MCM-41-supported mercapto palladium(O) complex: An efficient and recyclable catalyst for the heterogeneous Stille coupling reaction

Article abstract of DOI:10.1002/aoc.1580

The Stille cross-coupling reaction of organostannanes with aryl halides was achieved in the presence of a catalytic amount of MCM-41-supported mercapto palladium(O) complex (1 mol%) in DMF-H₂O (9:1) under air atmosphere in good to high yields. This MCM-41-supported palladium catalyst can be reused at least 10 times without any decrease in activity. Copyright

Full text of DOI:10.1002/aoc.1580

Full Paper
Received: 9 July 2009
Revised: 2 October 2009
Accepted: 2 October 2009
Published online in Wiley Interscience: 30 November 2009
(www.interscience.com) DOI 10.1002/aoc.1580
MCM-41-supported mercapto palladium(0)
complex: an efficient and recyclable catalyst
for the heterogeneous Stille coupling reaction
Hong Zhaoa,b, Guomin Zhenga, Wenyan Haoa and Mingzhong Caia∗
The Stille cross-coupling reaction of organostannanes with aryl halides was achieved in the presence of a catalytic amount of
MCM-41-supported mercapto palladium(0) complex (1 mol%) in DMF–H2O (9 : 1) under air atmosphere in good to high yields.
c
This MCM-41-supported palladium catalyst can be reused at least 10 times without any decrease in activity. Copyright ꢀ 2009
John Wiley & Sons, Ltd.
Keywords: Stille coupling reaction; supported catalyst; mercapto palladium complex; heterogeneous catalysis
Introduction
(2). Thepolymericligandshouldbeair-stableatroomtemperature,
which should allow its storage in normal bottles with unlimited
shelf-life (3).
Transition metal catalysts have been widely used in organic
synthesis. However, the high costs of transition metal catalysts
coupled with the toxic effects associated with many of them
have led to an increased interest in immobilizing catalysts onto
a support. This class of supported reagent can facilitate both the
isolation and recycling of the catalyst by filtration, thus providing
environmentally cleaner processes.[1]
The Stille reaction, the palladium-catalyzed cross-coupling of
organostannanes with organic halides and triflates, is one of the
most important, powerful and versatile tools for the formation of
carbon–carbon bonds.[2] This coupling reaction has been widely
applied in organic synthesis[3] since a wide variety of functionality
can be tolerated on either partner, the yields of coupled products
are high and the organotin reagents can be readily synthesized,
purifiedandstored.However,theStillereactiongenerallyproceeds
in the presence of a homogeneous phosphine palladium complex
such as Pd(PPh3)4 and PdCl2(PPh3)2, which makes the recovery
of the metal tedious if not impossible and might result in
unacceptablepalladiumcontaminationoftheproduct.Theforcing
conditionstypicallyatrefluxinTHFordioxaneandtherequirement
for dry, oxygen-free environments are also limitations of the Stille
Developments on the mesoporous material MCM-41 provided
a new possible candidate for a solid support for immobilization
of homogeneous catalysts.[9] MCM-41 has a regular pore diameter
of ca 5 nm and a specific surface area >700 m2 g−1 [10]
Its large
.
pore size allows passage of large molecules such as organic
reactants and metal complexes through the pores to reach
to the surface of the channel.[11] To date, a few palladium
complexesonfunctionalizedMCM-41supporthavebeenprepared
and used in organic reactions.[12] Recently, we have reported
the synthesis of the MCM-41-supported mercapto palladium(0)
complex [abbreviated as MCM-41-SH-Pd(0)] by very simple
procedures and found that this complex is a highly active and
recyclable catalyst for the Sonogashira reaction of aryl iodides.[7e]
In this paper, we wish to report that the Stille coupling reaction of
organostannanes with aryl halides can be easily achieved in the
presence of a catalytic amount of MCM-41-supported mercapto
palladium(0) complex [MCM-41-SH-Pd(0)] under aqueous and
aerobic conditions in good to high yields.
reaction. From a practical point of view, the development of Results and Discussion
more environmentally benign conditions for the reaction, for
Although phosphine ligands stabilize palladium and influence its
example the use of a heterogeneous palladium catalyst, would
be desirable.[4] So far, polymer-supported palladium catalysts
have successfully been used for the Heck reaction,[5] the Suzuki
reaction[6] and the Sonogashira reaction.[7] There are some
examples of heterogeneous palladium catalysts used to carry
out the Stille reaction.[8] Unfortunately, most of them have lower
catalytic activity compared with their soluble counterparts in the
Stille reaction. In addition, the activity of the recycled catalysts
gradually decreases because the palladium species leaches from
thesupportingpolymerorsilicagel.Toovercometheselimitations,
a novel methodology for creating insoluble and highly active
catalystsisneeded.Ourapproachwasguidedbythreeimperatives:
the polymeric reagent should be easily accessible by simple
procedures (1), starting from readily available and cheap reagents
reactivity, the simplest and cheapest Pd catalysts are of course
phosphine-free systems, specifically when used in low loading.
