A atom-efficient cross-coupling reaction of aryl iodides with triarylbismuths catalyzed by immobilization of palladium(II)-Schiff base complex in MCM-41

Article abstract of DOI:10.1016/j.tet.2016.01.052

The first phosphine-free heterogeneous atom-efficient cross-coupling of aryl iodides with triarylbismuths was achieved in NMP using K₂CO₃ as base at 110 °C in the presence of 2 mol % of an MCM-41-immobilized palladium(II)-Schiff base complex [MCM-41-N,N-Pd(OAc)₂], yielding a variety of unsymmetrical biaryls in good to excellent yields. This new heterogeneous palladium catalyst exhibits high catalytic activity and can be recovered by a simple filtration of the reaction solution and recycled for at least 10 consecutive trials without any decreases in activity. Our system not only avoids the use of phosphine ligands, but also solves the basic problem of palladium catalyst recovery and reuse.

Full text of DOI:10.1016/j.tet.2016.01.052

Accepted Manuscript
A atom-efficient cross-coupling reaction of aryl iodides with triarylbismuths catalyzed
by immobilization of palladium(II)- Schiff base complex in MCM-41
Caifeng Xu, Lin Yin, Bin Huang, Haiyi Liu, Mingzhong Cai
PII:
S0040-4020(16)30052-7
10.1016/j.tet.2016.01.052
TET 27459
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 25 November 2015
Revised Date: 24 January 2016
Accepted Date: 27 January 2016
Please cite this article as: Xu C, Yin L, Huang B, Liu H, Cai M, A atom-efficient cross-coupling reaction
of aryl iodides with triarylbismuths catalyzed by immobilization of palladium(II)- Schiff base complex in
MCM-41, Tetrahedron (2016), doi: 10.1016/j.tet.2016.01.052.
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ACCEPTED MANUSCRIPT
A atom-efficient cross-coupling reaction of aryl iodides with
triarylbismuths catalyzed by immobilization of palladium(II)-
Schiff base complex in MCM-41
Caifeng Xu, Lin Yin, Bin Huang, Haiyi Liu and Mingzhong Cai*
College of Chemistry & Chemical Engineering, Jiangxi Normal University,
Nanchang 330022, P. R. China
Fax: (+86)-791-8812-0388; E-mail: mzcai@jxnu.edu.cn
ABSTRACT
The first phosphine-free heterogeneous atom-efficient cross-coupling of aryl iodides
with triarylbismuths was achieved in NMP using K CO as base at 110 °C in the
2
3
presence of 2 mol% of an MCM-41-immobilized palladium(II)-Schiff base complex
MCM-41-N,N-Pd(OAc) ], yielding a variety of unsymmetrical biaryls in good to
[
2
excellent yields. This new heterogeneous palladium catalyst exhibits high catalytic
activity and can be recovered by a simple filtration of the reaction solution and
recycled for at least 10 consecutive trials without any decreases in activity. Our
system not only avoids the use of phosphine ligands, but also solves the basic problem
of palladium catalyst recovery and reuse.
Keywords: Cross-coupling; Supported palladium catalyst; Triarylbismuth; MCM-41;
Heterogeneous catalysis
1
. Introduction
1
Biaryl compounds are widely used as chiral phosphine ligands, monomers of
2
functional polymers, and as important intermediates in the preparation of natural
3
products, agrochemicals, and pharmaceutics. Among numerous methods accessing to

ACCEPTED MANUSCRIPT
4
biaryl structures, the palladium-catalyzed cross-coupling reaction of organometallic
5
6
compounds with aryl halides or triflates such as the Suzuki-Miyaura, Stille, and
7
Hiyama coupling reactions is one of the most important synthetic methods for the
construction of unsymmetrical biaryls. Although various organometallic compounds
such as organoboron, -tin, -silicon, -zinc, and -magnesium compounds have been
successfully used for the cross-coupling reactions, organobismuth compounds have
8
not been well explored. Organobismuth compounds are potentially useful candidates
for environmentally benign reagents since bismuth is known to be a low-level toxic
9
element. Importantly, organobismuth compounds can be easily prepared through
1
0
standard procedures. Triarylbismuths, unlike organoboron, organotin, and other
11
organometallic reagents, can react with three equivalents of an electrophilic reagent.
Recently, palladium-catalyzed cross-coupling reactions of organobismuth compounds
1
2
with electrophilic reagents for C–C bond formation have been reported. It is note-
worthy that only para- or meta-substituted triarylbismuths are used as the coupling
partners due to the steric requirement for this type of transformation. Among the
limited successful examples for the construction of C–C bonds, homogeneous palla-
dium complexes such as Pd(PPh ) , Pd(OAc) , or PdCl are usually used as catalysts
3
4
2
2
for these coupling reactions. However, these homogeneous palladium catalysts are
expensive, cannot be recycled, and difficult to separate from the product mixture,
which may have a very serious negative impact on their possible industrial appli-
cations, especially the pharmaceutical industry. In contrast, heterogeneous catalysts
can be easily separated from the reaction mixture by simple filtration and reused in
2

ACCEPTED MANUSCRIPT
successive reactions provided that the active sites have not become deactivated.
Heterogeneous catalysis also helps to minimize wastes derived from reaction workup,
1
3
contributing to the development of green chemical processes. Thus, the development
of supported palladium catalysts showing a much higher catalytic activity without
leaching is highly desirable. So far, supported palladium catalysts have successfully
been used for the Heck reaction, the Suzuki-Miyaura reaction, the Sonogashira
1
4
reaction, Hiyama reaction, and the Stille reaction, etc. In spite of the significant
advances in this area, there are very few reports that employ the heterogeneous
palladium complexes as catalysts for the cross-coupling reactions of triarylbismuths
1
5
with electrophiles.
The discovery of mesoporous material MCM-41 has given an enormous stimulus to
research in heterogeneous catalysis and provided a new possible candidate for a solid
16
support for immobilizing homogeneous catalysts. MCM-41 has a regular pore
2
-1
diameter of ca.5 nm and a specific surface area > 700 m g and rich silanol groups in
1
7
the inner walls. To date, functionalized MCM-41-immobilized palladium, rhodium,
molybdenum, and copper complexes have been prepared and successfully used in
1
8
organic reactions. In continuation of our efforts to develop greener synthetic path-
1
8g-j
ways for organic transformations,
we herein report the synthesis of an MCM-41-
immobilized palladium(II)-Schiff base complex [MCM-41-N,N-Pd(OAc) ] and its
2
successful application to the atom-efficient cross-coupling of triarylbismuths with aryl
iodides. The new heterogeneous palladium catalyst exhibits high catalytic activity in
the reaction and can easily be separated from the reaction mixture by a simple
3

