Synthesis of β-aryl ketones by heck arylation of allylic alcohols catalysed by a MCM-41-supported bidentate nitrogen palladium complex

Article abstract of DOI:10.3184/174751913X13668131126257

The Heck arylation reaction of aryl iodides with allylic alcohols catalysed by an mesoporous silica (MCM-41)-supported bidentate nitrogen palladium complex [MCM-41-2N-Pd(OAc)2] proceeded smoothly in the presence of tetrabutylammonium chloride (TBAC) in DMF to afford β-aryl ketones in good to excellent yields. This heterogeneous palladium catalyst can be recovered by simple filtration and reused several times without any decrease in activity.

Full text of DOI:10.3184/174751913X13668131126257

JOURNAL OF CHEMICAL RESEARCH 2013
RESEARCH PAPER 333
JUNE, 333–336
Synthesis of β-aryl ketones by Heck arylation of allylic alcohols catalysed
by a MCM-41-supported bidentate nitrogen palladium complex
Yixiang Huanga, Pingping Wangb, Jiaqin Liua and Mingzhong Caia*
aDepartment of Chemistry, Jiangxi Normal University, Nanchang 330022, P. R. China
bDepartment of Chemistry, Jiujiang University, Jiujiang 332000, P. R. China
The Heck arylation reaction of aryl iodides with allylic alcohols catalysed by an mesoporous silica (MCM-41)-sup-
ported bidentate nitrogen palladium complex [MCM-41-2N-Pd(OAc)2] proceeded smoothly in the presence of tetra-
butylammonium chloride (TBAC) in DMF to afford β-aryl ketones in good to excellent yields. This heterogeneous
palladium catalyst can be recovered by simple filtration and reused several times without any decrease in activity.
Keywords: supported catalyst, Heck arylation, bidentate nitrogen palladium complex, β-aryl ketone, heterogeneous catalysis,
MCM-41
β-Aryl ketones are important intermediates in organic synthe-
sis1–4 and, therefore, the development of efficient synthetic
methods is of significant interest. Although the palladium-
catalysed arylation of allylic alcohols with aryl iodides or
bromides has been applied for the synthesis of these com-
pounds,5–10 a mixture of carbonyl compounds and substituted
allylic alcohols is usually obtained since these arylation
reactions are poorly regioselective.11–13 Recently, Calo et al.14
described Heck arylation reactions of aryl bromides and
activated aryl chlorides with allylic alcohols catalysed by a
palladium-benzothiazole carbene complex in molten tetrabu-
tylammonium bromide (TBAB) as solvent, good to excellent
yields and high regioselectivity were obtained. Unfortunately,
the yield dropped seriously with recycling of the catalyst and
ionic liquid. It is well known that homogeneous palladium
catalysts are expensive and air sensitive, which limits their
industrial applications and it is difficult to recycle and reuse
these homogeneous catalysts due to their low stability toward
oxidation.15,16 In contrast, heterogeneous catalysts can be easily
separated from reaction mixtures by simple filtration and
reused in successive reactions provided that the active sites
have not become deactivated. The high costs of the transition-
metal catalysts coupled with toxic effects associated with
many transition metals has led to an increased interest in
immobilising catalysts onto a support. Heterogeneous cataly-
sis also helps to minimise wastes derived from reaction
work-up, contributing to the development of green chemical
processes.17–21 So far, supported palladium catalysts have
successfully been used for the Heck reaction.22–26 In spite of the
significant advances in this area, there are very few reports that
employ the heterogeneous palladium complexes as catalysts
for the Heck arylation reaction of allylic alcohols with aryl
halides.
