40-44 Pd(II) salen complex covalently anchored to multi-walled carbon nanotubes as a heterogeneous and reusable precatalyst for Mizoroki-Heck and Hiyama cross-coupling reactions

Article abstract of DOI:10.1002/aoc.3246

A Pd(II) salen complex anchored to multi-walled carbon nanotubes showed excellent catalytic activity and stability for the Mizoroki-Heck and Hiyama cross-couplings of aryl halides with olefins and phenylsiloxanes. Furthermore, the heterogeneous catalyst could be reused up to four times with the catalytic activity being recovered easily after simple manipulations.

Full text of DOI:10.1002/aoc.3246

Full Paper
Received: 28 July 2014
Revised: 2 October 2014
Accepted: 13 October 2014
Published online in Wiley Online Library: 19 November 2014
(wileyonlinelibrary.com) DOI 10.1002/aoc.3246
Pd(II) salen complex covalently anchored to
multi-walled carbon nanotubes as a
heterogeneous and reusable precatalyst for
Mizoroki–Heck and Hiyama cross-
†
coupling reactions
Barahman Movassagh*, Fatemeh S. Parvis and Mozhgan Navidi
A Pd(II) salen complex anchored to multi-walled carbon nanotubes showed excellent catalytic activity and stability for the
Mizoroki–Heck and Hiyama cross-couplings of aryl halides with olefins and phenylsiloxanes. Furthermore, the heterogeneous
catalyst could be reused up to four times with the catalytic activity being recovered easily after simple manipulations.
Copyright © 2014 John Wiley & Sons, Ltd.
Additional supporting information may be found in the online version of this article at the publisher’s web-site.
Keywords: cross-coupling reactions; Mizoroki–Heck reaction; Hiyama reaction; palladium salen complex; heterogeneous catalysis
[
4,7]
transformations.
The catalytic system for an efficient Heck
Introduction
reaction consists of a palladium source, ligand, base and solvent.
[
8]
[9]
The use of Schiff base complexes containing transition metal ions is
of significant importance due to their catalytic and biological
Usually, phosphane and phosphorus ligands are used in the
Mizoroki–Heck reaction, as they play an important role in stabili-
zation and in situ generation of Pd(0) species from Pd(II) com-
plexes. Because of the high cost, toxicity and thermal instability
of phosphine ligands, various phosphane-free catalytic
[1]
properties. Recently, there has been considerable interest in
exploring the catalytic activities of transition metals covalently
anchored to carbon nanotubes (CNTs) owing to their specific cata-
lytic applications compared to homogeneous complexes. Also,
functionalization of CNTs is an effective way to enhance their phys-
ical and chemical properties, and improve the solubility. Metal
nanoparticles and various transition metal complexes such as por-
phyrins and polymers have been used for the functionalization of
[
10]
systems
have been introduced as less complicated and envi-
ronmentally more desirable alternatives to the original
Pd–phosphane catalysts. However most of them show poor effi-
ciency and reusability in palladium-catalysed Mizoroki–Heck
[
11]
reactions.
Moreover, a major restriction on palladium-
[2]
CNTs. Transition metal Schiff base complexes have shown excel-
catalysed coupling processes has been the poor reactivity of
cheaper and more readily available aryl bromides and chlorides
in comparison with more active aryl iodides. Therefore, the
search for efficient catalysts for the cross-coupling of olefins with
deactivated aryl bromides and, eventually, activated aryl
chlorides is under way.
The most efficient methodologies for the construction of biaryls
are the palladium-catalysed cross-coupling transformations bet-
ween aryl halides and organometallic species. Among the various
organometallic coupling reagents, the organoboranes (Suzuki–
[
3]
lent catalytic activity when grafted on CNTs.