ACCEPTED MANUSCRIPT
filtration of the reaction solution, and its catalytic efficiency remains unaltered even
after recycling ten times.
2
. Results and discussion
Although phosphine ligands can stabilize palladium and influence its reactivity, the
simplest and cheapest palladium catalysts are of course phosphine-free systems,
specifically when used in low loading. It is well known that the catalysts containing
1
9
phosphine ligands at higher temperatures are unstable. Furthermore, the procedure
for preparing the supported phosphine palladium complexes is rather complicated
since the synthesis of the phosphine ligands requires multi-step sequences. Therefore,
the development of phosphine-free heterogeneous palladium catalysts having a high
activity and good stability is a topic of enormous importance. A novel MCM-41-
immobilized palladium(II)-Schiff base complex [MCM-41-N,N-Pd(OAc) ] was easily
2
2
0
synthesized starting from mesoporous material MCM-41, 3-aminopropyltriethoxy-
silane, pyridine-2-carboxaldehyde and Pd(OAc) according to Scheme 1. Firstly, the
2
reaction of 3-aminopropyltriethoxysilane with mesoporous material MCM-41 in
toluene at 100 °C for 24 h, followed by the silylation with Me SiCl in toluene at room
3
temperature for 24 h gave 3-aminopropyl-functionalized MCM-41 (MCM-41-NH2).
The latter was subsequently treated with pyridine-2-carboxaldehyde in dry ethanol at
8
0 °C for 12 h to afford the Schiff base-functionalized MCM-41 (MCM-41-N,N),
which reacted with Pd(OAc) in acetone under reflux for 72 h to generate the
2
MCM-41-immobilized palladium(II)-Schiff base complex [MCM-41-N,N-Pd(OAc)2]
4

ACCEPTED MANUSCRIPT
as a light yellow powder.
The small angle X-ray powder diffraction (XRD) analysis of the MCM-41-N,N-
Pd(OAc) indicated that, in addition to an intense diffraction peak (100), two higher
2
order diffraction peaks (110) and (200) were also detected and became weak and
diffuse, which could be due to contrast matching between the silicate framework and
organic moieties which are located inside the channels of MCM-41, therefore the
chemical bonding procedure did not diminish the structural ordering of the parent
MCM-41. Elemental analyses and X-ray photoelectron spectroscopy (XPS) were used
to characterize the MCM-41-immobilized palladium(II)-Schiff base complex. The N :
Pd mole ratio of the MCM-41-N,N-Pd(OAc) was determined to be 5.6. The XPS data
2
for MCM-41-N,N-Pd(OAc) , MCM-41-N,N, Pd(OAc) and metal Pd are listed in
2
2
Table 1. It can be seen that the binding energies of Si and O of MCM-41-N,N-
2p
1s
Pd(OAc) are similar to those of MCM-41-N,N. However the difference of N1s
2
binding energies between MCM-41-N,N-Pd(OAc) and MCM-41-N,N is 1.1 eV. The
2
binding energy of Pd3d5/2 in MCM-41-N,N-Pd(OAc) is 0.9 eV less than that in
2
5

ACCEPTED MANUSCRIPT
Pd(OAc) , but 1.9 eV larger than that in metal Pd. These results show that a
2
coordination bond between N and Pd is formed in MCM-41-N,N-Pd(OAc)2.
Table 1 XPS data for MCM-41-N,N-Pd(OAc) , MCM-41-N,N, Pd(OAc) and metal
2
2
a
Pd.
Sample
Pd3d5/2
N1s
Si2p
O1s
MCM-41-N,N-Pd(OAc)2 337.4
MCM-41-N,N
400.8
399.7
103.4
103.3
533.2
533.1
Pd(OAc)2
Metal Pd
338.3
335.5
a
The binding energies are referenced to C1s (284.6 eV) and the energy differences were
determined with an accuracy of ± 0.2 eV.
In our initial screening experiments, the cross-coupling of BiPh (1.0 equiv.) with
3
4
'-iodoacetophenone (3.2 equiv.) in the presence of MCM-41-N,N-Pd(OAc) was
2
chosen as the model reaction to optimize the reaction conditions and the results are
summarized in Table 2. At first, the base effect was examined with NMP as the
solvent at 100 ºC (Table 2, entries 1-9). It is evident that good yields were obtained
when inorganic bases such as CsF, K CO , KOAc and K PO were used and K CO
3
2
3
3
4
2
was the most effective (Table 2, entry 2), whereas NaOH and NaHCO afforded low
3
yields and organic bases such as Et N, Bu N and DBU were ineffective (Table 2,
3
3
entries 5-9), so K CO was finally selected as the base for the reaction. Our next
2
3
studies focused on the effect of solvent on the model reaction. Among the solvents
examined, NMP was found to be the best choice (Table 2, entry 2), DMF and DMSO
also afforded good yields (Table 2, entries 10 and 11). While other solvents such as
DME, EtOH, and MeCN were substantially less effective (Table 1, entries 12-14).
6

ACCEPTED MANUSCRIPT
Finally, the effect of reaction temperature on the model reaction was also investigated
and 110 ºC was found to be optimal, reducing reaction temperature to 80 °C resulted
in a decrease in yield (Table 2, entries 2, 15-17). Therefore, the optimal catalytic
system involved the use of MCM-41-N,N-Pd(OAc) (2 mol%), K CO (4.0 equiv.) in
2
2
3
NMP at 110 °C under Ar for 5 h (Table 2, entry 16). Furthermore, the atom efficiency
of triphenylbismuth, for which all three phenyl groups efficiently coupled with 3
equiv. of electrophilic coupling partner, was thoroughly established.
Table 2 Cross-coupling reaction of BiPh with 4'-iodoacetophenone (3.2 equiv.) in
3
a
different conditions.
b
Entry
Base
CsF
Solvent
Temp. (ºC)
Yield (%)
1
2
3
4
5
6
7
8
9
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
NMP
DMF
DMSO
DME
MeCN
EtOH
NMP
NMP
NMP
100
100
100
100
100
100
100
100
100
100
100
100
100
100
80
80
84
73
77
33
40
0
K CO3
2
KOAc
K PO4
3
NaOH
NaHCO3
Et N
3
Bu N
0
3
DBU
0
10
K CO3
2
76
79
49
43
31
61
91
90
11
K CO3
2
12
13
14
15
16
17
K CO3
2
K CO3
2
K CO3
2
K CO3
2
K CO3
2
110
120
K CO3
2
7

ACCEPTED MANUSCRIPT
a
All reactions were performed using 1.0 mmol of BiPh , 3.2 mmol of 4'-iodoacetophenone, 4.0
3
b
mmol of base in 3.0 mL of solvent under Ar for 5 h. Isolated yield based on BiPh used.
3
To examine the scope for this heterogeneous cross-coupling reaction, we have
investigated the reactions using a variety of aryl iodides and different triarylbismuths
as the substrates under the optimized reaction conditions (Scheme 2) and the results
are outlined in Table 3. As shown in Table 3, the cross-coupling reaction of BiPh3
with a variety of aryl iodides proceeded smoothly under the optimized conditions,
affording the corresponding biaryls 3a-i in good to excellent yields (entries 1-9).
Various electron-donating and electron-withdrawing groups such as methyl, methoxy,
chloro, nitro, ketone and ester on the benzene ring were well tolerated. The reactivity
of aryl iodides having electron-withdrawing groups was higher than that of aryl
iodides having electron-donating groups. For example, the reactions of 4'-iodoaceto-
phenone, methyl 4-iodobenzoate, 4-chloroiodobenzene, 4-cyanoiodobenzene, 4-nitro-
iodobenzene and 3-nitroiodobenzene afforded the desired coupled products 3a-3f in
8
5-93% yields within 5 h, while the reaction of 4-iodoanisole gave 3h in only 62%
yield after 24 h. The sterically hindered 2-iodotoluene also showed lower reactivity
and afforded 3i in 67% yield after 24 h (entry 9). However, the reaction of bulky
1
-iodonaphthalene with BiPh provided 89% yield of the desired product 3j under the
3
optimized reaction conditions (entry 10). In addition, the cross-coupling reaction of
heteroaryl iodides such as 2-iodopyridine and 2-iodothiophene with BiPh also
3
proceeded smoothly to give the corresponding coupled products 3k and 3l in good
yields (entries 11 and 12). The activity of this phosphine-free heterogeneous palla-
8