Developments on the mesoporous material MCM-41 pro-
vided a new possible candidate for a solid support for immo-
bilisation of homogeneous catalysts.27 MCM-41 has a regular
pore diameter of ca 5 nm and a specific surface area > 700 m2
g−1.28 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.29–31 It is generally accepted
that high surface area of a heterogeneous catalyst results in
high catalytic activity. Considering the fact that the MCM-41
support has an extremely high surface area and the catalytic
palladium species is anchored on the inner surface of the
mesopore of the MCM-41 support, we expect that a MCM-41-
immobilised palladium catalyst will exhibit high activity
and good reusability. To date, some palladium complexes
on functionalised MCM-41 supports have been prepared and
successfully used in Heck reactions.32–35 However, to the best
of our knowledge, no Heck arylation of allylic alcohols with
aryl halides catalysed by an MCM-41-supported palladium
complex has been reported. In continuing our efforts to develop
greener synthetic pathways for organic transformations,
our new approach, described in this paper, was to design and
synthesise an MCM-41-supported bidentate nitrogen palla-
dium complex, which was used as an effective heterogeneous
palladium catalyst for the Heck arylation of allylic alcohols
with aryl iodides.
The novel MCM-41-supported bidentate nitrogen palladium
complex [MCM-41-2N-Pd(OAc)2] was conveniently synthe-
sised from commercially available and inexpensive 3-(2-amin
oethylamino)propyltrimethoxysilane by immobilisation on
MCM-41, followed by reaction with palladium acetate in
acetone (Scheme 1). The X-ray powder diffraction (XRD)
analysis of the MCM-41-2N-Pd(OAc)2 indicated that, in addi-
tion to an intense diffraction peak (100), two higher order
peaks (110) and (200) with lower intensities were detected and
therefore the chemical bonding procedure did not diminish the
structural ordering of the MCM-41.
Elemental analyses and X-ray photoelectron spectroscopy
(XPS) were used to characterise the MCM-41-supported
bidentate nitrogen palladium complex. The N: Pd mole ratio of
the MCM-41-2N-Pd(OAc)2 was determined to be 6.22. The
XPS data for MCM-41-2N-Pd(OAc)2, MCM-41-2N, Pd(OAc)2
and metal Pd are listed in Table 1. It can be seen that the
binding energies of Si2p and O1s of MCM-41-2N-Pd(OAc)2
are similar to those of MCM-41-2N. However, the difference
of N1s binding energies between MCM-41-2N-Pd(OAc)2
and MCM-41-2N is 1.2 eV. The binding energy of Pd3d5/2 in
MCM-41-2N-Pd(OAc)2 is 0.7 eV less than that in Pd(OAc)2,
but 2.1 eV larger than that in metal Pd. These results show
that a coordination bond between N and Pd is formed in
MCM-41-2N-Pd(OAc)2.
In order to test the catalytic activity of the MCM-41-2N-
Pd(OAc)2, the arylation reactions of allylic alcohols with aryl
iodides were investigated (Scheme 2). The reaction of but-3-
en-2-ol (1.5 equiv.) with iodobenzene was chosen as a model
reaction, and the influences of various reaction parameters
such as base, the additive (TBAC) quantity, and palladium
catalyst quantity on the reaction were tested. The results are
summarised in Table 2. For the bases evaluated, NaHCO3 was
found to be the most effective (entry 3). The organic bases
such as Bu3N and DBU and other inorganic bases were less
effective. We then investigated the influence of the additive
(TBAC) quantity on the arylation reaction. It was found that
the additive (TBAC) quantity had an important influence
on the arylation reaction owing to the efficient controlling of
regioselectivity. When 1.0 equiv. TBAC was used as the addi-
tive, a high yield of 4-phenylbutan-2-one was formed due to
high regioselectivity (entry 3). Increasing further the additive
* Correspondent. E-mail: caimzhong@163.com

334 JOURNAL OF CHEMICAL RESEARCH 2013
Scheme 1
Table 1 XPS data for MCM-41-2N-Pd(OAc)2, MCM-41-2N,
products in good to excellent yields (entries 10 and 11).