In our initial screening experiments, the realization of a Stille
coupling reaction catalyzed by the MCM-41-supported mercapto
∗
Correspondence to: Mingzhong Cai, Department of Chemistry, Jiangxi Normal
University, Nanchang 330022, People’s Republic of China.
E-mail: caimzhong@163.com
a
Department of Chemistry, Jiangxi Normal University, Nanchang 330022,
People’s Republic of China
b
Department of Pharmacy, Guangdong Pharmaceutical College, Guangzhou
510240, People’s Republic of China
c
Appl. Organometal. Chem. 2010, 24, 92–98
Copyright ꢀ 2009 John Wiley & Sons, Ltd.

MCM-41-supported mercapto palladium(0) complex
1 mol % MCM-41-SH-Pd(0)
outlined in Table 2. The Stille coupling reactions of aryl iodides
with arylstannanes proceeded smoothly under mild conditions,
giving the corresponding biaryls in high yields (entries 1–3). The
couplingreactionof 2-iodothiophenewith p-tolyltributylstannane
afforded the corresponding 2-(p-tolyl)thiophene 3d in 81% yield
(entry 4). As expected, the reactivity of aryl bromides was lower
than that of aryl iodides and the coupling reactions of aryl bro-
mideswitharylstannanesrequiredlongerreactiontimes, affording
the corresponding biaryls in moderate to good yields. The sub-
stituent effects in the aryl iodides appeared to be less significant
than in the aryl bromides and the reactivity of aryl bromides with
electron-withdrawing substituents was higher than that of aryl
bromides with electron-donating substituents (entries 5 and 6).
Even if the coupling reactions of aryl bromides with arylstannanes
were carried out at 80 or 100 ◦C, no increase in yields was ob-
served. The reactions of less reactive tetramethylstannane with
aryl iodides gave the corresponding coupled products 3f and 3 g
in good yields after 8–9 h reaction times (entries 7 and 8).
The developed methodology was also applicable for the Stille
coupling reactions of alkynylstannanes and vinylstannanes with
aryl halides. The Stille coupling of aryl halides with a variety
of alkynylstannanes and vinylstannanes was investigated and
the experimental results are also summarized in Table 2. From
Table 2, we can see that the Stille coupling reactions of a
variety of aryl iodides with alkynylstannanes proceeded smoothly
in the presence of a catalytic amount of MCM-41-SH-Pd(0) in
DMF–H2O (9 : 1) at 60 ◦C to afford the corresponding coupled
products in high yields within 3 h (entries 9–14). The coupling
reactions of aryl bromides with alkynylstannanes under the same
conditions could also give the corresponding coupled products
in good yields after longer reaction times (12–16 h). The coupling
reactions of ethenyltributylstannane with aryl iodides could afford
functionalized styrenes in high yields (entries 17 and 18). As
shown in Table 2, the Stille coupling reactions of a variety of aryl
iodides with (Z)- or (E)-vinylstannanes could proceed smoothly
in the presence of a catalytic amount of MCM-41-SH-Pd(0) in
DMF–H2O (9 : 1) at 60 ◦C to afford the corresponding (Z)- or
(E)-1,2-disubstituted alkenes in high yields with the retention
of configuration (entries 19–26). The optimized catalyst system
was quite general and tolerant of a wide range of functional
groups such as nitro, cyano, halogen, methoxy and carbonyl. In
Ar
R3Sn
R1
X
+
R1
Ar
DMF/H2O (9:1), 60 °C
1
2
3
X = I, Br R = n-Bu, Me R1 = aryl, Me, alkynyl, alkenyl
Scheme 1. Stille coupling of organostannanes with aryl halides catalyzed
by MCM-41-SH-Pd(0).
palladium(0) complex in the absence of phosphine ligand under
aqueous and aerobic conditions was our goal. When we searched
for a cross-coupling protocol for use with iodobenzene and
p-tolyltributylstannane, we observed that iodobenzene could re-
act with p-tolyltributylstannane in the presence of 1 mol% of
MCM-41-SH-Pd(0) in DMF under phosphine-free and aerobic reac-
tion conditions at room temperature to afford the desired cross-
coupling product in 65% yield. Encouraged by this result, we con-
tinued our search to improve the yield of the product by optimiza-
tionof thereactionconditionsandtheresultsareshowninTable 1.