ACCEPTED MANUSCRIPT
dium catalyst is comparable to that of Pd(PPh ) . For example, the cross-coupling
3
4
reaction of 4'-iodoacetophenone (3.2 equiv.) with BiPh in the presence of 2 mol% of
3
MCM-41-N,N-Pd(OAc) in NMP using K CO (4 equiv.) as base at 110 °C for 5 h
2
2
3
gave a 91% yield of the desired product 3a (entry 1), the same reaction in the
presence of 5 mol% of Pd(PPh ) in NMP using K CO (4 equiv.) as base at 100 °C
3
4
2
3
1
2a
for 6 h gave 3a in 86% yield. In addition, use of lower palladium loading is the
attractive advantage of our phosphine-free heterogeneous palladium catalytic system.
The optimized reaction conditions were also applied to the cross-coupling reactions
of substituted triphenylbismuths such as tri(4-methylphenyl)bismuth and tri(4-chloro-
phenyl)bismuth with a variety of aryl and heteroaryl iodides, the results are also
summarized in Table 3. Various electron-donating and electron-withdrawing groups
such as methyl, cyano, chloro, nitro, ketone and ester on both aryl iodides and
triarylbismuths could be tolerated to give the desired biaryls 3m-3z in good to
excellent yields (entries 13-27). The method provides a quite general route for the
synthesis of unsymmetrical biaryls having various functionalities. The results above
prompted us to investigate the cross-coupling reaction of triarylbismuths with other
9

ACCEPTED MANUSCRIPT
aryl halides such as aryl bromides, aryl chlorides and aryl triflates, but these aryl
electrophiles were not reactive under heterogeneous catalysis even if the reaction was
carried out at higher temperatures or using CsF as base.
a
Table 3 Synthesis of a variety of biaryls.
b
Entry
Ar
R
Time (h)
Product
Yield (%)
1
2
3
4
5
6
7
8
9
4-MeCOC H4
H
5
3a
3b
3c
3d
3e
3f
91
90
85
93
90
87
79
62
67
89
72
75
90
87
84
61
75
68
86
88
92
87
91
70
6
4-CH OCOC H
H
5
3
6
4
4-ClC H4
H
5
6
4-O NC H
H
5
2
6
4
3-O NC H
H
5
2
6
4
4-NCC H4
H
5
6
Ph
H
6
3g
3h
3i
4-CH OC H
4
H
24
24
5
3
6
2-CH C H
4
H
3
6
10
1-naphthyl
2-pyridyl
2-thienyl
H
3j
11
H
6
3k
3l
12
13
14
15
16
17
18
19
20
21
22
23
24
H
6
4-MeCOC H4
4-CH3
4-CH3
4-CH3
4-CH3
4-CH3
4-CH3
4-Cl
4-Cl
4-Cl
4-Cl
4-Cl
4-Cl
5
3m
3n
3o
3p
3q
3r
3s
6
3-CH OCOC H
5
3
6
4
4-ClC H4
5
6
2-CH C H
4
24
5
3
6
2-pyridyl
2-thienyl
5
4-ClC H4
7
6
4-MeCOC H4
5
3t
6
3-O NC H
4
5
3u
3v
3w
3o
2
6
4-NCC H4
6
6
3-CH OCOC H
5
3
6
4
4-CH C H
4
24
3
6
1
0

ACCEPTED MANUSCRIPT
2
2
2
5
6
7
2-CH C H
4
4-Cl
4-Cl
4-Cl
24
6
3x
3y
3z
63
74
72
3
6
2-pyridyl
2-thienyl
7
a
Reaction was carried out with BiAr (1 mmol), aryl iodide (3.2 mmol), K CO (4 mmol) and 2
3
2
3
b
mol% palladium catalyst in NMP (3 mL) at 110 °C under Ar. Isolated yields.
In order to determine whether the catalysis was due to the MCM-41-N,N-Pd(OAc)2
complex or to a homogeneous palladium complex that comes off the support during
the reaction and then returns to the support at the end, we performed the hot filtration
2
1
test. We focused on the cross-coupling reaction of 1-iodonaphthalene with BiPh .
3
We filtered off the MCM-41-N,N-Pd(OAc) complex after 2 h of reaction time and
2
allowed the filtrate to react further. The catalyst filtration was performed at the
reaction temperature (110 °C) in order to avoid possible recoordination or precipi-
tation of soluble palladium upon cooling. We found that, after this hot filtration, no
further reaction was observed, indicating that leached palladium species from the
catalyst (if any) are not responsible for the observed activity. This result suggests that
the palladium catalyst remains on the support at elevated temperatures during the
reaction and points to a process of heterogeneous nature.
For a heterogeneous transition-metal catalyst, it is important to examine its ease of
separation, recoverability and reusability. This heterogeneous palladium catalyst can
be easily separated and recovered by a simple filtration of the reaction solution. We
next investigated the possibility to reuse of the catalyst by using the cross-coupling
reaction of 4-nitroiodobenzene with BiPh . After carrying out the reaction, the catalyst
3
was recovered by simple filtration and washed with distilled water, NMP and diethyl
ether. After being air-dried, it can be reused directly without further purification. The
11

ACCEPTED MANUSCRIPT
recovered palladium catalyst was used in the next run, and almost consistent activity
was observed for ten consecutive cycles (Figure 1). In addition, palladium leaching in
the supported catalyst was also determined. The palladium content of the catalyst was
found by ICP analysis to be 0.40 mmol/g after ten consecutive runs, only 2% of
palladium had been lost from the MCM-41 support. Generally, the continuous recycle
of resin-supported palladium catalysts results in a decrease in their activity within a
five-recycle run owing to leaching of the palladium species from the polymer supports.
The high stability and excellent reusability of the catalyst should result from the
chelating action of bidentate Schiff base ligand on palladium and the mesoporous
structure of the MCM-41 support. The result is important from a practical point of
view. The high catalytic activity, excellent reusability and the easy accessibility of the
MCM-41-N,N-Pd(OAc) complex make them a highly attractive heterogeneous
2
palladium catalyst for the parallel solution phase synthesis of diverse libraries of
compounds.
100
80
60
40
20
0
1
2
3
4
5
6
7
8
9
10
Reused times
Figure 1. Recycle of the MCM-41-N,N-Pd(OAc) catalyst.
2
1
2

