
2] (a) G.T. Crisp, Chem. Soc. Rev. 27 (1998) 427;
b) I.P. Beletskaya, A.V. Cheprakov, Chem. Rev. 100 (2000) 3009.
(
4
561.
18] Z.Y. Zhang, H.W. Hu, T.Y. Kao, React. Polym. Ion Exch.
[
[
(
Sorbents 12 (1990) 229.
[
[
[
3] R.F. Heck, Pure Appl. Chem. 50 (1978) 691.
4] R.F. Heck, Acc. Chem. Res. 12 (1979) 146.
[
[
[
[
[
19] A. Sekiguchi, W. Ando, J. Org. Chem. 44 (1979) 413.
20] A.R. George, R.G.W. Spickett, J. Chem. Soc. (1949) 2724.
21] F. Bergmann, D. Schapira, J. Org. Chem. 12 (1947) 57.
22] H.A. Dieck, R.F. Heck, J. Am. Chem. Soc. 96 (1974) 1133.
23] B.A. Patel, C.B. Ziegler, N.A. Cortese, J.E. Plevyak, T.C.
Zebovitz, M. Terpko, R.F. Heck, J. Org. Chem. 42 (1977) 3903.
24] T.A. Wittstruck, E.N. Trachtenberg, J. Am. Chem. Soc. 89 (1967)
5] M. Terasawa, K. Kaneda, T. Imanaka, S. Teranishi, J. Organo-
met. Chem. 162 (1978) 403.
6] C.M. Andersson, K. Karabelas, A. Hallberg, J. Org. Chem. 50
[
(1985) 3891.
[
[
7] Z.Y. Zhang, Y. Pan, H.W. Hu, T.Y. Kao, Synthesis (1991) 539.
8] B.M. Choudary, R.M. Sarma, K.K. Rao, Tetrahedron 48 (1992)
[
[
3803.
25] J.F.J. Dippy, J.E. Page, J. Chem. Soc. (1938) 357.
719.
[
9] M.Z. Cai, C.S. Song, X. Huang, Synthesis (1997) 521.