However, when primary allylic alcohols such as allyl alcohol
were used as the substrates under the same reaction conditions,
low conversion was observed and a complicated mixture of
carbonyl compounds and substituted allylic alcohols was
formed. We also investigated the arylation of secondary allylic
alcohols with aryl bromides, but the aryl bromides were not
reactive under the conditions optimised for aryl iodides.
In order to determine whether the catalysis was due to the
MCM-41-2N-Pd(OAc)2 complex or to a homogeneous palla-
dium complex that comes off the support during the reaction
and then returns to the support at the end, we performed the
hot filtration test.36 We focused on the arylation reaction of but-
3-en-2-ol with 4-nitroiodobenzene. We filtered off the MCM-
41-2N-Pd(OAc)2 complex after 1h of reaction time and allowed
the filtrate to react further. The catalyst filtration was per-
formed at the reaction temperature (100 °C) in order to avoid
Pd(OAc)2 and metal Pda
Sample
Pd3d5/2
337.5
N1s
Si2p
O1s
MCM-41-2N-Pd(OAc)2
MCM-41-2N
Pd(OAc)2
400.8
399.6
103.3
103.2
533.1
533.2
338.2
335.4
Metal Pd
a The binding energies are referenced to C1s (284.6 eV) and
the energy differences were determined with an accuracy of
0.2 eV.
quantity did not enhance the yield of 4-phenylbutan-2-one
(entry 9). The amount of supported palladium catalyst was also
screened and 0.6 mol% loading of palladium was found to be
optimal; a lower yield was observed and a longer reaction time
was required when the amount of the catalyst was decreased
(entry 10). Increasing the amount of palladium catalyst could
shorten the reaction time, but did not increase the yield of
4-phenylbutan-2-one (entries 11 and 12). Thus, the optimised
reaction conditions for this arylation reaction are MCM-41-
2N-Pd(OAc)2 (0.6 mol%) in DMF with NaHCO3 as base and
TBAC as the additive at 100 °C under Ar for 7h (entry 3).
With this promising result in hand, we started to investigate
the range of both allylic alcohols and aryl iodides under the
optimised conditions, and the results are summarised in Table
3. As shown in Table 3, the arylation reactions of but-3-en-2-ol
with a variety of aryl iodides proceeded smoothly under mild
conditions affording the corresponding 4-arylbutan-2-ones
3a–i in good to excellent yields (entries 1–9). Both electron-
donating and electron-withdrawing groups were well tolerated
and the reactivity of aryl iodides with electron-withdrawing
groups was higher than that of aryl iodides with electron-
donating groups. The sterically hindered aryl iodides such as
2-methoxyiodobenzene and 2-trifluoromethyliodobenzene
could also react with but-3-en-2-ol to afford the corresponding
arylation products 3c and 3i in good yields (entries 3 and 9).
The arylation reaction of the other secondary allylic alcohols
such as pent-4-en-3-ol with aryl iodides under the same condi-
tions also proceeded smoothly to give the desired arylation
Table 2 Reaction condition screening for the arylation reaction
of but-3-en-2-ol (1.5 equiv.) with iodobenzenea
Entry TBAC quantity
/mol%
Base Pd quantity Time Yieldb
/mol%
/h
/%
1
2
100
100
100
100
100
20
Bu3N
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.6
0.3
1.0
1.5
12
14
7
12
12
10
10
10
7
75
62
93
73
69
43
71
86
92
87
93
92
DBU
3
NaHCO3
Na2CO3
Cs2CO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
NaHCO3
4
5
6
7
50
8
80
9
120
100
100
100
10
11
12
18
5
3
a Reaction conditions: iodobenzene (1.0 mmol), but-3-en-2-ol
(1.5 mmol), base (2.5 mmol) in DMF (1.0 mL) at 100 °C under
Ar.
b Isolated yield.