ACCEPTED MANUSCRIPT
3
. Conclusion
In summary, we have developed a novel, phosphine-free, practical and economic
catalyst system for the atom-efficient cross-coupling reaction of triarylbismuths with
aryl iodides by using an MCM-41-immobilized palladium(II)-Schiff base complex
[
MCM-41-N,N-Pd(OAc) ] as catalyst and K CO as base in NMP. This new hetero-
2 2 3
geneous palladium catalyst can be conveniently prepared by a simple procedure from
commercially available and inexpensive reagents and exhibits high catalytic activity.
More importantly, the catalyst can easily be recovered by a simple filtration of the
reaction solution and recycled for at least 10 times without any decreases in activity
.
The atom-efficient cross-coupling reaction of triarylbismuths with aryl iodides
catalyzed by the MCM-41-N,N-Pd(OAc) complex provides a better and practical
2
procedure for the synthesis of a variety of unsymmetrical biaryls.
4
4
. Experimental
.1. Physical measurements and materials
All chemicals were reagent grade and used as purchased. All solvents were dried
10a,b
and distilled before use. Triarylbismuths were prepared by standard protocols.
The
products were purified by flash chromatography on silica gel. Mixture of EtOAc and
hexane was generally used as eluent. All cross-coupling products were characterized
by comparison of their spectra and physical data with authentic samples. IR spectra
1
were determined on a Perkin-Elmer 683 instrument. H NMR spectra were recorded
1
3

ACCEPTED MANUSCRIPT
on a Bruker Avance 400 MHz spectrometer with TMS as an internal standard in
13
CDCl as solvent. C NMR spectra (100 MHz) were recorded on a Bruker Avance
3
4
00 MHz spectrometer in CDCl as solvent. Melting points are uncorrected.
3
Palladium content was determined with inductively coupled plasma atom emission
Atomscan16 (ICP-AES, TJA Corporation). X-ray powder diffraction was obtained on
Damax–γA (Rigaku). X-ray photoelectron spectra was recorded on XSAM 800
(Kratos). Microanalyses were measured by using a Yanaco MT-3 CHN micro-
elemental analyzer.
4
.2. Preparation of the Schiff base-functionalized MCM-41 (MCM-41-N,N)
A solution of 2.2 g of 3-aminopropyltriethoxysilane in 15 mL of dry chloroform
was added to a suspension of 2.8 g of the MCM-41 in 180 mL of dry toluene. The
mixture was stirred for 24 h at 100 °C. Then the solid was filtered and washed by
CHCl (2 × 20 mL), and dried in vacuum at 160 °C for 5 h. The product was then
3
soaked in a solution of 4.5 g of Me SiCl in 80 mL of dry toluene at room temperature
3
under stirring for 24 h. Then the solid was filtered, washed with acetone (3 × 20 mL)
and diethyl ether (3 × 20 mL), and dried in vacuum at 120 °C for 5 h. The dried white
solid (3.3 g) was then reacted with pyridine-2-carboxaldehyde (0.502 g, 4.7 mmol) in
2
0 mL of dry ethanol at 80 °C for 12 h. The solid product was filtered, washed with
ethanol (3 × 20 mL) and diethyl ether (20 mL), and dried in vacuum at 120 °C for 5 h
to obtain 3.45 g of hybrid material MCM-41-N,N. The nitrogen content was found to
be 2.42 mmol/g by elemental analysis.
4
.3. Preparation of the MCM-41-N,N-Pd(OAc) catalyst
2
1
4

ACCEPTED MANUSCRIPT
In a small Schlenk tube, 2.50 g of the above-functionalized MCM-41 material
(
MCM-41-N,N) was mixed with 0.274 g (1.22 mmol) of Pd(OAc) in 50 mL of dry
2
acetone. The mixture was refluxed for 72 h under an argon atmosphere. The solid
product was filtered by suction, washed with acetone, distilled water and acetone
successively and dried at 70 °C/26.7 Pa under Ar for 5 h to give 2.63 g of a light
yellow palladium complex [MCM-41-N,N-Pd(OAc) ]. The nitrogen and palladium
2
content was found to be 2.29 mmol/g and 0.41 mmol/g, respectively.
4
.4. Typical procedure for the heterogeneous cross-coupling reaction of aryl
iodides with triarylbismuths
An oven-dried Schlenk tuble equipped with a magnetic stirring bar was charged
with MCM-41-N,N-Pd(OAc) (49 mg, 0.02 mmol Pd), aryl iodide (3.2 mmol),
2
triarylbismuth (1.0 mmol), and K CO (4.0 mmol) followed by anhydrous NMP (3
2
3
mL) under Ar. The reaction mixture was stirred in an oil bath at 110 °C for 5-24 h.
The reaction mixture was cooled to room temperature and filtered. The MCM-41-
N,N-Pd(OAc) complex was washed with distilled water (2 × 5 mL), NMP (2 × 5 mL)
2
and Et O (2 × 5 mL) and reused in the next run. The filtrate was quenched with water,
2
and extracted with ethyl acetate (2 × 30 mL). The combined ethyl acetate extract was
washed with dilute hydrochloric acid (10 mL), saturated sodium bicarbonate solution
(10 mL), brine (2 × 10 mL), and dried over anhydrous magnesium sulfate. The
solvent was removed under reduced pressure and the residue was purified by flash
column chromatography on silica gel.
2
2
4
.4.1. 4-Acetylbiphenyl (3a). White solid, m.p. 118–119 °C (ref. m.p. 120–121 °C).
1
5

ACCEPTED MANUSCRIPT
1
H NMR (400 MHz, CDCl ): δ = 8.03 (d, J = 8.0 Hz, 2H), 7.68 (d, J = 8.0 Hz, 2H),
3
7
.62 (d, J = 7.6 Hz, 2H), 7.47 (t, J = 7.6 Hz, 2H), 7.40 (t, J = 7.6 Hz, 1H), 2.64 (s, 3H).
1
3
C NMR (100 MHz, CDCl ): δ = 197.8, 145.8, 139.9, 135.9, 129.0, 128.9, 128.3,
3
-1
1
27.3, 127.2, 26.7. IR (KBr, cm ): 1681, 1639, 1618, 1265, 1069, 954, 766.
2
2
4
.4.2. 4-Methoxycarbonylbiphenyl (3b). White solid, m.p. 115–116 °C (ref. m.p.
1
1
17–118 °C). H NMR (400 MHz, CDCl ): δ = 8.11 (d, J = 8.0 Hz, 2H), 7.66 (d, J =
3
8
3
1
.0 Hz, 2H), 7.62 (d, J = 8.0 Hz, 2H), 7.47 (t, J = 7.6 Hz, 2H), 7.39 (t, J = 7.6 Hz, 1H),
1
3
.94 (s, 3H). C NMR (100 MHz, CDCl ): δ = 167.0, 145.7, 140.0, 130.1, 129.0,
3
-1
28.9, 128.2, 127.3, 127.1, 52.2. IR (KBr, cm ): 1718, 1607, 1565, 1438, 1290, 1271,
115, 1071, 752.
1
2
2
1
4
.4.3. 4-Chlorobiphenyl (3c). White solid, m.p. 76–77 °C (ref. m.p. 78–79 °C). H
NMR (400 MHz, CDCl ): δ = 7.55 (d, J = 7.6 Hz, 2H), 7.52 (d, J = 8.4 Hz, 2H),
3
1
3
7
1
7
.46-7.34 (m, 5H). C NMR (100 MHz, CDCl ): δ = 140.0, 139.7, 133.4, 128.9,
3
-1
28.8, 128.4, 127.6, 127.0. IR (KBr, cm ): 3067, 3035, 1594, 1479, 1400, 1099, 833,
59.
2
2
4
.4.4. 4-Nitrobiphenyl (3d). Yellow solid, m.p. 112–113 °C (ref. m.p. 112–114 °C).
1
H NMR (400 MHz, CDCl ): δ = 8.29 (d, J = 8.4 Hz, 2H), 7.73 (d, J = 8.4 Hz, 2H),
3
1
3
7
1
1
.63 (d, J = 8.0 Hz, 2H), 7.53-7.44 (m, 3H). C NMR (100 MHz, CDCl ): δ = 147.7,
3
-1
47.1, 138.8, 129.2, 129.0, 127.8, 127.4, 124.1. IR (KBr, cm ): 1640, 1596, 1576,
514, 1347, 1118, 1070, 854, 741.
1
5b
1
4
.4.5. 3-Nitrobiphenyl (3e). Yellow solid, m.p. 60–61 °C (ref. m.p. 60–61 °C). H
1
6