Transition metal-catalysed cross-coupling reactions to form a
new carbon–carbon (Csp2–Csp2) bond have been recognized
as powerful synthetic tools and a major area of interest in multi-
ple organic transformations for academic and industrial
[
4]
processes. The palladium-catalysed coupling of aryl halides
with olefins (the Mizoroki–Heck reaction) or aryltrialkoxysilanes
(
Hiyama cross-coupling) is a powerful tool for the preparation
of various substituted olefins and biaryls. The former reaction
has been used in the synthesis of natural products, agrochemi-
cals and pharmaceuticals, and the products of the latter reac-
[
12,13]
[14]
Miyaura),
organostannanes (Stille)
(Hiyama) are the most commonly employed partners because of
and organosilanes
[
5]
[15]
[
6]
tion have found widespread applications as organocatalysts,
[
6]
agrochemicals, organic materials for organic light-emitting
[
6]
[6]
diodes and pharmaceutically active compounds. Unlike
other carbon–carbon coupling reactions, the Mizoroki–Heck
reaction has the ability to tolerate a variety of functional groups
such as ketone, aldehyde, amino, cyano, carbonyl, hydroxyl,
ester, or nitro groups, thus avoiding the need for protection
and deprotection of functional groups during organic
* Correspondence to: Barahman Movassagh, Department of Chemistry, K.N. Toosi University
of Technology, PO Box 16315-1618, Tehran, Iran. E-mail: bmovass1178@yahoo.com
†
This paper is dedicated to Professor Kristin Bowman-James, University of Kansas.
Department of Chemistry, K. N. Toosi University of Technology, PO Box 16315-
1618, Tehran, Iran
Appl. Organometal. Chem. 2015, 29, 40–44
Copyright © 2014 John Wiley & Sons, Ltd.

Pd-Salen@MWCNTs as heterogeneous catalyst for Heck and Hiyama reactions
comparable excellent yields, high stereoselectivities and wide
functional group tolerances. However, the toxicity of tin reagents in
Stille couplings, and difficulties in the preparation and purification
of organoboranes are disadvantages. On the other hand,
organosilanes (Hiyama) are easily prepared, environmentally benign
General Procedure for Mizoroki–Heck Coupling Reaction
A mixture of aryl halide (1.0 mmol), alkene (1.1 mmol), triethylamine
(1.1 mmol), DMF (1 ml) and the catalyst (0.006 mmol, 0.6 mol% Pd)
was stirred at 130 °C under atmospheric conditions. (For aryl bro-
mides or chlorides, tetrabutylammonium bromide (TBAB; 1.0
mmol) was also added.) The progress of the reaction was moni-
tored using TLC. After completion of the reaction, the mixture was
cooled to room temperature, poured into water (10 ml) and ex-
[15,16]
and stable agents under many reaction conditions.
Experimental
3
tracted with CHCl (3 × 10 ml). The combined organic extracts were
General
washed with brine (2 × 10 ml), dried (Na SO ) and concentrated in
2
4
vacuum. The crude product was further purified by preparative TLC
silica gel) using n-hexane–EtOAc (9:1) to afford the desired prod-
All melting points were determined using a Büchi B-540 melting
point apparatus. IR spectra were recorded with an ABB Bomem
model FTLA 2000 spectrophotometer using KBr pellets. NMR spec-
(
1
13
uct. The products were characterized using IR, H NMR and
NMR spectroscopies (see supporting information).
C
1
13
tra were recorded at 300 ( H) and 75 ( C) MHz with a commercial
Bruker AQS-300 instrument using CDCl as solvent. Solvents and
3
all chemicals were purchased from Merck and Aldrich and were
used as received. Aryltrialkoxysilanes were prepared from
bromobenzene and tetraethoxysilanes/tetramethoxysilanes fol-
General Procedure for Hiyama Coupling Reaction
The catalyst (5.3 mg, 0.8 mol% Pd) was added to a solution of aryl
halide (1 mmol), phenyltrialkoxysilane (1.5 mmol) and tetra-
[
17]
lowing a literature report.
butylammonium fluoride (TBAFꢁ3H O; 631 mg, 2 mmol) in toluene
2
(2 ml). The reaction mixture was heated to 90 °C under atmospheric
Catalyst Synthesis
conditions. The progress of the reaction was monitored using TLC.
After completion, the reaction mixture was cooled to room temper-
ature, and the solvent was evaporated. Then EtOAc (10 ml) was
added to the reaction mixture, and the catalyst was recovered with
centrifugation. The organic layer was washed with water (2 × 5 ml),
Ligand and catalyst were synthesized following a procedure
[
18]
reported in our previous work, which is briefly explained in the
following paragraphs.
Synthesis of Schiff base ligand
4
dried over anhydrous MgSO , filtered and concentrated in vacuum.