Scheme 2

JOURNAL OF CHEMICAL RESEARCH 2013 335
Table 3 Heterogeneous arylation reaction of allylic alcohols
used for at least six consecutive trials without any decrease
in activity. The heterogeneous arylation reaction of allylic
alcohols with aryl iodides catalysed by the MCM-41-2N-
Pd(OAc)2 complex provides a better and practical procedure
for the synthesis of a variety of β-aryl ketones.
with aryl iodidesa
Entry
R
Ar
Time/h Product Yield/%b
1
2
Me
Me
Me
Me
Me
Me
Me
Me
Me
Et
Ph
7
8
3a
3b
3c
3d
3e
3f
3g
3h
3i
93
90
87
94
96
87
98
92
78
95
85
3-CH3C6H4
2-CH3OC6H4
4-ClC6H4
3
12
5
Experimental
4
5
4-CH3COC6H4
4-CH3OC6H4
4-NO2C6H4
4-BrC6H4
2-CF3C6H4
4-NO2C6H4
2-CH3OC6H4
5
All chemicals were reagent grade and used as purchased. DMF was
dried and distilled before use. The products were purified by flash
chromatography on silica gel. Mixture of EtOAc and hexane are
generally used as eluent. All coupling products were characterised by
comparison of their spectra and physical data with authentic samples.
6
9
7
4
8
6
9
12
4
10
11
3j
3k
1
IR spectra were determined on a Perkin-Elmer 683 instrument. H
Et
12
NMR spectra were recorded on a Bruker Avance 400 MHz spectro-
meter with TMS as an internal standard in CDCl3 as solvent. 13C NMR
spectra (100 MHz) were recorded on a Bruker Avance 400 MHz spec-
trometer in CDCl3 as solvent. Palladium content was determined with
an inductively coupled plasma atom emissionAtomscan16 (ICP-AES,
TJA Corporation) instrument. X-ray powder diffraction was obtained
on a Damx-rA (Rigaka) instrument. X-ray photoelectron spectra was
recorded on an XSAM 800 (Kratos) instrument. Microanalyses were
recorded by using a Yanaco MT-3 CHN microelemental analyser.
The mesoporous material MCM-41 was easily prepared according to
a literature procedure.37
Synthesis of MCM-41-2N: A solution of 3-(2-aminoethylamino)pro
pyltrimethoxysilane (1.54 g) in dry chloroform (18 mL) was added to
a suspension of the MCM-41 (2.2 g) in dry toluene (180 mL). The
mixture was stirred for 24h at 100 °C. Then the solid was filtered and
washed by CHCl3 (2 × 20 mL), and dried under reduced pressure at
160 °C for 5h. The dried white solid was then soaked in a solution of
Me3SiCl (3.1 g) in dry toluene (100 mL) at room temperature under
stirring for 24h. Then the solid was filtered, washed with acetone
(3 × 20 mL) and diethyl ether (3 × 20 mL), and dried under reduced
pressure at 120 °C for 5h to obtain 3.49 g of hybrid material MCM-41-
2N. The nitrogen content was found to be 1.84 mmol g−1 by elemental
analysis.
a Reaction conditions: 1 (1.5 mmol), 2 (1.0 mmol), MCM-41-2N-
Pd(OAc)2 (0.6 mol%), TBAC (1.0 equiv.), NaHCO3 (2.5 mmol) in
DMF (1.0 mL) at 100 °C under Ar.
b Isolated yield.
possible recoordination or precipitation of soluble palladium
upon cooling. We found that, after this hot filtration, no further
reaction was observed. This result suggests that the palladium
catalyst remains on the support at elevated temperatures during
the reaction and points to a process of a heterogeneous nature.
For a heterogeneous transition-metal catalyst, it is important
to examine its ease of separation, recoverability and reusabil-
ity. This heterogeneous palladium catalyst can be easily recov-
ered by a simple filtration of the reaction solution. We also
investigated the possibility of reusing the catalyst by using the
arylation reaction of but-3-en-2-ol with 4-nitroiodobenzene.