ACCEPTED MANUSCRIPT
NMR (400 MHz, CDCl ): δ = 8.43 (s, 1H), 8.18 (d, J = 8.4 Hz, 1H), 7.90 (d, J = 8.0
3
1
3
Hz, 1H), 7.63-7.57 (m, 3H), 7.51-7.40 (m, 3H). C NMR (100 MHz, CDCl ): δ =
3
-1
1
48.7, 142.8, 138.6, 133.0, 129.7, 129.2, 128.5, 127.1, 122.0, 121.9. IR (KBr, cm ):
1
640, 1596, 1576, 1514, 1347, 1118, 1070, 854, 741.
2
2
1
4
.4.6. 4-Cyanobiphenyl (3f). White solid, m.p. 86–87 °C (ref. m.p. 85–86 °C). H
NMR (400 MHz, CDCl ): δ = 7.70 (d, J = 8.4 Hz, 2H), 7.66 (d, J = 8.4 Hz, 2H), 7.58
3
1
3
(
d, J = 8.0 Hz, 2H), 7.48 (t, J = 7.6 Hz, 2H), 7.41 (t, J = 7.6 Hz, 1H). C NMR (100
MHz, CDCl ): δ = 145.6, 139.1, 132.6, 129.1, 128.7, 127.7, 127.2, 119.0, 110.9. IR
3
-1
(
KBr, cm ): 2227, 1641, 1606, 1566, 1485, 1136, 1072, 956, 848, 771.
2
2
1
4
.4.7. Biphenyl (3g). White solid, m.p. 68–69 °C (ref. m.p. 69–70 °C). H NMR
(
400 MHz, CDCl ): δ = 7.54 (d, J = 8.0 Hz, 4H), 7.38 (t, J = 7.6 Hz, 4H), 7.28 (t, J =
3
1
3
7
.6 Hz, 2H). C NMR (100 MHz, CDCl ): δ = 141.3, 128.9, 127.4, 127.3. IR (KBr,
3
-1
cm ): 1640, 1619, 1564, 1137, 1072, 955, 863, 731.
2
2
1
4
.4.8. 4-Methoxybiphenyl (3h). White solid, m.p. 89–90 °C (ref. m.p. 87–88 °C). H
NMR (400 MHz, CDCl ): δ = 7.55 (d, J = 7.6 Hz, 2H), 7.53 (d, J = 8.8 Hz, 2H), 7.42
3
1
3
(
t, J = 7.6 Hz, 2H), 7.30 (t, J = 7.2 Hz, 1H), 6.98 (d, J = 8.8 Hz, 2H), 3.85 (s, 3H). C
NMR (100 MHz, CDCl ): δ = 159.1, 140.8, 133.8, 128.7, 128.2, 126.8, 126.7, 114.2,
3
-1
5
5.4. IR (KBr, cm ): 2920, 1607, 1489, 1252, 1202, 1036, 834, 761.
2
3 1
4
.4.9. 2-Methylbiphenyl (3i). Oil. H NMR (400 MHz, CDCl ): δ = 7.39 (t, J = 7.6
3
13
Hz, 2H), 7.35-7.29 (m, 3H), 7.28-7.20 (m, 4H), 2.26 (s, 3H). C NMR (100 MHz,
CDCl ): δ = 142.0, 135.4, 130.4, 129.9, 129.3, 128.1, 127.3, 126.9, 126.8, 125.8, 20.6.
3
1
7

ACCEPTED MANUSCRIPT
-1
IR (film, cm ): 3060, 3021, 2925, 1599, 1480, 1440, 1381, 1010, 748, 702.
2
4 1
4
.4.10. 1-Phenylnaphthalene (3j). Oil. H NMR (400 MHz, CDCl ): δ = 7.91-7.80
3
1
3
(
m, 3H), 7.55-7.36 (m, 9H). C NMR (100 MHz, CDCl ): δ = 140.9, 140.4, 133.9,
3
1
31.7, 130.2, 128.8, 128.4, 127.8, 127.4, 127.3, 127.1, 126.1, 125.9, 125.5. IR (film,
-1
cm ): 3057, 1592, 1507, 1494, 1447, 1395, 802, 778, 761, 703.
2
5 1
4
.4.11. 2-Phenylpyridine (3k). Oil. H NMR (400 MHz, CDCl ): δ = 8.67 (t, J = 1.2
3
Hz, 1H), 8.01-7.96 (m, 2H), 7.71-7.66 (m, 2H), 7.48-7.36 (m, 3H), 7.20-7.15 (m, 1H).
1
3
C NMR (100 MHz, CDCl ): δ = 157.5, 149.7, 139.4, 136.8, 129.0, 128.8, 126.9,
3
-1
1
22.1, 120.6. IR (film, cm ): 3062, 1587, 1565, 1468, 1449, 1425, 1152, 1020, 746,
6
94.
2
5
1
4
.4.12. 2-Phenylthiophene (3l). White solid, m.p. 36–37 °C (ref. m.p. 37–38 °C). H
NMR (400 MHz, CDCl ): δ = 7.59-7.55 (m, 2H), 7.35-7.18 (m, 5H), 7.04-7.01 (m,
3
1
3
1
1
8
H). C NMR (100 MHz, CDCl ): δ = 144.6, 134.5, 129.0, 128.2, 127.6, 126.1,
3
-1
24.9, 123.2. IR (KBr, cm ): 3073, 3027, 1600, 1531, 1488, 1446, 1256, 1211, 1073,
50, 827, 756, 699.
1
2e
4
1
8
3
1
.4.13. 4-Acetyl-4'-methylbiphenyl (3m). White solid, m.p. 102–103 °C (ref. m.p.
1
03–104 °C). H NMR (400 MHz, CDCl ): δ = 8.00 (d, J = 8.0 Hz, 2H), 7.65 (d, J =
3
.0 Hz, 2H), 7.52 (d, J = 7.6 Hz, 2H), 7.27 (d, J = 7.6 Hz, 2H), 2.62 (s, 3H), 2.40 (s,
1
3
H). C NMR (100 MHz, CDCl ): δ = 197.7, 145.7, 138.2, 136.9, 135.6, 129.7,
3
-1
28.9, 127.1, 126.9, 26.6, 21.2. IR (KBr, cm ): 1679, 1640, 1603, 1563, 1398, 1268,
137, 1070, 807.
1
1
8

