Efficient polymer-supported Pd catalysts for the heck reaction

Article abstract of DOI:10.1002/cjoc.201090179

Some efficient polymer-supported palladium catalysts have been synthesized. Their catalytic effects were evaluated in the Heck reaction of iodobenzene with acrylates or styrene. High catalytic activities were achieved with turn over frequencies (TOF) up to 28000 and 6250, respectively. For the reaction of iodobenzene with styrene, high stereoselectivity was obtained. Additionally, the catalysts could be recovered by a simple filtration progress and can be reused for at least 5 times with a slow progressive decrease in activity.

Full text of DOI:10.1002/cjoc.201090179

FULL PAPER
Efficient Polymer-Supported Pd Catalysts for the Heck
Reaction
a,b
a
a
a
Liu, Yuxia (刘玉霞)
Jia, Jun (贾俊)
Tan, Haohan (谭浩瀚)
Sun, Yanan (孙亚楠)
,a
Tao, Jingchao* (陶京朝)
a
Department of Chemistry, Zhengzhou University, Zhengzhou, Henan 450052, China
b
Department of Material and Chemistry Engineering, Henan Institute of Engineering, Zhengzhou, Henan 450007,
China
Some efficient polymer-supported palladium catalysts have been synthesized. Their catalytic effects were
evaluated in the Heck reaction of iodobenzene with acrylates or styrene. High catalytic activities were achieved
with turn over frequencies (TOF) up to 28000 and 6250, respectively. For the reaction of iodobenzene with styrene,
high stereoselectivity was obtained. Additionally, the catalysts could be recovered by a simple filtration progress
and can be reused for at least 5 times with a slow progressive decrease in activity.
Keywords polymer-supported, palladium, Heck reaction
Introduction
to recovery catalysts. Equally useful catalysts can be
prepared by entrapping or immobilizing metal nanopar-
The Heck reaction between aryl halides and alkenes
is a significant example of carbon-carbon bond forming
reactions. The use of palladium metal catalysts in Heck
C— C coupling reactions has been overviewed. Usu-
ally aryl halides are reacted with alkenes in the presence
of palladium and a suitable base in a single step under
44
ticles, and generating and depositing active metal par-
45-53
ticles onto solid supports.
Whilst numerous exam-
ples of this approach have been reported, many of these
exhibit only limited lifetimes and levels of recyclability
due to the complex/ligand degradation and metal leach-
ing from the supported ligand. These problems are par-
ticularly prevalent for complexes based on phosphines
in which fast ligand exchange occurs. Therefore, herein
we reported the synthesis of some efficient polymer-
supported palladium catalysts and their catalytic activity
in Heck reaction.
1
-4
5
-8
mild conditions. Much effort has been made to de-
velop new catalysts to replace air- and moisture-sen-
sitive phosphine ligands, which also allow the use of
other aryl derivatives. These new catalysts include pal-
9
-12
ladacycles,
lysts,
N-heterocyclic carbene-palladium cata-
1
3,14
15
a macrocyclic recoverable triolefin complex
1
6,17
and thiourea-Pd(0) complexes.
Roviello and
reported a series of cyclopalladated
1
8-20
Experimental
co-workers
derivatives of Schiff bases as thermally stable and
soluble catalysts for the Heck reaction. Some published
results seem to suggest the possibility of the presence of
palladium nanoparticles in the Heck reaction with the
Materials and methods
All chemicals were used as purchased unless other-
wise noted. Solvents were dried and freshly distilled
prior to use. Heck reactions were performed under a dry
nitrogen atmosphere using Schlenk techniques. Ele-
mental analyses of the products were obtained from a
Carlo Erba 1106 elemental analyzer. IR spectra were
collected on a Bruker VECTOR22 spectrophotometer in
KBr pellets. The surface area was determined on a Carlo
Erba model surface analyzer. Gas chromatographic
analysis were carried out on an Agilent-5890, capillary
column length 15 m, with helium in combination with a
flame ionization detector. The products were identified
by comparison of their GC and GC-MS features with
those of authentic samples. Conversions and yields were
2
1,22
participation of palladacycles.