We tested different temperatures for the Stille coupling reaction
catalyzed by MCM-41-SH-Pd(0) in DMF. A temperature of 60 ◦C
was found to be the most effective. Other temperatures such as
25, 40 and 80 ◦C were substantially less effective. We then turned
our attention to investigate the effect of solvents on the Stille
coupling reaction. When the reactions were conducted in DMF,
NMP and HMPA, high yields (85, 83 and 82%, respectively) of the
coupling products were isolated. Use of THF, CH3CN and benzene
as solvents led to slower reactions and the desired coupling
products were formed in 19–47% yields (entries 8–11). Running
the reaction in DMF–H2O (9 : 1) at 60 ◦C for 5 h gave the desired
4-methyldiphenyl in 86% yield (entry 7). Increasing the amount
of palladium catalyst could shorten the reaction time, but did
not increase the yield of 4-methyldiphenyl (entry 13). The low
palladium concentration usually led to a long period of reaction,
which was consistent with our experimental result (entry 12).
Thus, the optimized reaction conditions for this Stille coupling
reaction are MCM-41-SH-Pd(0) (1 mol%) in DMF–H2O (9 : 1) at
60 ◦C under aerobic conditions for 5 h.
We have investigated the reactions using a variety of organos-
tannanes and a wide range of aryl halides as the substrates under
the optimized reaction conditions (Scheme 1) and the results are
Table 1. Stille coupling of iodobenzene with p-tolyltributylstannane under the various reaction conditionsa
Entry
Solvent
MCM-41-SH-Pd(0) (mol%)
Temperature (◦C)
Time (h)
Yield (%)b
TOF
1
2
DMF
DMF
DMF
DMF
NMP
1
1
25
40
60
80
60
60
60
65
80
80
80
60
60
20
12
5
65
76
85
81
83
82
86
31
19
41
47
84
85
3.3
6.3
3
1
17.0
20.3
16.6
16.4
17.2
1.3
4
1
4
5
1
5
6
HMPA
1
5
7
DMF–H2O (9 : 1)
THF
1
5
8
1
24
24
24
24
12
3
9
PhH
1
0.8
10
11
12
13
CH3CN
1
1.7
CH3CN–H2O (9 : 1)
DMF–H2O (9 : 1)
DMF–H2O (9 : 1)
1
2.0
0.5
2
14.0
14.2
a All reactions were performed using 1.0 mmol of iodobenzene, 1.1 mmol of p-tolyltributylstannane in 2 ml of solvent under aerobic conditions.
b Isolated yield based on the iodobenzene used.
c
Appl. Organometal. Chem. 2010, 24, 92–98
Copyright ꢀ 2009 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/aoc

H. Zhao et al.
Table 2. Stille coupling reactions of organostannanes with aryl halidesa
Entry
Ar
X
R1
R
Time (h)
Product
Yield (%)b
TOF
1
2
Ph
I
4-MeC6H4
4-MeC6H4
Ph
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
Me
5
4
3a
3b
3c
3d
3c
3e
3f
86
90
87
81
62
80
74
72
87
90
88
85
89
87
69
77
85
82
85
81
83
84
87
85
82
84
17.2
22.5
14.5
13.5
2.6
4-O2NC6H4
4-MeOC6H4
2-Thienyl
I
3
I
6
4
I
4-MeC6H4
Ph
6
5
4-MeOC6H4
4-O2NC6H4
3-MeOCOC6H4
4-MeOC6H4
4-MeC6H4
Br
24
15
8
6
Br
Ph
5.3
7
I
I
Me
9.3
8
Me
Me
9
3g
3h
3i
8.0
9
I
PhC
PhC
PhC
C
C
C
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
n-Bu
3
29.0
30.0
29.3
28.3
29.7
29.0
4.3
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
4-MeOCOC6H4
3-O2NC6H4
3-MeC6H4
I
3
I
3
3j
I
C4H9C
C4H9C
C4H9C
C4H9C
C
C
C
C
3
3k
3l
4-O2NC6H4
3-CNC6H4
I
3
I
3
3m
3k
3i
3-MeC6H4
Br
Br
I
16
12
5
4-MeOCOC6H4
3-MeOCOC6H4
4-MeOC6H4
4-O2NC6H4
4-MeC6H4
PhC
C
6.4
CH2 CH
3n
3o
3p
3q
3r
17.0
16.4
21.3
20.3
16.6
21.0
21.8
21.3
16.4
21.0
I
CH2 CH
5
I
(Z)-PhCH CH
(Z)-PhCH CH
(E)-PhCH CH
(E)-PhCH CH
(Z)-C4H9CH CH
(Z)-C4H9CH CH
(E)-C4H9CH CH
(E)-C4H9CH CH
4
I
4
4-MeOC6H4
4-MeC6H4
I
5
I
4
3s
3t
4-O2NC6H4
3-NCC6H4
I
4
I
4
3u
3v
3w
4-MeOC6H4
4-ClC6H4
I
5
I
4
a All reactions were performed using 1.0 mmol of aryl halide, 1.1 mmol of organostannane and 0.01 mmol of MCM-41-SH-Pd(0) in DMF–H2O (9 : 1)
(2 ml) under aerobic conditions.
b Isolated yield based on aryl halide used.