A mixture of salicylaldehyde and 1,3-diamino-2-propanol in a 2:1 ra-
tio and absolute ethanol were heated to reflux until the completion
of the reaction. The yellow precipitate was separated, washed with
diethyl ether and dried in vacuum to obtain the desired Schiff base.
The crude product was further purified by preparative TLC (silica
gel) using n-hexane as eluent to afford the desired product. The
1
13
products were characterized using IR, H NMR and C NMR spectros-
copies (see supporting information).
ꢀ
1
M.p. 100–102 °C. IR (KBr): ν
1632 cm .
C¼N
Palladium complex synthesis
General Procedure for Recycling of Catalyst
A solution of the ligand in acetonitrile was magnetically stirred
followed by addition of PdCl salt (ligand-to-PdCl ratio =1:1). The
The reaction mixture of either Mizoroki–Heck or Hiyama reaction
was cooled to room temperature and the catalyst was separated
from the reaction mixture by centrifugation, washed with water
2
2
reaction mixture was refluxed for 1 h. The product (Pd(II)-Salen)
was filtered off, washed with diethyl ether and dried in vacuum as
and CHCl and dried in vacuum at 70 °C for 24 h before being used
3
ꢀ
1
a yellow solid. M.p. 250 °C (dec.). IR (KBr): νC¼N 1615 cm
.
in subsequent reactions.
Preparation of Pd(II) salen complex anchored to multi-walled carbon nano-
tubes (Pd-Salen@MWCNTs)
Results and Discussion
Purchased MWCNTs–CO H (200 mg) were chlorinated using thionyl
2
chloride (50 ml) in N,N-dimethylformamide (DMF; 2 ml) at 65 °C for
Recently, stabilization of Pd(II) complexes on high-surface-area
2
4 h. The solid was then separated by filtration and washed with
materials and their use in Mizoroki–Heck and Hiyama cross-
[
19]
anhydrous tetrahydrofuran (THF; 60 ml), and dried in vacuum to
obtain MWCNTs–COCl. Then, MWCNTs–COCl (100 mg) were added
to a solution of the previously prepared Pd(II)-Salen (200 mg) in
degassed CHCl (16 ml), and the suspension was refluxed for 20 h
under nitrogen. The solid was then filtered and washed with THF
coupling reactions have been reported.
We previously devel-
oped air-/moisture-stable and reusable Pd-Salen@MWCNTs (Fig. 1)
as an efficient heterogeneous catalyst in the Suzuki–Miyaura and
[
18]
Sonogashira–Hagihara reactions, and in the solvent-free synthe-
3
[
18]
sis of ynones. In this paper, we extend the scope of this catalytic
system to coupling of aryl halides (iodides, bromides and chlorides)
with various olefins (Mizoroki–Heck reaction) and aryl iodides or
(2 × 20 ml) and CH Cl (2 × 20 ml) and dried in vacuum to afford
2 2
the desired catalyst. The catalyst was characterized using attenu-
ated total reflection infrared spectroscopy (ATR), Raman spectros-
copy, inductively coupled plasma (ICP), X-ray diffraction, X-ray
photoelectron spectroscopy, transmission electron microscopy
and thermogravimetric–differential thermal analysis data. The ATR
spectrum of the catalyst showed a band at 1708 cm associated
with C¼O stretching of the ester linkage between the CNT and
the Schiff base complex. Moreover, the metal content of the com-
plex was found to be 16.2 ppm using ICP, and the ratio of Pd/N in
the catalyst was obtained to be 1.82%.
ꢀ
1
Figure 1. Heterogeneous Pd-Salen@MWCNTs catalyst.