ACCEPTED MANUSCRIPT
2
4
4
.4.14. 3-Methoxycarbonyl-4'-methylbiphenyl (3n). White solid, m.p. 92–93 °C (ref.
1
m.p. 91–92 °C). H NMR (400 MHz, CDCl ): δ = 8.26 (s, 1H), 7.98-7.96 (m, 1H),
3
7
.75-7.72 (m, 1H), 7.50 (d, J = 8.0 Hz, 2H), 7.46 (t, J = 7.6 Hz, 1H), 7.24 (d, J = 8.0
1
3
Hz, 2H), 3.92 (s, 3H), 2.38 (s, 3H). C NMR (100 MHz, CDCl ): δ = 167.1, 141.4,
3
1
37.6, 137.2, 131.3, 130.7, 129.7, 128.8, 128.1, 128.0, 127.0, 52.2, 21.1. IR (KBr,
-1
cm ): 2953, 1722, 1642, 1602, 1583, 1435, 1311, 1250, 1112, 1081, 815, 758.
2
6
4
1
7
.4.15. 4-Chloro-4'-methylbiphenyl (3o). White solid, m.p. 122–123 °C (ref. m.p.
1
22–123 °C). H NMR (400 MHz, CDCl ): δ = 7.47 (d, J = 7.6 Hz, 2H), 7.43 (d, J =
3
13
.6 Hz, 2H), 7.36 (d, J = 8.0 Hz, 2H), 7.22 (d, J = 8.0 Hz, 2H), 2.37 (s, 3H). C NMR
(
100 MHz, CDCl ): δ = 139.6, 137.5, 137.1, 133.1, 129.6, 128.9, 128.2, 126.9, 21.1.
3
-1
IR (KBr, cm ): 1638, 1618, 1563, 1415, 1261, 1138, 1122, 1067, 952, 864.
2
5 1
4
7
1
.4.16. 4-Methyl-2'-methylbiphenyl (3p). Oil. H NMR (400 MHz, CDCl ): δ =
3
1
3
.26-7.13 (m, 8H), 2.39 (s, 3H), 2.27 (s, 3H). C NMR (100 MHz, CDCl ): δ = 142.0,
3
39.1, 136.4, 135.5, 130.4, 129.9, 129.2, 128.9, 127.1, 125.8, 21.2, 20.6. IR (film,
-1
cm ): 3021, 2922, 1660, 1602, 1516, 1483, 1453, 1109, 1007, 822, 757, 728.
2
5 1
4
8
2
1
1
.4.17. 2-(4-Methylphenyl)pyridine (3q). Oil.
H NMR (400 MHz, CDCl ): δ =
3
.66-8.64 (m, 1H), 7.88 (d, J = 7.2 Hz, 2H), 7.65 (t, J = 2.8 Hz, 2H), 7.26-7.22 (m,
1
3
H), 7.16-7.11 (m, 1H), 2.37 (s, 3H). C NMR (100 MHz, CDCl ): δ = 157.5, 149.7,
3
-1
49.6, 138.9, 136.7, 129.5, 126.8, 121.8, 120.2, 21.3. IR (film, cm ): 3008, 2920,
662, 1615, 1589, 1563, 1467, 1433, 1299, 1185, 1152, 1016, 829, 773, 742.
2
5
4
.4.18. 2-(4-Methylphenyl)thiophene (3r). White solid, m.p. 63–64 °C (ref. m.p.
1
9

ACCEPTED MANUSCRIPT
1
6
2
0–62 °C). H NMR (400 MHz, CDCl ): δ = 7.50 (d, J = 8.0 Hz, 2H), 7.27-7.21 (m,
3
1
3
H), 7.18 (d, J = 8.0 Hz, 2H), 7.06 (t, J = 4.4 Hz, 1H), 2.36 (s, 3H). C NMR (100
MHz, CDCl ): δ = 144.6, 137.3, 131.7, 129.6, 127.9, 125.9, 124.3, 122.6, 21.2. IR
3
-1
(
KBr, cm ): 2919, 2851, 1637, 1501, 1431, 851, 809, 687.
1
5b
4
1
8
.4.19. 4,4'-Dichlorobiphenyl (3s). White solid, m.p. 148–149 °C (ref.
m.p.
1
47–149 °C). H NMR (400 MHz, CDCl ): δ = 7.46 (d, J = 8.0 Hz, 4H), 7.39 (d, J =
3
1
3
.0 Hz, 4H). C NMR (100 MHz, CDCl ): δ = 138.4, 133.8, 129.1, 128.2. IR (KBr,
3
-1
cm ): 1641, 1564, 1475, 1139, 1089, 815.
1
2e
4
1
8
.4.20. 4-Acetyl-4'-chlorobiphenyl (3t). White solid, m.p. 101–102 °C (ref. m.p.
1
04–105 °C). H NMR (400 MHz, CDCl ): δ = 8.03 (d, J = 8.4 Hz, 2H), 7.64 (d, J =
3
13
.4 Hz, 2H), 7.55 (d, J = 8.0 Hz, 2H), 7.43 (d, J = 8.0 Hz, 2H), 2.64 (s, 3H). C NMR
(
100 MHz, CDCl ): δ = 197.6, 144.4, 138.3, 136.0, 134.4, 129.1, 129.0, 128.5, 127.0,
3
-1
2
6.7. IR (KBr, cm ): 1677, 1638, 1618, 1081, 985, 615.
1
5b
4
.4.21. 4-Chloro-3'-nitrobiphenyl (3u). Yellow solid, m.p. 91–92 °C (ref.
m.p.
1
9
0–92 °C). H NMR (400 MHz, CDCl ): δ = 8.39 (s, 1H), 8.22-8.18 (m, 1H), 7.87 (d,
3
J = 7.6 Hz, 1H), 7.61 (t, J = 7.6 Hz, 1H), 7.55 (d, J = 7.6 Hz, 2H), 7.45 (d, J = 7.6 Hz,
1
3
2
1
9
H). C NMR (100 MHz, CDCl ): δ = 148.8, 141.6, 137.1, 134.8, 132.8, 129.9,
3
-1
29.4, 128.4, 122.3, 121.8. IR (KBr, cm ): 1642, 1565, 1525, 1498, 1354, 1122, 1070,
56, 823.
2
7
4
.4.22. 4-Chloro-4'-cyanobiphenyl (3v). White solid, m.p. 130–131 °C (ref. m.p.
1
1
25–127 °C). H NMR (400 MHz, CDCl ): δ = 7.73 (d, J = 8.0 Hz, 2H), 7.65 (d, J =
3
2
0