all reactions, only 1 mol% of MCM-41-SH-Pd(0) based on the aryl
halides was used; the molar turnover numbers (TON) were larger
than those in the corresponding coupling reaction catalyzed by
the homogeneous palladium complexes or other heterogeneous
palladiumcatalystsreported.[8] Recently,Souzaet al.reportedStille
cross-coupling reaction of aryl iodides with arylstannanes using
[8e]
[8g]
Pd–CaCO3
or Pd–BaSO4
as catalyst reservoir; the soluble
Pd(0)/Pd(II) species was found to be the true catalyst, but the
catalystscanbereusedonlythreetimes. Bernecheaet al. described
dendrimer-encapsulated Pd nanoparticles as catalytic precursors
in the Stille reaction in water;[8d] although the catalyst exhibited
high activity for the cross-coupling reaction of aryl iodides
with phenyltin trichlorides, the preparation of the dendrimer
is rather complicated. Most of the Stille cross-coupling reactions
catalyzed by the homogeneous palladium complexes or other
heterogeneous palladium catalysts were conducted under inert
atmosphere;however,theStillecross-couplingreactionscatalyzed
by MCM-41-SH-Pd(0) proceeded smoothly under air atmosphere.
InordertodeterminewhetherthecatalysiswasduetotheMCM-
41-SH-Pd(0) 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
test.[13] We focused on the coupling reaction of iodobenzene
with p-tolyltributylstannane. We filtered off the MCM-41-SH-Pd(0)
complex after 1 h of reaction time and allowed the filtrate to
react further. The catalyst filtration was performed at the reaction
temperature (60 ◦C) in order to avoid possible recoordination or
A
B
1
2
3
4
5
6
7
8
2θ (degrees)
Figure 1. XRD patterns of the catalyst before (A) and after (B) reactions.
precipitation of soluble palladium upon cooling. We found that,
after this hot filtration, no further reaction was observed and no
palladium could be detected in the hot filtered solution by atomic
absorption spectroscopy. This result suggests that the palladium
catalyst remains on the support at elevated temperatures during
the reaction. The X-ray powder diffraction analysis patterns of the
catalyst before and after reactions are displayed in Fig. 1. We can
see that an intense diffraction peak (100) of the MCM-41-SH-Pd(0)
c
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Copyright ꢀ 2009 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2010, 24, 92–98

MCM-41-supported mercapto palladium(0) complex
only 5.2% of palladium had been lost from the MCM-41 support.
The high stability and excellent reusability of the catalyst should
result from the strong coordination of the mercapto ligand on
palladium and the mesoporous structure of MCM-41 support. The
result is important from a practical point of view. The high catalytic
activity, excellentreusabilityandtheeasyaccessibilityoftheMCM-
41-SH-Pd(0) make them a highly attractive supported palladium
catalyst for the parallel solution phase synthesis of diverse libraries
of compounds.
Table 3. X-ray photoelectron spectra data for MCM-41-SH-Pd(0)
before and after reactionsa
Sample
Pd3d5/2
S2p
Si2p
O1s
Cl2p
MCM-41-SH-Pd(0) (fresh)
MCM-41-SH-Pd(0) (used)
MCM-41-SH
336.8
336.7
164.2 103.2 533.0
164.1 103.3 533.1
163.8 103.2 533.0
PdCl2
338.3
199.2
a The binding energies are referenced to C1s (284.6 eV) and the energy
differences were determined with an accuracy of 0.2 eV.
Conclusions
In summary, we have developed a novel, efficient, practical
and green catalyst system for the Stille coupling reaction of
organostannanes with aryl halides using the MCM-41-supported
mercapto palladium(0) complex as catalyst in DMF–H2O (9 : 1)
under aerobic conditions. This MCM-41-supported palladium
catalyst can be reused 10 times without any decrease in activity.
The advantages of our heterogeneous catalytic system over
others are: (1) the preparation of the heterogeneous MCM-41-SH-
Pd(0) catalyst is quite simple and convenient from commercially
available and cheap reagents; (2) the reaction conditions are very
mild, i.e. only 1 mol% palladium catalyst, aqueous medium and air
atmosphere; and (3) the catalyst has excellent performance and
reusability.