Appl. Organometal. Chem. 2015, 29, 40–44
Copyright © 2014 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc

B. Movassagh, F. S. Parvis and M. Navidi
a
Table 1. Optimization of reaction conditions
in 82–95% isolated yield (Table 2, entries 1–5, 7–9). However, the
reaction of sterically hindered 2-iodoanisole with styrene gives a
lower yield (Table 2, entry 6). Under these same conditions,
coupling of bromobenzene with styrene gives a poor yield (26%)
after 24 h (Table 2, entry 10); therefore, TBAB (1 equiv.) was added
to the reaction mixture for the cross-coupling of aryl bromides or
chlorides with alkenes. A variety of aryl bromides bearing
electron-donating and electron-withdrawing groups were
examined. Activated aryl bromides, such as 4-bromobenzonitrile,
Entry Base Solvent Temperature Amount
°C) of catalyst
mol% Pd)
Yield
(%)
TON
b
(
(
1
2
3
4
5
6
7
8
9
Et
Et
Et
Et
3
3
3
3
N
N
N
N
DMF
DMF
25
60
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.4
0.6
0.8
1.0
17
28
42
1-bromo-4-nitrobenzene and 4-bromobenzaldehyde, coupled
25
rapidly in high to excellent yields (Table 2, entries 16–18). The
Mizoroki–Heck cross-coupling of chlorobenzene with styrene and
DMF
90
47
78
DMF
115
130
140
130
130
130
80
87
145
158
152
140
130
122
—
4-methoxystyrene was also investigated under similar reaction
Et
3
N
N
N
N
N
N
N
DMF
DMF
95
conditions (Table 2, entries 21 and 22). Compared with the corre-
sponding bromo analogues, the reaction of the chloro derivatives
gives poor yields and requires longer times.
In continuation of this study, we also applied the catalyst to the
Hiyama cross-coupling reaction of aryl halides with pheny-
ltrialkoxysilanes. Initially, the coupling of iodobenzene (1 mmol)
Et
Et
Et
Et
Et
Et
3
91
3
3
3
3
3
DMAc
NMP
DMSO
84
78
73
1
1
1
1
1
1
1
1
1
0
2
H O
No reaction
1
2
3
4
5
6
7
8
Neat
130
130
130
130
130
130
130
130
82
76
40
46
58
85
85
81
137
127
67
and phenyltriethoxysilane (1.5 mmol) in the presence of TBAFꢁ3H O
2
DIPEA DMF
(2 mmol) and the catalyst in air was chosen as a model reaction to
t
KO Bu DMF
determine the optimum reaction conditions (Table 3). The effect of
2
K CO
3
DMF
DMF
DMF
DMF
DMF
77
Et
3
Et
3
Et
3
Et
3
N
145
142
106
81
Table 2. Reaction of various aryl halides with olefins in the presence of
N
N
N
a
the catalyst in DMF
a
Reaction conditions: iodobenzene (1 mmol), styrene (1.1 mmol), base
1.1 mmol), solvent (1 ml) at various temperatures under air.
(
b
Isolated yields.
1
R
2
R
Entry
ArX
Product Time Yield TON
b
(
h)
(%)
bromides with phenylsiloxanes (Hiyama reaction) under aerobic
conditions and examine its reusability.
1
PhI
PhI
Ph
4-MeOC6H4
4-ClC6H4
CN
H
H
H
H
H
H
H
H
H
H
H
H
H
H
3a
3b
3c
0.25
1.5
1.5
2
95 158
83 138
82 137
87 145
91 152
70 117
83 138
90 150
92 153
26 43
85 142
76 127
87 145
80 133
79 132
89 148
93 155
88 147
81 135
84 140
23 38
15 25
37 62
29 48
2
Optimized conditions for the Mizoroki–Heck coupling reaction
were obtained using the reaction of iodobenzene (1 mmol) and
styrene (1.1 mmol) in the presence of the catalyst under various
atmospheric conditions (Table 1). The reaction rates are markedly de-
pendent on the solvent, base and temperature, as well as the con-
centration of the palladium complex. Various organic and inorganic
bases were screened, and the yield of the products is reduced when
3
PhI
4
PhI
3d
3b
3e
3f
5
4-MeOC H I
6
4
Ph
2
6
2-MeOC H I
6
4
Ph
2
7
1-I-naphthalene
4-MeC H I
Ph
2
8
6
4
2
CO Me
3 g
3 h
3a
2
9
2-I-thiophene
PhBr
2
CO Bu
0.5
t
inorganic bases such as KO Bu or K CO are employed (Table 1,
10
11
12
13
14
15
16
17
18
Ph
24
2
3
c
entries 13 and 14). A considerable increase in product formation is
observed in the presence of organic bases, such as triethylamine, in
DMF at a high temperature. Several other solvents, including
dimethylacetamide (DMAc), N-methylpyrrolidin-2-one (NMP), dim-
ethylsulfoxide (DMSO) and water, as well as neat condition were also
surveyed under similar conditions, but compared with DMF all give
inferior results (Table 1, entries 7–11). Then, various amounts of cata-
lyst between 0.4 and 1.0 mol% were investigated for the reaction
PhBr
Ph
3a
5
c
PhBr
4-MeOC6H4
3b
6
c
PhBr
2
CO Et
3i
4
c
PhBr
CN
3d
4.5
6
c
4-MeC H Br
6
4
Ph
Ph
Ph
Ph
Ph
Me 3j
c
4-NCC H Br
6
4
H
H
H
H
H
H
H
H
H
3k
3
c
2
6 4
4-O NC H Br
3l
3
c
4-OHCC H Br
6
4
3m
5
c
(Table 1, entries 5, 15–18). Among the various amounts, 0.6 mol%
19 1-Br-naphthalene
20 1-Br-naphthalene
3f
7
c
of the catalyst is found to be the best (Table 1, entry 5). Therefore,
2
CO Et
3n
5
c
it was decided to use Et N as the base and DMF as solvent at 130
21
22
23
24
PhCl
Ph
3a
24
3
c
°C in the presence of 0.6 mol% of the catalyst as the optimal condi-
4-MeCOC H Cl
Ph
Ph
Ph
3o
24
24
24
6
4
c
tions in further studies.