ACCEPTED MANUSCRIPT
13
7
.6 Hz, 2H), 7.52 (d, J = 8.0 Hz, 2H), 7.45 (d, J = 7.6 Hz, 2H). C NMR (100 MHz,
CDCl ): δ = 144.4, 137.6, 135.0, 132.7, 129.3, 128.5, 127.6, 118.8, 111.3. IR (KBr,
3
-1
cm ): 2225, 1642, 1607, 1568, 1485, 1122, 1068, 954, 810.
1
4
.4.23. 4-Chloro-3'-methoxycarbonylbiphenyl (3w). White solid, 94–95 °C. H NMR
(
400 MHz, CDCl ): δ = 8.22 (s, 1H), 8.01 (d, J = 7.6 Hz, 1H), 7.74-7.70 (m, 1H),
3
1
3
7
.55-7.48 (m, 3H), 7.41 (d, J = 7.6 Hz, 2H), 3.94 (s, 3H). C NMR (100 MHz,
CDCl ): δ = 166.9, 140.2, 138.6, 133.9, 131.3, 130.9, 129.1, 129.0, 128.7, 128.4,
3
-1
1
28.1, 52.2. IR (KBr, cm ): 2951, 1725, 1596, 1587, 1479, 1440, 1307, 1244, 1112,
+
1
092, 755. HRMS (ESI): calcd for C H ClO [M] 246.0448; found 246.0453.
1
4
11
2
2
8 1
4
.4.24. 4-Chloro-2'-methylbiphenyl (3x). Oil. H NMR (400 MHz, CDCl ): δ = 7.37
3
1
3
(
dd, J = 8.4, 1.6 Hz, 2H), 7.27-7.15 (m, 6H), 2.25 (s, 3H). C NMR (100 MHz,
CDCl ): δ = 140.7, 140.4, 135.3, 132.8, 130.5, 130.4, 129.7, 128.3, 127.6, 125.9, 20.4.
3
-1
IR (film, cm ): 3021, 2954, 1656, 1595, 1496, 1479, 1397, 1091, 1006, 833, 759,
7
28.
2
5 1
4
8
2
1
1
.4.25. 2-(4-Chlorophenyl)pyridine (3y). Oil. H NMR (400 MHz, CDCl ): δ =
3
.69-8.66 (m, 1H), 7.93 (dd, J = 8.6, 2.2 Hz, 2H), 7.78-7.65 (m, 2H), 7.43 (dd, J = 8.4,
13
.4 Hz, 2H), 7.26-7.21 (m, 1H). C NMR (100 MHz, CDCl ): δ = 156.2, 149.5, 137.8,
3
-1
36.9, 135.1, 128.9, 128.2, 122.4, 120.3. IR (film, cm ): 3047, 3005, 1606, 1587,
562, 1464, 1434, 1087, 1012, 831, 773.
2
5
4
.4.26. 2-(4-Chlorophenyl)thiophene (3z). White solid, m.p. 82–83 °C (ref. m.p.
1
8
3–84 °C). H NMR (400 MHz, CDCl ): δ = 7.55-7.51 (m, 2H), 7.37-7.23 (m, 4H),
3
2
1

ACCEPTED MANUSCRIPT
1
3
7
1
8
.10-7.05 (m, 1H). C NMR (100 MHz, CDCl ): δ = 143.1, 133.2, 133.0, 129.0,
3
-1
28.2, 127.1, 125.2, 123.4. IR (KBr, cm ): 3076, 1530, 1486, 1428, 1404, 1095, 850,
17, 696.
Acknowledgements
We thank the National Natural Science Foundation of China (No. 21272044) and
Scientific Research Fund of Education Department of Jiangxi Province (KJLD13022)
for financial support.
References
1
. (a) Thiel, F. Angew. Chem. Int. Ed. 1999, 38, 2345–2347; (b) Nicolaou, K. C.;
Boddy, C. N. C. J. Am. Chem. Soc. 2002, 124, 10451–10455.
2
. (a) Meier, H. Angew. Chem. Int. Ed. 2005, 44, 2482–2506; (b) Tian, H.; Yang, S.
Chem. Soc. Rev. 2004, 33, 85–97; (c) Lemieux, R. P. Acc. Chem. Res. 2001, 34,
845–853.
3
. (a) Yamamoto, T.; Maruyama, T.; Zhou, Z.; Ito, T.; Fukada, T.; Yomeda, Y.;
Begum, F.; Ikeda, T.; Sasaki, S.; Takezoe, H.; Fukada, A.; Kubota, K. J. Am.
Chem. Soc. 1994, 116, 4832–4845; (b) Nicolaou, K. C.; Boddy, C. N. C.; Brase,
S.; Winssinger, N. Angew. Chem. Int. Ed. 1999, 38, 2096–2152; (c) Hassan, J.;
Penalva, V.; Lavenot, L.; Cozzi, C.; Lamaire, M. Tetrahedron 1998, 54, 13793–
1
3804; (d) Arvela, R. K.; Leadbeater, N. E. Org. Lett. 2005, 7, 2101–2104.
. Sevignon, M.; Gozzi, C.; Schulz, E.; Lemaire, M. Chem. Rev. 2002, 102,
359–1469.
4
1
5
. (a) Miyaura, N.; Suzuki, A. Chem. Rev. 1995, 95, 2475–2483; (b) Martin, R.;
Buchwald, S. L. Acc. Chem. Res. 2008, 41, 1461–1473; (c) Han, F.-S. Chem.
Soc. Rev. 2013, 42, 5270–5298; (d) Liu, L.; Dong, Y.; Pang, B.; Ma, J. J. Org.
Chem. 2014, 79, 7193–7198; (e) Gurung, S. K.; Thapa, S.; Kafle, A.; Dickie, D.
A.; Giri, R. Org. Lett. 2014, 16, 1264–1267.
2
2