Table 4. Stille reaction of methyl 4-iodobenzoate with 1-phenyl-2-
tributylstannylethyne catalyzed by recycled catalyst
O
C
+
I
Bu3Sn
11 mmol
Ph
O
MeO
10 mmol
0.1 mmol MCM-41-SH-Pd(0)
(1st-10th use)
C
Ph
DMF/H2O (9:1), 60 °C, 3 h
MeO
3i
Entry
Catalyst cycle
Isolated yield (%)
TON
TOF
Experimental
1
2
3
1st
10th
90
88
90
88
30.0
29.3
All chemicals were of reagent grade and used as purchased. All
coupling products were characterized by comparison of their
spectra and physical data with authentic samples. IR spectra were
determined on a Perkin-Elmer 683 instrument. 1H NMR spectra
were recorded on a Bruker AC-P400 (400 MHz) spectrometer
with TMS as an internal standard in CDCl3 as solvent. 13C
NMR spectra were recorded on a Bruker AC-P400 (100 MHz)
spectrometer in CDCl3 as solvent. Microanalyses were measured
using a Yanaco MT-3 CHN microelemental analyzer. Melting
points are uncorrected. The atomic absorption spectroscopy was
obtained on AA-6300 atomic absorption spectrometer. X-ray
powder diffraction was obtained on Damx-rA (Rigaka). X-ray
photoelectronspectrawererecordedonanXSAM800(Kratos).The
BET surface area was measured on an ASAP2010 (Micromeritics) by
N2 physical adsorption–desorption at 77.4 K. The sulfur content
in the catalyst was determined using a VarioEL III CHNOS
microelemental analyzer. The palladium content of the MCM-
41-SH-Pd(0) was determined with inductively coupled plasma
atom emission Atomscan16 (ICP-AES, TJA Corporation). The
MCM-41-supportedmercaptopalladium(0)complex[MCM-41-SH-
Pd(0)] was conveniently synthesized from commercially available
and cheap γ -mercaptopropyltriethoxysilane via immobilization
on MCM-41, followed by reacting with palladium chloride in
acetone, and then the reduction with hydrazine hydrate in ethanol
according to our previous procedures.[7e] The sulfur and palladium
contents of the MCM-41-SH-Pd(0) were determined to be 0.81 and
0.38 mmol g−1, respectively. The MCM-41-SH-Pd(0) had surface
area of 643.5 m2 g−1, pore volume of 0.52 cm3 g−1, and diameter
of 2.1 nm.
1st to 10th consecutive
Average 89
Total of 890
remainedafterreactions,whichindicatesthatthebasicstructureof
the catalyst was not damaged during the Stille coupling reactions.
The X-ray photoelectron spectra data of the catalyst before and
after reactions are listed in Table 3. It can be seen that the binding
energies of Si2p, O1s, S2p and Pd3d5/2 of the catalyst used are similar
to those of the fresh one.
The MCM-41-SH-Pd(0) complex catalyst can be easily recovered
by simple filtration. We also examined the reuse of the catalyst
by using the coupling reaction of methyl4-iodobenzoate with
1-phenyl-2-tributylstannylethyne. In general, the continuous
recycling of resin-supported palladium catalysts is difficult
owing to leaching of the palladium species from the polymer
supports, which often reduces their activity within a five-
recycle run. Kang et al.[8a] reported that a silica-supported
poly[3-(2-cyanoethylsulfanyl)propylsiloxane palladium] complex
was an efficient catalyst for Stille reaction of aryl iodides with
organostannanes; the activity of the recovered catalyst was tested
for the coupling of iodobenzene with 2-thienylstannane for two
recycles and it was found that the yield of the coupled product
decreased by 8 and 5%, respectively. However, when the reaction
of methyl 4-iodobenzoate with 1-phenyl-2-tributylstannylethyne
wasperformedevenwith1 mol%ofMCM-41-SH-Pd(0),thecatalyst
couldberecycled10timeswithoutanylossofactivity. Thereaction
promoted by the tenth recycled catalyst gave 3i in 88% yield
(Table 4, entry 2). The average yield of 3i in consecutive reactions
promoted by the first through to the tenth recycled catalyst
was 89% (entry 3). The palladium content of the catalyst was
determined by ICP to be 0.36 mmol g−1 after 10 consecutive runs;
General Procedure for the Stille Coupling Reaction
Aryl halide (1.0 mmol), MCM-41-SH-Pd(0) (26 mg, 0.01 mmol Pd)
and DMF–H2O (9 : 1, 2 ml) were added to a flask, and the
c
Appl. Organometal. Chem. 2010, 24, 92–98
Copyright ꢀ 2009 John Wiley & Sons, Ltd.
www.interscience.wiley.com/journal/aoc

H. Zhao et al.
resulting mixture was stirred at room temperature for 5 min.
To this suspension was added organostannane (1.1 mmol), and
the reaction mixture was stirred at 60 ◦C for 3–24 h. The mixture
was diluted with Et2O (30 ml). The MCM-41-SH-Pd(0) catalyst was
separated from the mixture by filtration, washed with distilled
water (2 × 5 ml), EtOH (2 × 5 ml) and Et2O (2 × 5 ml) and reused in
the next run. The ethereal solution was treated with 20% aqueous
KF (10 ml) for 30 min before being dried and concentrated. The
solvent was removed under vacuum, and the residue was purified
by flash chromatography on silica gel to give the desired product.