The resulting optimized conditions were then applied to the
coupling reactions of activated, nonactivated or deactivated aryl
4-O NC H Cl
6 4
3l
2
c
4-NCC H Cl
6
4
3k
a
3
Reaction conditions: aryl halide (1 mmol), olefin (1.1 mmol), Et N (1.1
3
halides 1 with various vinylic substrates 2 in DMF/Et N at 130 °C
mmol), Pd-Salen@MWCNTs (0.6 mol%) in DMF (1 ml), 130 °C,
under air.
in the presence of 0.6 mol% of the catalyst (Table 2). The results
show that the catalyst is remarkably active and tolerates a range
of functional groups. As expected, the reaction of aryl iodides
proceeds smoothly within 0.25 to 2 h to give the desired products
b
c
Isolated yields.
TBAB (1 mmol) was added.
wileyonlinelibrary.com/journal/aoc
Copyright © 2014 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2015, 29, 40–44

Pd-Salen@MWCNTs as heterogeneous catalyst for Heck and Hiyama reactions
Table 3. Optimization of reaction of phenyltriethoxysilane with
iodobenzene in the presence of the catalyst
Table 5. Recycling of catalyst for the reaction of iodobenzene with sty-
a
a
rene and phenyltriethoxysilane
b
b
Entry
Cycle
Mizoroki–Heck yield (%)
Hiyama yield (%)
1
2
3
4
1
2
3
4
95
93
89
81
93
92
85
78
Entry Solvent
Temperature Amount of catalyst Yield
TON
b
(°C)
(mol% Pd)
(%)
1
2
3
4
5
6
7
8
9
THF
—
50
90
100
90
25
60
90
90
90
90
90
0.8
0.8
0.8
0.8
0.8
0.8
0.8
1.0
0.7
0.6
0.4
47
32
64
67
26
57
93
93
81
77
44
59
40
a
Reaction conditions were the same as that of Table 2, entry 1 (3a) for
the Mizoroki–Heck reaction, and Table 4, entry 1 (5a) for the Hiyama
reaction.
DMF
80
DMF
84
b
Isolated yields.
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
33
71
116
93
Among the various catalyst amounts, 0.8 mol% of the catalyst is
found to be the best (Table 3, entry 7). Therefore, it was decided to
use toluene as solvent, 90 °C as temperature and 0.8 mol% of the
catalyst as the optimal conditions in further studies.
115
128
110
10
11
To survey the generality of the catalytic protocol, we investi-
gated the reaction using various aryl halides coupled with
phenylsiloxanes under the optimized conditions. The results
are summarized in Table 4. We examined the electronic and steric
effects of various aryl halides bearing electron-releasing and
electron-withdrawing groups on the resulting yields and reaction
times. As is evident from Table 4, the cross-coupling reactions of
aryl iodides and bromides with phenylsiloxanes all proceed
smoothly to give the desired products in good to excellent yields.