The use of heterogeneous catalysts for commonly
homogeneously catalyzed organic reactions may help to
resolve some industrially important problems, such as
the recovery of the catalyst from the reaction mixture
and its reuse in order to lower the product costs. There-
fore, attention has also been paid to the search for new,
efficient, and recyclable heterogeneous catalysts. In-
corporation/grafting of metal complexes into suitable
2
3-42
solids such as polymers
or porous siliceous materi-
4
3
als have been demonstrated to be promising methods
*
E-mail: jctao@zzu.edu.cn; Tel./Fax: 0086-0371-67767200
Received November 4, 2009; revised December 21, 2009; accepted January 7, 2010.
Project supported by the National Natural Science Foundation of China (No. 20372059) and the Doctoral Foundation of Henan Institute of Engi-
neering (No. D09002).
Chin. J. Chem. 2010, 28, 967— 973
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
967

Liu et al.
FULL PAPER
calculated by GC using n-dodecane as internal standard.
Chloromethylated P(S-DVB), 4% cross-linked, was ob-
tained from Shanghai Resin Company.
ide, styrene and base under nitrogen. The required
amount of the catalyst and additional solvent were
added. The reaction mixture was heated under stirring at
the desired temperature under argon until reaction com-
pletion as monitored by GC analyses. After cooling, 10
mL of diethyl ether was added to the reaction mixture
and the shrinked catalyst was recovered by filtration,
washed with water, acetone and diethyl ether, dried un-
der vacuum and reused in the next run. After separation
from the insoluble catalyst, the combined organic phase
was dried with Na SO . After removal of the solvent
Catalysts preparation
General method for the synthesis of polymer-
supported Schiff-bases La— Li and L'a— L'd The
formylation of poly(styrene-divinylbenzene) and the
acetylation of poly(styrene-divinylbenzene) were per-
5
4-56
formed as previously described in literature.
The
Schiff-bases were prepared by the reaction of the for-
mylated poly(styrene-divinylbenzene) and different
amines. A great excess of amines were used. The reac-
tion was performed under nitrogen in dry pyridine (30
mL) at 110 ℃ for up to 12 h. Then the reaction mixture
was filtrated. The products were isolated, washed with
methanol and dried in vacuo over night. The formations
of the Schiff-bases were confirmed by IR spectroscopy
and elemental analyses.
2
4
under reduced pressure, the product was isolated by thin
layer chromatography and analyzed by gas chromatog-
raphy (1,1-diphenylethylene t ＝8.6 min, trans-1,2-di-
r
phenylethylene t ＝7.0 min).
r
Results and discussion
Synthesis and characterization
Synthesis of the polymer-supported palladium
Synthesis of the polymer-supported Schiff-bases
Using commercially available Merrifield resin and
cross-linked (4%) polystyrene as starting materials, the
polymer supported Schiff-bases were readily prepared
via the following procedures (Schemes 1 and 2). The
formylation of poly(styrene-divinylbenzene) and the
acetylation of poly(styrene-divinylbenzene) were per-
－
1
catalysts A solution of 0.1 mol•L
2 4
Li PdCl in
methanol was previously prepared and the calculated
amounts of the polymer-supported Schiff-bases and 1
equiv. of anhydrous sodium acetate were added. The
suspension was maintained at room temperature for 12 h
under stirring. Then the reaction mixture was filtrated.
The products were isolated, washed with methanol and
dried in vacuo over night. The formations of the cyclo-
palladated imines were confirmed by IR spectroscopy
and elemental analyses.
5
4-56
formed as previously described in literature.