1-(4-Methylphenyl)-2-phenylethyne (3 h)
White solid, 73–74 ◦C (lit.[15] m.p. 74–75 ◦C). IR (KBr) ν (cm−1) 3029,
2918, 2859, 2215, 1594, 1509, 818, 690. The 1H NMR and 13C NMR
spectra were identical to those reported in the literature.
Methyl 4-(phenylethynyl)benzoate (3i)
White solid, 120 ◦C. IR (KBr) ν (cm−1) 2948, 2218, 1717, 1605,
1438, 1280, 1109, 770. 1H NMR (CDCl3) δ 8.04–8.02 (m, 2H, Ar–H),
7.61–7.58 (m, 2H, Ar–H), 7.56–7.54 (m, 2H, Ar–H), 7.38–7.36 (m,
3H, Ar–H), 3.93 (s, 3 H, OCH3). 13C NMR (CDCl3) δ 166.6 (CO), 131.8
(CH × 2), 131.5 (CH × 2), 129.5 (CH × 2), 129.4 (C), 128.8 (CH), 128.5
(CH × 2), 128.0 (C), 122.7 (C), 92.4 ( C), 88.6 ( C), 52.3 (CH3). Anal.
calcd for C16H12O2: C, 81.34; H, 5.12. Found: C, 81.07; H, 4.93.
4-Methyldiphenyl (3a)
White solid, m.p. 47 ◦C (lit.[14] m.p. 47.5 ◦C). IR (KBr) ν (cm−1) 3053,
1486, 823, 757, 689. The 1H NMR and 13C NMR spectra were
identical to those reported in the literature.
1-(3-Nitrophenyl)-2-phenylethyne (3j)
4-Methyl-4ꢁ-nitrodiphenyl (3b)
Yellow solid, 69–70 ◦C (lit[16] m.p. 68–69 ◦C). IR (KBr) ν (cm−1
3081, 2210, 1597, 1530, 1517, 1347, 810, 759, 692. The 1H NMR and
13C NMR spectra were identical to those reported in the literature.
)
Yellow solid, m.p. 142–144 ◦C (lit.[14] m.p. 142–143 ◦C). IR (KBr) ν
(cm−1) 3079, 2921, 1595, 1514, 1484, 1339, 825, 754, 697. The 1H
NMR and 13C NMR spectra were identical to those reported in the
literature.
1-(3-Methylphenyl)-1-hexyne (3k)
4-Methoxydiphenyl (3c)
Oil. IR (neat) ν (cm−1) 3037, 2959, 2932, 2228, 1603, 1580, 1093,
783. 1H NMR (CDCl3) δ 7.22–7.13 (m, 3H, Ar–H), 7.06 (d, J = 7.6 Hz,
1H, Ar–H), 2.40 (t, J = 7.2 Hz, 2H, CCH2), 2.30 (s, 3H, ArCH3),
1.60–1.54 (m, 2H, CH2), 1.51–1.39 (m, 2H, CH2), 0.94 (t, J = 7.2 Hz,
3H, CH3). 13C NMR (CDCl3) δ 137.8 (C), 132.2 (CH), 128.6 (CH), 128.4
(CH), 128.1 (CH), 123.9 (C), 90.0 ( C), 80.7 ( C), 30.9 (CH2), 22.1
White solid, 89–90 ◦C (lit.[14] m.p. 88–89 ◦C). IR (KBr) ν (cm−1) 3065,
3030, 2961, 1606, 1486, 1038, 832, 759. The 1H NMR and 13C NMR
spectra were identical to those reported in the literature.
2-(4-Methylphenyl)thiophene (3d)
(CH2), 21.2 (ArCH3), 19.1 (CH2), 13.7 (CH3). Anal. calcd for C13H16
C, 90.64; H, 9.36. Found: C, 90.48; H, 9.23.
:
White solid, 63–64 ◦C. IR (KBr) ν (cm−1) 3074, 3023, 2912, 2854,
1533, 1500, 1431, 850, 809. 1H NMR (CDCl3) δ 7.49 (d, J = 8.0 Hz,
2H, Ar–H), 7.25–7.23 (m, 1H, Ar–H), 7.22–7.19 (m, 1H, Ar–H), 7.16
(d, J = 8.0 Hz, 2H, Ar–H), 7.04–7.02 (m, 1H, Ar–H), 2.34 (s, 3H,
CH3). 13C NMR (CDCl3) δ 144.6 (C), 137.4 (CH), 131.7 (CH), 129.6 (CH
× 2), 128.0 (CH), 125.9 (C), 124.3 (CH × 2), 122.6 (C), 21.2 (CH3).
Anal. calcd for C11H10S: C, 75.82; H, 5.78. Found: C, 75.59; H, 5.94.
1-(4-Nitrophenyl)-1-hexyne (3l)
Yellow oil.[15] IR (neat) ν (cm−1) 3081, 2934, 2873, 2230, 1594, 1519,
1343, 854. The 1H NMR and 13C NMR spectra were identical to
those reported in the literature.