Under the same reaction conditions, aryl chlorides give trace
amounts of the corresponding products even after 24 h (Table 4,
entries 13 and 14). Generally, compared with the corresponding
bromo analogues, the reaction of aryl iodides requires shorter
times. The reactions of sterically hindered 2-iodoanisole and
a
Reaction conditions: phenyltriethoxysilane (1.5 mmol), iodobenzene
1 mmol), TBAF.3H O (2 mmol), Pd-Salen@MWCNTs in solvent
2 ml) at various temperatures.
(
(
2
b
Isolated yields.
various reaction parameters such as solvent, temperature and
catalyst concentration was evaluated. As the results in Table 3 show,
toluene is the most suitable solvent for the reaction. Next, various
temperatures and amounts of catalyst were screened. Increasing
the temperature from 25 °C to higher (60 and 90 °C) leads to a
substantial rate acceleration of the reaction (Table 3, entries 5–7).
2
-iodotoluene with phenyltriethoxysilane give lower yields (Table 4,
Table 4. Pd-Salen@MWCNTs-catalysed Hiyama cross-coupling of aryl
halides with phenylsiloxanes
a
entries 4 and 5). This catalytic complex was compatible with a wide
range of functional groups, such as carbonyl, nitro, cyano and
methoxy, on aryl halides.
Finally, the recovery and reusability of the catalyst were investi-
gated using the reaction of iodobenzene with styrene (Heck reac-
tion) and iodobenzene with phenyltriethoxysilane (Hiyama reaction)
as representative reactants, in the presence of 0.6 and 0.8 mol%, re-
spectively, of Pd-Salen@MWCNTs in order to study the recyclability
of this heterogeneous catalyst. The recycling process was repeated
for four cycles with some decrease in the catalytic activity of the
catalyst (Table 5).
Entry
ArX
R
Time
h)
Product
Yield
TON
b
(
(%)
1
2
3
4
5
6
7
8
9
PhI
Et
Et
4
5a
5b
5c
5d
5e
5f
93
91
116
114
91
2-I-thiophene
4
4-MeOC
2-MeOC
6
H
H
4
I
Et
7
73
Another point of great concern for most anchored catalysts is the
possibility that some active metal migrates from the solid support
to the liquid phase and that this leached metal would become
6
4
I
Et
8.5
7
66
83
2-MeC
4-MeCOC
4-MeC
6
H
4
I
Et
70
88
6
H
4
I
Et
4.5
5.5
5
93
116
103
100
101
93
[
20]
6
H
4
I
Me
5g
5h
5a
5j
82
responsible for a significant part of the catalytic activity. In order
to determine if leaching was a problem, an experiment was per-
formed with the Mizoroki–Heck coupling reaction of iodobenzene
and styrene at 130 °C under air. After 15 min, the catalyst was
separated from the reaction mixture, and the amount of the Pd
species dissolved into solution caused by leaching was determined
using ICP after evaporation of the solution to dryness. The ICP result
shows that about 0.8% of the total amount of the original Pd
species is lost into solution during the course of the reaction.
1-I-naphthalene Me
80
PhBr
1,4-Br
4-O NC
4-NCC
PhCl
4-MeCOC
4-NCC
4-O NC
Et
Et
Et
Et
Et
Et
Et
Et
8
81
10
11
12
13
14
15
16
2
C
6
H
4
10
74
2
6
4
H Br
8
9
5k
5l
90
113
108
—
6
H
4
Br
86
24
24
24
24
5a
5f
Trace
Trace
Trace
Trace
6
H
4
Cl
Cl
Cl
—
6
H
4
5l
—
2
6
H
4
5k
—
a
Reaction conditions: aryl halide (1 mmol), phenylsiloxane (1.5 mmol),
TBAF.3H O (2 mmol), and 0.8 mol% of the catalyst in toluene
2 ml) at 90 °C.
Conclusions
2
(
b
Mizoroki–Heck and Hiyama couplings were performed in the pres-
ence of the air-/moisture-stable and recyclable Pd-Salen@MWCNTs
Isolated yields.