The
－
1
disappearance of absorption at 1265 cm for the C—Cl
bonds of the Merrifield resin and a strong absorption
－
1
band at 1698 cm for the carbonyl group indicate that
the chloromethylated polymer was successfully oxi-
dized to the corresponding formylated polymer. The
Determination of Pd-loading Aqua regia (2.0—
5
2
.0 mL) was added to the heterogeneous catalyst (50—
－
1
00 mg). The mixture was placed inside a high-pressure
strong absorption band at 1682 cm of the acetylated
polystyrene gives a signal of successful acetylation. An
excess of amines in the preparation of the Schiff-bases
were always used. It is important to choose a suitable
Teflon tube and leaching was carried out under micro-
wave conditions (50, 600 and 450 W pulses, respec-
tively, t＝30 min). After cooling to room temperature,
the mixture was filtered through a 0.2 mm Teflon fiter
and measured by ICP-OES (λ＝340.458 nm, ion line).
The background was measured at ∆λ＝±0.0278 nm.
Scheme 1 Synthesis of the polymer-supported catalysts 1a—1i
Heck reaction
Heck reaction between aryl halides and n-butyl
acrylates A Schlenk tube was charged with the ap-
propriate aryl halide, n-butyl acrylate and base under
nitrogen. The required amount of the catalyst and addi-
tional solvent were added. The reaction mixture was
heated under stirring at the desired temperature under
argon until reaction completion as monitored by GC
analyses. After cooling, 10 mL of diethyl ether was
added to the reaction mixture. The shrinked catalyst was
recovered by filtration, washed with water, acetone and
diethyl ether, dried under vacuum and reused in the next
run. After separation from the insoluble catalyst, the
organic solution was carefully withdrawn and analyzed
by gas chromatography (trans-3-phenyl-n-butyl acrylate
t
r
＝8.4 min).
Heck reaction of iodobenzene with styrene
A
Schlenk tube was charged with the appropriate aryl hal-
9
68
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 967— 973

Efficient Polymer-Supported Pd Catalysts for the Heck Reaction
Scheme 2 Synthesis of the polymer-supported catalysts 2a—2d
Table 1 Characterization of polymer-supported Schiff-bases
La—Li and L'a—L'd.
Elemental analysis/% IR (C＝N)
Lagind
R
－
1
C
N
H
ν
max/cm
La
81.94
0.65 7.20
1625
Lb
Lc
81.14
79.68
0.76 7.29
0.63 7.15
1618
1640
Ld
Le
81.64
79.50
0.84 7.34
1.46 7.23
1624
1639
solvent to well swelling the polymer for the imidization
of the polymeric carbonyl compounds. Pyridine was
adopted as the best one in which the imidization could
proceed smoothly. The formation of the Schiff-bases
was demonstrated by the presence of the absorption
Lf
79.74
0.76 7.17
1627
－
1
peak at about 1620—1640 cm in the IR spectra. Addi-
tionally, the formation of the Schiff-bases was also de-
termined by the elemental ananlysis data. Elemental
ananlysis: 0.63%—1.88% N, corresponding to ligand
loading 0.45—1.34 mmol/g. The resusts were listed in
Table 1.
Lg
Lh
Li
81.12
80.52
82.85
85.06
0.73 7.27
0.89 7.24
0.65 7.34
0.88 7.40
1637
1630
1629
1632
Synthesis of the supported palladium catalysts
Characterization of the polymer supported Pd catalysts
is listed in Table 2. A decrease in surface area was
found while immobilizing the ligand and the metal ions
on the polymer support. It was might due to blocking of
the pores after supporting the ligand and the metal ions.
5
7,58
L'a
Similar results were observed by Ram.
Surface areas
of the catalysts 2 are larger than that of the catalysts 1
with corresponding substituent on the imine N atom.
This is in good accordance with the fact that the cata-
lysts 2 have higher Pd loading than catalysts 1. All the
polymer supported catalysts were found to be thermo
stable up to 150 ℃ and not sensitive to oxygen and
moisture. It was might because the metal center was
stabilized by the five-member ring. The cyclopalladated
imine complex might be formed according to litera-
L'b
L'c
80.92
81.88
0.63 7.38
0.86 7.77
1626
1634
L'd
86.42
1.03 7.32
1632
showed good activities. Especially, 1b showed the
highest TON of 83300 and TOF of 28000 (Entry 2).