4-Nitrodiphenyl (3e)
1-(3-Cyanophenyl)-1-hexyne (3m)
Yellow solid, 113 ◦C (lit.[14] m.p. 112–113 ◦C). IR (KBr) ν (cm−1
3076, 1595, 1576, 1514, 1480, 1346, 853, 740, 699. The 1H NMR and
13C NMR spectra were identical to those reported in the literature.
)
Oil. IR (neat) ν (cm−1) 3069, 2958, 2873, 2232, 1597, 1478, 896, 798,
683. 1H NMR (CDCl3) δ 7.66 (s, 1H, Ar–H), 7.60–7.53 (m, 2H, Ar–H),
7.39 (t, J = 7.6 Hz, 1H, Ar–H), 2.42 (t, J = 7.2 Hz, 2H, CCH2),
1.61–1.56 (m, 2H, CH2), 1.50–1.45 (m, 2H, CH2), 0.96 (t, J = 7.2 Hz,
3H, CH3). 13CNMR(CDCl3)δ 135.7(CH), 135.0(CH), 130.7(CH), 129.1
(CH), 125.7 (C), 118.3 (CN), 112.6 (C), 93.4 ( C), 78.5 ( C), 30.5
(CH2), 22.0 (CH2), 19.1 (CH2), 13.7 (CH3). Anal. calcd for C13H13N: C,
85.26; H, 7.10; N, 7.65. Found: C, 85.31; H, 7.27; N, 7.42.
Methyl 3-methylbenzoate (3f)
Oil. IR(neat)ν (cm−1)3026, 2952, 1722, 1592, 1498, 1284, 1205, 746,
684. 1H NMR (CDCl3) δ 7.77–7.75 (m, 2H, Ar–H), 7.26 (d, J = 8.0 Hz,
1H, Ar–H), 7.23 (d, J = 8.0 Hz, 1H, Ar–H), 3.84 (s, 3H, OCH3), 2.39 (s,
3H, CH3). 13C NMR (CDCl3) δ 167.3 (CO), 138.1 (C), 133.7 (CH), 130.2
(CH), 129.9 (CH), 128.3 (CH), 126.8 (C), 52.0 (OCH3), 21.2 (CH3).
Methyl 3-ethenylbenzoate (3n)
Oil. IR (neat) ν (cm−1) 3090, 2952, 2844, 1723, 1631, 1582, 1200,
762, 707. 1H NMR (CDCl3) δ 8.07 (s, 1H, Ar–H), 7.92–7.87 (m, 1H,
Ar–H), 7.57 (d, J = 8.0 Hz, 1H, Ar–H), 7.46–7.36 (m, 1H, Ar–H),
6.77–6.70 (m, 1H, CH), 5.84–5.79 (m, 1H, CH), 5.33–5.30 (m,
1H, CH), 3.91 (s, 3H, OCH3). 13C NMR (CDCl3) δ 167.0 (CO), 137.9
(C), 136.0 ( CH), 130.5 (CH), 129.4 (CH), 128.8 ( CH2), 128.6 (CH),
127.4 (C), 115.1 (CH), 52.1 (OCH3).
4-Methylanisole (3g)
Oil. IR (neat) ν (cm−1) 3032, 2963, 2836, 1614, 1488, 1039, 818, 720.
1H NMR (CDCl3) δ 7.05 (d, J = 8.0 Hz, 2H, Ar–H), 6.78 (d, J = 8.0 Hz,
2H, Ar–H), 3.73 (s, 3H, OCH3), 2.26 (s, 3H, CH3). 13C NMR (CDCl3)
δ 157.7 (C–OCH3), 129.9 (CH × 2), 128.6 (CH × 2), 113.8 (C), 55.2
(OCH3), 20.4 (CH3).
c
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Copyright ꢀ 2009 John Wiley & Sons, Ltd.
Appl. Organometal. Chem. 2010, 24, 92–98

MCM-41-supported mercapto palladium(0) complex
4-Methoxystyrene (3o)
(E)-1-(4-Methoxyphenyl)-1-hexene (3v)
Oil. IR (neat) ν (cm−1) 3080, 2968, 1636, 1608, 1576, 1458, 1310,
1240, 836. 1H NMR (CDCl3) δ 7.34 (d, J = 8.0 Hz, 2H, Ar–H), 6.85
(d, J = 8.0 Hz, 2H, Ar–H), 6.68–6.62 (m, 1H, CH), 5.63–5.58 (m,
1H, CH), 5.13–5.10 (m, 1H, CH), 3.76 (s, 3H, OCH3). 13C NMR
(CDCl3) δ 160.0 (C–OCH3), 134.7 ( CH), 130.6 (CH × 2), 127.3
Oil. IR (neat) ν (cm−1) 2957, 1608, 1511, 1464, 1174, 1038, 965,
804. 1H NMR (CDCl3) δ 7.27 (d, J = 8.4 Hz, 2H, Ar–H), 6.83 (d,
J = 8.4 Hz, 2H, Ar–H), 6.32 (d, J = 16.0 Hz, 1H, CH), 6.09 (dt,
J = 16.0, 7.2 Hz, 1H, CH), 3.80 (s, 3H, OCH3), 2.22–2.16 (m, 2H,
CCH2), 1.47–1.34 (m, 4H, CH2CH2), 0.93 (t, J = 7.2 Hz, 3H, CH3).