ACCEPTED MANUSCRIPT
6
. (a) Stille, J. K. Angew. Chem. Int. Ed. 1986, 25, 508–524; (b) Mee, S. P. H.; Lee,
V.; Baldwin, J. E. Angew. Chem. Int. Ed. 2004, 43, 1132–1136; (c) Li, J.-H.;
Liang, Y.; Wang, D.-P.; Liu, W.-J.; Xie, Y.-X.; Yin, D.-L. J. Org. Chem. 2005, 70,
2832–2834. (d) Zhou, W.-J.; Wang, K.-H.; Wang, J.-X. J. Org. Chem. 2009, 74,
5599–5602.
7
. (a) Hiyama, T. In Metal-catalyzed Cross-Coupling Reactions; Diederich, F.;
Stang, P. J. Eds., Wiley-VCH: New York, 1998; Chapter 10; (b) Hiyama, T. J.
Organomet. Chem. 2002, 653, 58–61; (c) Denmark, S. E.; Sweis, R. F. Acc.
Chem. Res. 2002, 35, 835–846; (d) Zhang, L.; Wu, J. J. Am. Chem. Soc. 2008,
130, 12250–12251; (e) Molander, G. A.; Iannazzo, L. J. Org. Chem. 2011, 76,
9102–9108; (f) Cheng, K.; Hu, S.; Zhao, B.; Zhang, X.-M.; Qi, C. J. Org. Chem.
2013, 78, 5022–5025.
8. (a) Barton, D. H. R.; Ozbalik, N.; Ramesh, M. Tetrahedron 1988, 44,
5661–5668; (b) Suzuki, H.; Murafuji, T.; Azuma, N. J. Chem. Soc. Perkin Trans.
1 1992, 1593–1600; (c) Rao, M. L. N.; Shimada, S.; Tanaka, M. Org. Lett. 1999,
1, 1271–1274; (d) Venkatraman, S.; Li, C.-J. Tetrahedron Lett. 2001, 42,
781–784.
9
. (a) Suzuki, H.; Ikegami, T.; Matano, Y. Synthesis 1997, 249–267; (b) Elliott, G.
I.; Konopelski, J. P. Tetrahedron 2001, 57, 5683–5705.
1
1
0. (a) Organobismuth Chemistry; Suzuki, H.; Matano, Y. Eds.; Elsevier;
Amsterdam, 2001; (b) Ohe, T.; Tanaka, T.; Kuroda, M.; Cho, C. S.; Ohe, K.;
Uemura, S. Bull. Chem. Soc. Jpn. 1999, 72, 1851–1855; (c) Urano, M.; Wada, S.;
Suzuki, H. Chem. Commun. 2003, 1202–1203.
1. (a) Rao, M. L. N.; Banerjee, D.; Jadhav, D. N. Tetrahedron Lettt. 2007, 48,
6644–6647; (b) Rao, M. L. N.; Jadhav, D. N.; Banerjee, D. Tetrahedron 2008,
64, 5762–5772; (c) Rao, M. L. N.; Venkatesh, V.; Jadhav, D. N. Synlett 2009,
2597–2600; (d) Chen, J.-V.; Chen, S.-C.; Tang, Y.-J.; Mou, C.-Y.; Tsai, F.-Y. J.
Mol. Catal. A: Chem. 2009, 307, 88–92; (e) Rao, M. L. N.; Venkatesh, V.;
Jadhav, D. N. J. Organomet. Chem. 2009, 693, 2494–2498.
1
2. (a) Rao, M. L. N.; Yamazaki, O.; Shimada, S.; Tanaka, T.; Suzuki, Y.; Tanaka, M.
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ACCEPTED MANUSCRIPT
Org. Lett. 2001, 3, 4103–4105; (b) Gagnon, A.; Duplessis, M.; Alsabeh, P.;
Barabe, F. J. Org. Chem. 2008, 73, 3604–3607; (c) Shimada, S.; Yamazaki, O.;
Tanaka, T.; Rao, M. L. N.; Suzuki, Y.; Tanaka, M. Angew. Chem., Int. Ed. 2003,
42, 1845–1848; (d) Yamazaki, O.; Tanaka, T.; Shimada, S.; Suzuki, Y.; Tanaka,
M. Synlett 2004, 1921–1924; (e) Rao, M. L. N.; Banerjee, D.; Dhanorkar, R. J.
Tetrahedron Lett. 2010, 51, 6101–6104; (f) Rao, M. L. N.; Banerjee, D.;
Dhanorkar, R. J. Synlett 2011, 1324–1330.
1
3. (a) Poliakoff, M.; Fitzpatrick, J. M.; Farren, T. R.; Anastas, P. T. Science 2002,
297, 807–810; (b) Kirschnig, A.; Monenschein, H.; Wittenberg, R. Angew. Chem.
Int. Ed. 2001, 40, 650–679; (c) Clapham, B.; Reger, T. S.; Janda, K. D.
Tetrahedron 2001, 57, 4637–4662.
1
4. (a) Leadbeater, N. E.; Marco, M. Chem. Rev. 2002, 102, 3217–3274; (b) Yin, L.;
Liebscher, J. Chem. Rev. 2007, 107, 133–173; (c) Molnar, A. Chem. Rev. 2011,
111, 2251–2320.
1
5. (a) Chen, J.-V.; Chen, S.-C.; Tang, Y.-J.; Mou, C.-Y.; Tsai, F.-Y. J. Mol. Catal. A:
Chem. 2009, 307, 88–92; (b) Zhou, W.-J.; Wang, K.-H.; Wang, J.-X.; Huang,
D.-F. Eur. J. Org. Chem. 2010, 416–419; (c) Zhao, H.; Yin, L.; Cai, M. Eur. J.
Org. Chem. 2013, 1337–1345.
1
6. (a) Kresge, C. T.; Leonowicz, M. E.; Roth, W. J.; Vartuli, J. C.; Beck, J. S.
Nature 1992, 359, 710–714; (b) Jia, M.; Seifert, A.; Thiel, W. R. Chem. Mater.
2003, 15, 2174–2180; (c) Taguchi, A.; Schuth, F. Micropor. Mesopor. Mater.
2005, 77, 1–45; (d) Martin-Aranda, R. M.; Cejka, J. Top. Catal. 2010, 53,
141–153.
1
7. Beck, J. S.; Vartuli, J. C.; Roth, W. J.; Leonowicz, M. E.; Kresge, C. T.; Schmitt,
K. D.; Chu, C. T.-W.; Olson, D. H.; Sheppard, E. W.; McCullen, S. B.; Higgins,
J. B.; Schlenker, J. L. J. Am. Chem. Soc. 1992, 114, 10834–10843.
1
8. (a) Mehnert, P. C.; Weaver, D. W.; Ying, J. Y. J. Am. Chem. Soc. 1998, 120,
1
2289–12296; (b) Shyu, S.-G.; Cheng, S.-W.; Tzou, D.-L. Chem. Commun. 1999,
337–2338; (c) Mukhopadhyay, K.; Sarkar, B. R.; Chaudhari, R. V. J. Am. Chem.
2
Soc. 2002, 124, 9692–9693; (d) Nunes, C. D.; Valente, A. A.; Pillinger, M.;
2
4

ACCEPTED MANUSCRIPT
Fernandes, A. C.; Romao, C. C.; Rocha, J.; Goncalves, I. S. J. Mater. Chem.
2002, 12, 1735–1742; (e) Jia, M.; Seifert, A.; Thiel, W. R. Chem. Mater. 2003,
15, 2174–2180; (f) Baleizao, C.; Corma, A.; Garcia, H.; Leyva, A. J. Org. Chem.
2004, 69, 439–446; (g) Cai, M.; Zheng, G.; Ding, G. Green Chem. 2009, 11,
1687–1693; (h) Cai, M.; Peng, J.; Hao, W.; Ding, G. Green Chem. 2011, 13,
190–196; (i) Xiao, R.; Yao, R.; Cai, M. Eur. J. Org. Chem. 2012, 4178–4184; (j)
Zhao, H.; He, W.; Yao, R.; Cai, M. Adv. Synth. Catal. 2014, 356, 3092–3098.
9. (a) Holy, N. P. Chemtech. 1980, 366–371; (b) Masllorens, J.; Moreno-Manas, M.;
Pla-Quintana, A.; Roglans, A. Org. Lett. 2003, 5, 1559–1562; (c) Shimizu, K.;
Koizumi, S.; Hatamachi, T.; Yoshida, H.; Komai, S.; Kodama, T.; Kitayama, Y. J.
Catal. 2004, 228, 141–151.
1
2
2
2
2
0. Lim, M. H.; Stein, A. Chem. Mater. 1999, 11, 3285–3295.
1. Lempers, H. E. B.; Sheldon, R. A. J. Catal. 1998, 175, 62–69.
2. Bai, L.; Zhang, Y. M.; Wang, J.-X. QSAR Comb. Sci. 2004, 23, 857–882.
3. Rosa, G. R.; Rosa, C. H.; Rominger, F.; Dupont, J.; Monteiro, A. L. Inorg. Chim.
Acta 2006, 359, 1947–1954.
24. Zhang, Z. H.; Wang, Z. Y. J. Org. Chem. 2006, 71, 7485–7487.
25. Nandurkar, N. S.; Bhanage, B. M. Tetrahedron 2008, 64, 3655–3660.
26. Zhao, H.; Wang, Y.; Sha, J. C.; Sheng, S. R.; Cai, M. Z. Tetrahedron 2008, 64,
7517–7523.
2
7. Martin, R.; Buchwald, S. L. J. Am. Chem. Soc. 2007, 129, 3844–3845.
8. Chen, S.-N.; Wu , W.-Y.; Tsai, F.-Y. Tetrahedron 2008, 64, 8164–8168.
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