Additionally, Catalysts 1b and 2b, which were prepared
from hydroxylamine, had the highest catalytic activities
5
9
ture. It is also confirmed from the C＝N double bond
－
1
in IR spectrum (shift about 10 cm to lower wave
numbers) and the percentage of C, H and N in the ele-
mental analysis. The Pd loading of the supported cata-
lysts were determined by ICP-OES. The results showed
that the Pd loading of the supported catalysts was from
(
Entries 2 and 11). It indicated that the presence of the
hydroxyl group near the coordination center could in-
crease the catalytic activity. Although the TONs for
Heck reaction with the synthesized catalysts were not
high enough (the highest TON reported previously for
Heck reaction was 9600000 in the coupling of iodoben-
zene and n-butyl acylate under a higher temperature
0
.30 to 0.64 mmol/g.
Catalytic activity tests
6
0,61
(
140 ℃) using small molecule catalyst
), the lower
Heck reaction of aryl halides with n-butyl acry-
late First, the Heck reactions of iodobenzene with
n-butyl acrylate catalyzed by catalysts 1 or 2 were ex-
reaction temperature and the reusability of the polymer
supported catalysts were still more appreciable. The
catalyst 2 showed higher catalytic activities than the
catalyst 1 (Entries 10—13). It was perhaps due to the
effect of the methyl group in catalysts 2 which can en-
hance the swell of the catalyst in the used solvent and
therefore benefit their catalytic activities.
amined in a number of solvents, such as DMF, CH
3
CN,
1,4-dioxane, toluene, THF, etc. The results are listed in
Table 3. Of all solvent tested, DMF was found to be the
best one. In the catalyzed coupling reaction of iodonen-
zene with n-butyl acrylate, all the tested catalysts
Chin. J. Chem. 2010, 28, 967— 973
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
969

Liu et al.
FULL PAPER
a
Table 2 Characterization of the polymer supported Pd catalysts
Elemental analysis/%
IR (C＝N)
Pd loading
mmol/g
2
－
1
Ligand
Surface area/(m •g )
－
1
C
N
H
ν
max/cm
1620
1610
1632
1611
1633
1619
1632
1620
1621
1622
1619
1627
1627
1
a
46.5
48.3
47.1
46.8
47.5
78.2
48.1
48.6
47.9
52.3
58.6
58.0
53.1
73.88
68.14
70.31
71.57
73.77
71.74
69.94
71.02
74.41
75.78
74.57
75.54
74.80
0.49
0.45
0.49
0.61
1.03
0.62
0.68
0.61
0.64
1.05
0.88
0.93
0.83
6.74
6.18
6.32
6.46
6.71
6.53
6.39
6.43
6.74
6.62
6.38
6.45
6.37
0.35
0.30
0.35
0.42
0.36
0.38
0.45
0.39
0.43
0.64
0.58
0.60
0.52
1
b
1
c
1
d
1
e
1
f
1
g
1
h
1
i
2
a
2
b
2
c
2
d
a
2
－
1
Surface area of the support: 4% P(S-DVB)CH
2
Cl＝45.28 m •g .
a
Table 3 Heck reaction of aryl halides with n-butyl acrylate
－
4
b
c
d
Entry
X (R)
I (H)
Catalyst/(10 mmol•Pd)
t/h
4.5
3.0
4.5
5.0
6.0
5.0
7.5
4.0
7.5
4.5
2.5
3.0
4.5
48
T/℃
100
100
100
100
100
100
100
100
100
100
100
100
100
140
140
140
140
140
Yield /%
100
100
100
99
TON
TOF
1
2
3
4
5
6
7
8
9
1a (1.1)
45500
83300
62500
41200
71400
49500
41700
55000
58100
41700
45500
35700
45500
23530
25000
36000
25300
10100
28000
15600
8240
11900
9900
5500
13800
7750
9260
18200
11900
10100
490
I (H)
1b (0.6)
1c (0.8)
I (H)
I (H)
1d (1.2)
1e (0.7)
I (H)
100
99
I (H)
1f (1.0)
I (H)
1g (1.2)
100
99
I (H)
1h (0.9)
1i (0.8)
I (H)
93
10
11
12
13
14
15
16
17
18
I (H)
2a (1.2)
100
100
100
100
80
I (H)
2b (1.1)
2c (1.4)
I (H)
I (H)
2d (1.1)
1b (1.7)
1b (1.8)
1b (1.2)
1b (1.6)
1b (2.0)
Br (H)
Br (o-NO2)
48
90
521
Br (m-NO
2
)
48
86
750
Br (p-NO2)
Br (p-CH3)
48
81
527
48
52
13000
270
a
b
c
Reaction conditions: PhI (5 mmol), Et
3
N (6 mmol), n-butyl acrylate (6 mmol), DMF (5 mL). Determined by GC. TON: turn over
d
－
1
number (mol product per mol catalyst), not optimized. TOF: turn over frequency (mol product per mol catalyst h ).