Appl. Organometal. Chem. 2015, 29, 40–44
Copyright © 2014 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/aoc

B. Movassagh, F. S. Parvis and M. Navidi
[
8] a) L. L. Hill, J. M. Smith, W. S. Brown, L. R. Moore, P. Guevera, E. S. Pair,
J. Porter, J. Chou, C. J. Wolterman, R. Craciun, D. A. Dixon,
K. H. Shaughnessy, Tetrahedron 2008, 64, 6920; b) A. F. Littke,
G. C. Fu, J. Am. Chem. Soc. 2001, 123, 6989.
catalyst. In the presence of this catalyst, aryl iodides and bromides
could be coupled with a variety of vinylic substrates in high to excel-
lent yields. This thermally stable catalyst was also used for the
Hiyama cross-coupling reaction of aryl halides with phenylsiloxanes.
The catalyst shows not only high catalytic activity, but also offers
many practical advantages such as thermal stability, oxygen insensi-
tivity and recyclability. The catalyst was reused for four consecutive
runs in both reactions with consistent activity. Easy preparation and
separation of the catalyst and excellent catalytic performance make
it a good heterogeneous system and a useful alternative to other
heterogeneous palladium catalysts.
[9] a) R. B. Bedford, S. L. Welch, Chem. Commun. 2001, 192;
b) D. Morales-Morales, R. Redón, C. Yung, C. M. Jensen, Chem.
Commun. 2000, 1619.
10] a) A. L. Gottumukkala, J. F. Teichert, D. Heijnen, N. Eisink, S. V. Dijk,
C. Ferrer, A. V. D. Hoogenband, A. J. Miannaard, J. Org. Chem.
[
2
006, 71, 426; b) H. J. Li, L. Wang, Eur. J. Org. Chem. 2006, 5099;
c) G. A. Grasa, A. C. Hillier, S. P. Nolan, Org. Lett. 2001, 3, 1077;
d) Z. Zhou, M. Liu, X. Wu, H. Yu, G. Xu, Y. Xie, Appl. Organometal.
Chem. 2013, 27, 562; e) M. Gholinejad, V. Karimkhani, I. Kim, Appl.
Organometal. Chem. 2014, 28, 221; f) S. Mohanty, D. Suresh,
M. S. Balakrishna, J. T. Mague, J. Organometal. Chem. 2009, 694,
2114; g) M. Gholinejad, H. R. Shahsavari, Inorg. Chim. Acta 2014,
Acknowledgements
4
21, 433.
Financial support from the K. N. Toosi University of Technology Re-
search Council is gratefully acknowledged.
[
[
[
11] X. Cui, Y. Zhou, N. Wang, L. Liu, Q. X. Guo, Tetrahedron Lett. 2007, 48,
163.
12] J. Tsuji, Palladium Reagents and Catalysts: New Perspectives for the 21st
Century, Wiley, New York, 2004.
13] a) X. F. Wu, P. Anbarasan, H. Neumann, M. Beller, Angew. Chem. Int. Ed.
2010, 49; b) J. Hassan, M. Sevigon, C. Gozzi, E. Schulz, M. Lemair, Chem.
Rev. 2002, 102, 1359.
14] a) J. K. Stille, Angew. Chem. Int. Ed. 1986, 25, 508; b) P. Espinet,
A. M. Echavarren, Angew. Chem. Int. Ed. 2004, 43, 4704.
15] a) T. Hiyama, J. Organometal. Chem. 2002, 653; b) Y. Hatanaka,
T. Hiyama, J. Org. Chem. 1998, 53, 918.
16] a) T. Hiyama, in Metal-Catalyzed Cross-Coupling Reactions (Eds.: F.
Diederich, P. J. Stang), Wiley-VCH, Weinheim, 1998, chap. 10;
b) T. Nokami, Y. Tomida, T. Kamei, K. Itami, J.-I. Yoshida, Org. Lett.
References
[1] a) P. A. Vigoto, V. Peruzzo, S. Tamburini, Coord. Chem. Rev. 2012, 256,
[
[
[
953; b) A. Garoufis, S. K. Hadjikakou, N. Hadjiliadis, Coord. Chem. Rev.
2
2
009, 253, 1384; c) R. N. Prabhu, R. Ramesh, J. Organometal. Chem.
012, 718, 43; d) A. Dewan, Bull. Korean Chem. Soc. 2014, 35, 1855;
e) K. J. Miller, J. H. Baag, M. M. Abu-Omar, Inorg. Chem. 1999, 38,
510; f) P. Liu, X.-J. Feng, R. He, Tetrahedron 2010, 66, 631;
g) N. T. S. Phan, D. H. Brown, P. Styring, Tetrahedron Lett. 2004, 45,
915; h) V. Ayala, A. Corma, M. Iglesias, J. A. Rinćon, F. Sánchez,
4
7
2
2
006, 8, 729; c) C. M. So, H. W. Lee, C. P. Lau, F. Y. Kwong, Org. Lett.