13C NMR (CDCl3) δ 158.6 (C–OCH3), 130.9 (C), 129.1 ( CH), 129.0
(
CH2), 116.3 (C), 114.3 (CH × 2), 56.0 (OCH3).
(
CH), 127.0 (CH × 2), 113.9 (CH × 2), 55.3 (OCH3), 32.7 (CH2), 31.7
(CH2), 22.3 (CH2), 14.0 (CH3). Anal. calcd for C13H18O: C, 82.06; H,
9.54. Found: C, 82.25; H, 9.71.
(Z)-1-(4-Nitrophenyl)-2-phenylethene (3p)
Yellowsolid, 60.5–61.5 ◦C. IR(KBr)ν (cm−1)1627, 1592, 1505, 1342,
1
1105, 920, 856, 778, 696. H NMR (CDCl3) δ 8.07 (d, J = 8.8 Hz,
(E)-1-(4-Chlorophenyl)-1-hexene (3w)
2H, Ar–H), 7.37 (d, J = 8.8 Hz, 2H, Ar–H), 7.26–7.19 (m, 5H, Ar–H),
6.82 (d, J = 12.4 Hz, 1H, CH), 6.62 (d, J = 12.4 Hz, 1H, CH). 13
C
Oil. IR (neat) ν (cm−1) 2957, 1593, 1490, 1469, 1091, 1005, 966, 809.
1H NMR (CDCl3) δ 7.59 (d, J = 8.4 Hz, 2H, Ar–H), 7.07 (d, J = 8.4 Hz,
2H, Ar–H), 6.30 (d, J = 16.0 Hz, 1H, CH), 6.20 (dt, J = 16.0, 7.2 Hz,
1H, CH), 2.21–2.18 (m, 2H, CCH2), 1.47–1.32 (m, 4H, CH2CH2),
0.92 (t, J = 7.2 Hz, 3H, CH3). 13C NMR (CDCl3) δ 138.7 (CH × 2),
132.0 (C), 130.5 (CH × 2), 128.6 ( CH), 128.5 (C), 127.1 ( CH), 32.7
(CH2), 31.5 (CH2), 22.3 (CH2), 14.0 (CH3). Anal. calcd for C12H15Cl: C,
74.01; H, 7.76. Found: C, 73.79; H, 7.57.
NMR (CDCl3) δ 146.6 (C–NO2), 144.2 (C), 136.1 (C), 134.0 ( CH),
129.7 (CH × 2), 128.8 (CH × 2), 128.6 (CH × 2), 128.0 (CH), 127.9
(
CH), 123.6 (CH × 2). Anal. calcd for C14H11NO2: C, 74.65; H, 4.92;
N, 6.22. Found: C, 74.38; H, 4.71; N, 6.34.
(Z)-1-(4-Methylphenyl)-2-phenylethene (3q)
Oil. IR (neat) ν (cm−1) 3012, 2921, 1599, 1492, 1447, 919, 821, 772.
1H NMR (CDCl3) δ 7.28–7.19 (m, 5H, Ar–H), 7.15 (d, J = 8.0 Hz, 2H,
Ar–H), 7.03 (d, J = 8.0 Hz, 2H, Ar–H), 6.56 (s, 2H, CH), 2.32 (s,
3H, CH3). 13C NMR (CDCl3) δ 137.4 (C), 136.9 (C), 134.3 (C), 130.2
Acknowledgments
We thank the National Natural Science Foundation of China
(project no. 20862008) and the Natural Science Foundation of
Jiangxi Province of China (2007GZW0172, 2008GQH0034) for
financial support.
(
CH), 129.6 ( CH), 128.9 (CH × 2), 128.8 (CH × 2), 128.7 (CH ×
2), 128.2 (CH × 2), 127.0 (CH), 21.3 (CH3). Anal. calcd for C15H14: C,
92.74; H, 7.26. Found: C, 92.50; H, 7.31.
(E)-1-(4-Methoxyphenyl)-2-phenylethene(3r)
White solid, 134–135 ◦C (lit.[5b] m.p. 135–136 ◦C). IR (KBr) ν (cm−1
)
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2963, 1602, 1513, 1465, 1112, 967, 813. The 1H NMR and 13C NMR
spectra were identical to those reported in the literature.
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Appl. Organometal. Chem. 2010, 24, 92–98