In the case of the Heck reaction between n-butyl
acrylate and bromobenzene or substituted bromoben
zenes catalyzed by the most active catalyst 1b, only
higher catalyst loadings (Entries 14—18). It was shown
that bromobenzenes with electron-withdrawing group
(Entries 15—17) showed better activity than that of
electron-donating group derived bromobenzens (Entries
14 and 18).
5
2%—90% of yields were obtained with much lower
turnovers even at higher temperature (140 ℃) and with
9
70
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 967— 973

Efficient Polymer-Supported Pd Catalysts for the Heck Reaction
Heck reaction of iodobenzene with styrene cata-
lyzed by supported catalysts 1 Heck reaction be-
tween iodobenzene and styrene catatylzed by small
molecules cyclopalladated imines catalysts has also
compared to that of the reaction of idiobenzene and sty-
rene. The values of TOF were consistently lower than
the reaction of idiobenzene and n-butyl acrylates. The
ratio of the two diphenylethylene isomers determined by
GC was in the range of 9/1 — 15/1 (stilbene/
1,1-diphenylethylene).
6
2,63
been reported.
So the catalytic effect of catalyst 1
are also tested in the cross-coupling of iodobenzene
with styrene. The results obtained with GC method were
listed in Table 4. From the results we could see that only
two kinds of diphenylethylene isomers, anti-stilbene and
Recyclability of the catalysts The well known
advantages of polymer supported metal catalysts are
their easy separation and reusability. So we study the
recyclability of 1a and 2a on behalf of other catalogs.
The corresponding results are represented in Table 5.
1,1-diphenylethylene, were obtained with high yields
(
93%—100%) and high regioselectivity (90%—94%).
However, lower catalytic activity had been observed
a
Table 4 Heck reaction of iodobenzene with styrene in DMF
－
4
b
c
d
Entry
Catalyst/(10 mmol•Pd)
t/h
17
8.0
10
10
29
10
10
10
17
Conversion /%
A/B
9.4/1
15/1
Selectivity/%
TON
TOF
1
2
3
4
5
6
7
8
9
1a (1.2)
100
100
100
98
90
94
93
90
91
91
90
92
41700
50000
38500
32700
58000
41000
43000
33000
61000
2450
6250
3850
3270
2000
4100
4300
3300
3600
1b (1.0)
1c (1.3)
13.5/1
9.5/1
10.5/1
10.3/1
9.3/1
11.5/1
9.0/1
1d (1.5)
1e (0.8)
93
1f (1.2)
98
1g (1.1)
95
1h (1.5)
100
98
1i (0.8)
90
a
b
c
Reaction conditions: PhI (5 mmol), Et
3
N (6 mmol), styrene (6 mmol), DMF (5 mL). Determined by GC. TON: turn over number (mol
d
－
1
product per mol catalyst), not optimized. TOF: turn over frequency ( mol product per mol catalyst h ).