009, 11, 317; d) K. Cheng, B. Zhao, S. Hu, X.-M. Zhang, C. Qi,
J. Catal. 2004, 224, 170.
[
[
[
2] a) J. Guerra, M. A. Herrero, Nanoscale 2010, 2, 1390; b) J. Jin, Z. Dong,
J. He, R. Li, J. Ma, Nanoscale Res. Lett. 2009, 4, 578; c) H. X. Wu, R. Tong,
X. Q. Qiu, H. F. Yang, Y. H. Lin, R. F. Cai, S. X. Qian, Carbon 2007, 45, 152.
3] a) M. Salavati-Niasari, M. Bazarganipour, Appl. Surf. Sci. 2009, 255, 7610;
b) M. Salavati-Niasari, M. Bazarganipour, Transit. Met. Chem. 2009,
Tetrahedron Lett. 2013, 54, 6211; e) S.-N. Chen, W.-Y. Wu, F.-Y. Tsai,
Tetrahedron 2008, 64, 8164; f) C. Diebold, A. Derible, J.-M. Becht,
C. L. Drian, Tetrahedron 2013, 69, 264; g) E. Alacid, C. Nájera, Adv.
Synth. Catal. 2006, 348, 945.
[
[
17] A. S. Manoso, C. Ahn, A. Soheili, C. J. Handy, R. Correia, W. M. Seganish,
P. Deshong, J. Org. Chem. 2004, 69, 8305.
18] a) M. Navidi, N. Rezaei, B. Movassagh, J. Organometal. Chem.
34, 605.
4] a) I. P. Beletskaya, A. V. Cheprakov, Chem. Rev. 2000, 100, 3009;
b) C. E. Tucker, J. G. de Vries, Top. Catal. 2002, 19, 111; c) R. F. Heck, in
Comprehensive Organic Synthesis, Vol. 4 (Eds.: B. M. Trost, I. Fleming),
Pergamon Press, Oxford, 1991, p. 833; d) M. Oestrich, The Mizoroki-
Heck Reaction, 4th edn, Wiley, Chichester, 2009.
2
013, 743, 63; b) M. Navidi, B. Movassagh, S. Rayati, Appl. Catal.
A 2013, 452, 24.
[
[
19] a) A. Modak, J. Mondal, A. Bhaumik, Green Chem. 2012, 14, 2840;
b) A. Modak, J. Mondal, V. K. Aswal, A. Bhaumik, J. Mater. Chem. 2010,
[
5] a) G. Ren, X. Cui, E. Yang, F. Yang, Y. Wu, Tetrahedron 2010, 66,
20, 8099.
4
1
022; b) L. F. Tietze, W. Ruhr, Angew. Chem. Int. Ed. 1995, 34,
366; c) J. G. de Vries, Can. J. Chem. 2001, 79, 1086.
20] a) S. Paul, J. H. Clark, Green Chem. 2003, 5, 635; b) E. B. Mubofu,
J. H. Clark, D. J. Macquarrie, Green Chem. 2001, 3, 23.
[
6] a) A. C. Spivey, T. Fekner, S. E. Spey, J. Org. Chem. 2000, 65, 3154; b)
M. E. Matheron, M. Porchas, Plant Dis. 2004, 88, 665; c) J. N. Moorthy,
P. Venkatakrishnan, D.-F. Huang, T. J. Chow, Chem. Commun. 2008,
Supporting Information
2146; d) P. Lloyd-Williams, E. Giralt, Chem. Soc. Rev. 2001, 30, 145.
[
7] a) E. Peris, R. H. Crabtree, Coord. Chem. Rev. 2004, 248, 2239;
b) R. N. Prabhu, R. Ramesh, Tetrahedron Lett. 2012, 53, 5961;
c) R. F. Heck, Acc. Chem. Res. 1979, 12, 146.
Additional supporting information may be found in the online
version of this article at the publisher’s web-site.
wileyonlinelibrary.com/journal/aoc
Copyright © 2014 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2015, 29, 40–44