After carrying out the reaction, the catalyst was separated by
simple filtration and washed with distilled water, EtOH, and
Et2O. After being air-dried, it can be reused directly without
further purification. The recovered palladium catalyst was
used in the next run, and almost consistent activity was
observed for six consecutive cycles (Table 4, entries 1–6). In
general, the continuous recycle 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. The high stability and excellent reus-
ability of the catalyst may result from the chelating action of
the bidentate 2-aminoethylamino 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-41-2N-Pd(OAc)2 complex make it a highly attractive
heterogeneous palladium catalyst for the parallel solution
phase synthesis of diverse libraries of compounds.
Preparation of MCM-41-2N-Pd(OAc)2: In a small Schlenk tube, the
hybrid material MCM-41-2N (2.03 g) was mixed with Pd(OAc)2
(0.137 g, 0.61 mmol) in dry acetone (50 mL). The mixture was
refluxed for 72h 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 5h to give 2.12 g
of a light yellow palladium complex [MCM-41-2N-Pd(OAc)2]. The
nitrogen and palladium content was found to be 1.68 mmol g−1 and
0.27 mmol g−1, respectively.
Synthesis of β-aryl ketones; general procedure
An oven-dried Schlenk tuble equipped with a magnetic stirring bar
was charged with MCM-41-2N-Pd(OAc)2 (22 mg, 0.006 mmol Pd),
aryl iodide (1.0 mmol), allylic alcohol (1.5 mmol), TBAC (1.0 mmol),
and NaHCO3 (2.5 mmol) followed by anhydrous DMF (1 mL) under
Ar. The reaction mixture was stirred in an oil bath at 100 °C for 4–12h.
The mixture was cooled to room temperature, diluted with diethyl
ether (30 mL) and filtered. The MCM-41-2N-Pd(OAc)2 complex was
washed with distilled water (2 × 5 mL), EtOH (2 × 5 mL), and Et2O
(2 × 5 mL) and reused in the next run. The filtrate was washed with
water (2 × 10 mL) and dried over anhydrous magnesium sulfate. The
solvent was removed and the residue was purified by flash column
chromatography on silica gel (hexane–ethyl acetate = 10:1).
4-Phenylbutan-2-one: Oil.14 IR (film): ν (cm−1) 3020, 2925, 1717,
1610, 1449, 1365, 910, 696; 1H NMR (400 MHz, CDCl3): δ 7.33–7.28
(m, 2H), 7.24–7.20 (m, 3H), 2.92 (t, J = 7.6 Hz, 2H), 2.78 (t, J =
7.6 Hz, 2H), 2.16 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 207.9,
141.0, 128.5, 128.3, 126.1, 45.2, 30.1, 29.8.
In summary, we have developed a novel, practical and
economic catalyst system for the arylation reaction of allylic
alcohols with aryl iodides by using an MCM-41-supported
bidentate nitrogen palladium complex as catalyst with TBAC
as an additive in DMF. This novel heterogeneous palladium
catalyst can be very conveniently prepared by a simple two-
step procedure from commercially available and cheap reagents
and recycled by a simple filtration of the reaction solution and
Table 4 Arylation of but-3-en-2-ol with 4-nitroiodobenzene
catalysed by recycled catalysta
4-(3-Methylphenyl)butan-2-one: Oil.7 IR (film): ν (cm−1) 3016,
2922, 1716, 1609, 1365, 1160, 779, 699; 1H NMR (400 MHz, CDCl3):
δ 7.17 (t, J = 7.2 Hz, 1H), 7.02–6.96 (m, 3H), 2.86 (t, J = 7.6 Hz, 2H),
2.75 (t, J = 7.6 Hz, 2H), 2.32 (s, 3H), 2.14 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 208.0, 141.0, 138.1, 129.1, 128.4, 126.9, 125.3,
45.3, 30.1, 29.7, 21.4.