a
Table 5 Heck reaction of iodobenzene with n-butyl acrylate in DMF catalyzed by recycled catalysts 1a and 2a
－
4
b
c
d
Entry
Catalyst (10 mmol•Pd)
t/h
Yield /%
TON
TOF
1
2
3
4
5
6
7
8
9
1a (1.1)
4.5
5.0
6.5
8.0
9.5
4.5
5.5
7.0
7.5
8.5
100
100
100
100
100
100
100
100
100
100
45500
38500
38500
38500
38500
41700
41700
41700
41700
10100
7700
5920
4800
4050
9260
7580
5960
5560
4900
1a cycle 2
1a cycle 3
1a cycle 4
1a cycle 5
2a (1.2)
2a cycle 2
2a cycle 3
2a cycle 4
3a cycle 5
1
0
41700
a
b
c
Reaction conditions: PhI (5 mmol), Et
3
N (6 mmol), n-butyl acrylate (6 mmol), DMF (5 mL), T (100 ℃). Determined by GC. TON:
d
－
1
turn over number (mol product per mol catalyst), not optimized. TOF: turn over frequency (mol product per mol catalyst h ).
Chin. J. Chem. 2010, 28, 967— 973
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
971

Liu et al.
FULL PAPER
It can be seen clearly that the TOF decreased with the
runs of reuse, but the TON was kept and the conver-
sions were still 100% at 100 ℃ with longer time. The
results may prove that the catalysts we have prepared
can be reused at least 5 times without apparent loss of
activities. This may prompt the wide-spread application
of Heck reaction to the industry.
16 Dai, M.; Liang, B.; Wang, C.; Chen, J.; Yang, Z. Org. Lett.
2004, 6, 221.
17 Yang, D.; Chen, Y. C.; Zhu, N. Y. Org. Lett. 2004, 6, 1577.
18 Caruso, U.; Di Matola, A.; Panunzi, B.; Roviello, A.; Sirigu,
A. Polymer 2001, 42, 3973.
19 Caruso, U.; De Maria, A.; Panunzi, B.; Roviello, A. J. Pol.
Sci. A 2002, 40, 2987.
20
Cariati, F.; Caruso, U.; Centore, R.; Marcolli, W.; De Maria,
A.; Panunzi, B.; Roviello, A.; Tuzi, A. Inorg. Chem. 2002,
Conclusion
4
1, 6597.
In summary, we describe the preparation and cata-
lytic activity of two serials of new polymer sup-
ported-Pd catalysts. The catalysts exhibited good activ-
ity in Heck cross-coupling reactions between iodoben-
zene and n-butyl arcylates with TOF numbers up to
2
2
1
2
Reetz, M. T.; de Vries, J. G. Chem. Commun. 2004, 1559.
De Vries, A. H. M.; Mulders, J. M. C. A.; Mommers, J. H.
M.; Henderickx, H. J. W.; De Vries, J. G. Org. Lett. 2003,
1
8, 3285.
2
2
3
4
Cornils, B.; Herrmann, W. A. J. Catal. 2003, 216, 23.
McNamara, C. A.; Dixon, M. J.; Bradley, M. Chem. Rev.
28000 or between iodobenzene and styrene with TOF
numbers up to 6250. Furthermore, for the Heck cou-
pling reaction of iodobenzene with styrene, high stereo-
selectivity was obtained (anti-stilbene/1,1-diphenyl-
ethylene up to 15∶1), which was comparable to the
results of corresponding homogeneous catalysts. Addi-
tionally, the catalysts could be recovered by a simple
filtration progress. They can also be reused for at least 5
times with a slow progressive decrease in activity.
2
002, 102, 3275.
25
26
27
28
De Miguel, Y. R.; Brule, E.; Margue, R. G. J. Chem. Soc.
Perkin Trans. 1 2001, 3085.
Clapham, B.; Reger, T. S.; Janda, K. D. Tetrahedron 2001,
5
7, 4637.
Gonzalez-Arellano, C.; Corma, A.; Iglesias, M.; Sanchez, F.
Adv. Synth. Catal. 2004, 346, 1758.
Dell_Anna, M. M.; Mastrorilli, P.; Muscio, F.; Nobile, C. F.;
Suranna, G. P. Eur. J. Inorg. Chem. 2002, 1094.
Acknowledgements
29 Dahan, A.; Portnoy, M. Org. Lett. 2003, 5, 1197.
30
Datta, A.; Ebert, K.; Plenio, H. Organometallics 2003, 22,
685.
We thank Zhang Zongpei of Zhengzhou University
for the element analysis.
4
3
3
1
2
Yang, Y. C.; Luh, T. Y. J. Org. Chem. 2003, 68, 9870.
Lin, K. H.; Song, M. P.; Cai, D.; Hao, X. Q.; Wu, Y. J. Tet-
rahedron Lett. 2003, 44, 3955.
References
3
3
3
3
3
3
3
3
4
5
6
7
8
9
Yamada, Y. M. A.; Takeda, K.; Takahashi, H.; Ikegami, S.
Tetrahedron 2004, 60, 4097.
De Vos, D. E.; Dams, M.; Sels, B. F.; Jacobs, P. A. Chem.
Rev. 2002, 102, 3615.
1
Beletskaya, I. P.; Cheprakov, A. V. Chem. Rev. 2000, 100,
009.
Littke, A. F.; Fu, G. C. Angew. Chem. 2002, 114, 4350.
Littke, A. F.; Fu, G. C. Angew. Chem., Int. Ed. 2002, 41,
3
2
3
Clark, J. H.; Macquarrie, D. J.; Mubofu, E. B. Green Chem.
4
176.
Wang, J.; Xu, S.; Tao, X. C. Chin. J. Org. Chem. 2008, 28,
2 (in Chinese).
2
000, 2, 53.
4
5
6
7
Zhou, J. M.; Zhou, R. X.; Mo, L. Y.; Zhao, S. F.; Zheng, X.
M. J. Mol. Catal. A: Chem. 2002, 178, 289.
Chanthateyanonth, R.; Alper, H. J. Mol. Catal. A: Chem.
5
Mino, T.; Shirae, Y.; Sasai, Y.; Sakamoto, M.; Fujita, T. J.
Org. Chem. 2006, 71, 6834.
Li, S.; Lin, Y. J.; Xie, H. B.; Zhang, S. B.; Xu, J. N. Org.
Lett. 2006, 8, 391.
Altava, B.; Burguete, M. I.; Verdugo, E. G.; Karbass, N.;
Luis, S. V.; Puzary, A.; Sans, V. Tetrahedron Lett. 2006, 47,
2
003, 201, 23.
Tsai, F. Y.; Wu, C. L.; Mou, C. Y.; Chao, M. C.; Lin, H. P.;
Liu, S. T. Tetrahedron Lett. 2004, 45, 7503.
Shimizu, K.; Koizumi, S.; Hatamachi, T.; Yoshida, H.;
Komai, S.; Kodama, T.; Kitayama, Y. J. Catal. 2004, 228,
2
311.
1
41.
8
9
Xu, C.; Gong, J. F.; Yue, S. F.; Zhu, Y.; Wu, Y. J. Dalton
Trans. 2006, 39, 4730.
Dupont, J.; Pfeffer, M.; Spencer, J. Eur. J. Inorg. Chem.
4
0
1
Yang, H. Q.; Zhang, G. Y.; Hong, X. L.; Zhu, Y. X. J. Mol.
Catal. A: Chem. 2004, 210, 143.
Zhou, J. M.; Yang, Y. L.; Zhao, L.; Li, X. K.; Zhou, R. X.;
Zheng, X. M. Chin. J. Org. Chem. 2008, 28, 825 (in
Chinese).
Lin, K. H.; Yu, Z. Y.; Zhong, Y. H.; Cheng, Z. X. Chin. J.
Org. Chem. 2008, 28, 2149 (in Chinese).
Kim, N.; Kwon, M. S.; Park, C. M.; Park, J. Tetrahedron
Lett. 2004, 45, 7057.
4
2
001, 1917.
1
1
0
1
Bedford, R. B. Chem. Commun. 2003, 1787.
Ma, J.; Cui, X. L.; Zhang, B.; Song, M. P.; Wu, Y. J. Tet-
rahedron 2007, 63, 5529.
Ma, N.; Zhu, Z. W.; Wu, Y. J. Tetrahedron 2007, 63, 4625.
Herrmann, W. A. Angew. Chem., Int. Ed. 2002, 41, 1290.
Yong, B. S.; Nolan, S. P. Chemtracts-Org. Chem. 2003, 16,
42
43
44
45
1
1
1
2
3
4
Luo, C. C.; Zhang, Y. H.; Wang, Y. G. J. Mol. Catal. A:
Chem. 2005, 229, 7.
Mehnert, C. P.; Weaver, D. W.; Ying, J. Y. J. Am. Chem.
2
05.
1
5
Masllorens, J.; Moreno-Mañas, M.; Pla-Quintana, A.; Ro-
glans, A. Org. Lett. 2003, 5, 1559.
9
72
www.cjc.wiley-vch.de
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Chin. J. Chem. 2010, 28, 967— 973

Efficient Polymer-Supported Pd Catalysts for the Heck Reaction
Soc. 1998, 120, 12289.
Choudary, B. M.; Madhi, S.; Chowdari, N. S.; Kantam, M.
L.; Sreedhar, B. J. Am. Chem. Soc. 2002, 124, 14127.
Yuranov, I.; Moeckli, P.; Suvorova, E.; Buffat, P.;
Kiwi-Minsker, L.; Renken, A. J. Mol. Catal. A: Chem. 2003,
54 Frechet, J. M.; Schuerch, C. J. Am. Chem. Soc. 1971, 93,
492.
55 Blackburn, G. M.; Brown, M. J.; Harris, M. P. J. Chem. Soc.
1969, 676.
56 Letsinger, R. L.; Kornet, M. J.; Mahadevan, V.; Jerian, D.
M. J. Am. Chem. Soc. 1964, 86, 5163.
4
6
7
4
1
92, 239.
48
49
50
Srivastava, R.; Venkatathri, N.; Srinivas, D.; Ratnasamy, P.
Tetrahedron Lett. 2003, 44, 3649.
Waghmode, S. B.; Wagholikar, S. G.; Sivasanker, S. Bull.
Chem. Soc. Jpn. 2003, 76, 1989.
Calò, V.; Nacci, A.; Monopoli, A.; Fornaro, A.; Sabbatini,
L.; Cioffi, N.; Ditaranto, N. Organometallics 2004, 23,
57 Gokak, D. T.; Kamath, B. V.; Ram, R. N. J. Appl. Polym.
Sci. 1988, 35, 1523.
58 Patel, D. R.; Dalal, M. K.; Ram, R. N. J. Mol. Catal. A:
Chem. 1996, 109, 141.
59 Xu, C.; Gong, J. F.; Guo, T.; Zhang, Y. H.; Wu, Y. J. J. Mol.
Catal. A: Chem. 2008, 279, 69.
5
154.
60 Yang, F.; Zhang, Y. M.; Zheng, R.; Tang, J.; He, M. Y. J.
Organomet. Chem. 2002, 651, 146.
61 Beletskaya, I. P.; Kashin, A. N.; Karlstedt, N. B. J. Or-
ganomet. Chem. 2001, 622, 89.
62 Nowotny, M.; Hanefeld, U. Chem. Commun. 2000, 1877.
63 Papp, A.; Galbacs, G.; Molnar, A. Tetrahedron Lett. 2005,
46, 7725.
51
52
53
Pröckl, S. S.; Kleist, W.; Gruber, M. A.; Köhler, K. Angew.
Chem., Int. Ed. 2004, 43, 1881.
Papp, A.; Miklo's, K.; Forgo, P.; Molna′r, A. J. Mol. Catal.
A: Chem. 2005, 229, 107.
Lin, K. H.; Zeng, Q. B.; Shao, M.; Zhong, Y. H.; Zhang, F.
F.; Yu, Z. Y.; Li, M. X. CN 101024197A, 2010.
(E0911041 Sun, H.; Lu, Z.)
Chin. J. Chem. 2010, 28, 967— 973
© 2010 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.cjc.wiley-vch.de
973