Cycle
Yield/%b
Cycle
Yield/%b
1
3
5
98
96
96
2
4
6
97
97
95
a Reaction conditions: 4-nitroiodobenzene (1.0 mmol), but-3-
en-2-ol (1.5 mmol), MCM-41-2N-Pd(OAc)2 (0.6 mol%), TBAC
(1.0 mmol), NaHCO3 (2.5 mmol) in DMF (1.0 mL) at 100 °C for 4h
under Ar.
4-(2-Methoxyphenyl)butan-2-one: Oil. IR (film): ν (cm−1) 3023,
2926, 1726, 1683, 1608, 1456, 1097, 781, 701; 1H NMR (400 MHz,
CDCl3): δ 7.21–7.12 (m, 2H), 6.89–6.83 (m, 2H), 3.82 (s, 3H), 2.88
(t, J = 7.6 Hz, 2H), 2.72 (t, J = 7.6 Hz, 2H), 2.14 (s, 3H); 13C NMR
b Isolated yield.

336 JOURNAL OF CHEMICAL RESEARCH 2013
(100 MHz, CDCl3): δ 208.7, 157.4, 130.0, 129.3, 127.5, 120.5, 110.2,
55.2, 43.7, 29.9, 25.0. Anal. Calcd for C11H14O2: C, 74.13; H, 7.92.
Found: C, 73.87; H, 7.75%.
Received 12 January 2013; accepted 9 March 2013
Paper 1301719 doi: 10.3184/174751913X13668131126257
Published online: 12 June 2013
4-(4-Chlorophenyl)butan-2-one: Oil.6 IR (film): ν (cm−1) 2927,
1
1716, 1492, 1362, 1160, 1093, 811; H NMR (400 MHz, CDCl3):
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T. Maschmeyer, R.G. Bell and Q. Ge, Science, 1998, 280, 705.
30 T. Maschmeyer, F. Rey, G. Sankar and J.M. Thomas, Nature, 1995, 378,
159.
4-(4-Nitrophenyl)butan-2-one: Oil.6 IR (film): ν (cm−1) 2958, 1710,
1
1605, 1520, 1342, 1169, 1109, 857; H NMR (400 MHz, CDCl3):
δ 8.14 (d, J = 8.4 Hz, 2H), 7.36 (d, J = 8.4 Hz, 2H), 3.00 (t, J = 7.2 Hz,
2H), 2.82 (t, J = 7.2 Hz, 2H), 2.17 (s, 3H); 13C NMR (100 MHz,
CDCl3): δ 206.7, 149.0, 146.5, 129.3, 123.8, 44.2, 30.1, 29.3.
4-(4-Bromophenyl)butan-2-one: Oil.8 IR (film): ν (cm−1) 2927,
1716, 1489, 1367, 1161, 1072, 1011, 808; 1H NMR (400 MHz,
CDCl3): δ 7.39 (d, J = 8.4 Hz, 2H), 7.06 (d, J = 8.4 Hz, 2H), 2.84 (t,
J = 7.4 Hz, 2H), 2.73 (t, J = 7.4 Hz, 2H), 2.13 (s, 3H); 13C NMR
(100 MHz, CDCl3): δ 207.4, 140.0, 131.5, 130.1, 119.9, 44.8, 30.1,
29.0.
4-(2-Trifluoromethylphenyl)butan-2-one: Oil. IR (film): ν (cm−1)
2901, 1717, 1609, 1494, 1361, 1312, 1155, 1111, 1046, 916, 725;
1H NMR (400 MHz, CDCl3): δ 7.61 (d, J = 8.0 Hz, 1H), 7.45 (t, J =
7.4 Hz, 1H), 7.33–7.28 (m, 2H), 3.06 (t, J = 7.6 Hz, 2H), 2.75 (t, J =
7.6 Hz, 2H), 2.15 (s, 3H); 13C NMR (100 MHz, CDCl3): δ 207.2,
1
2
139.8, 132.0, 131.1, 128.4 (q, JCF = 30 Hz), 126.3, 126.0 (q, JCF
=
6 Hz), 123.2, 45.2, 29.8, 26.6. Anal. Calcd for C11H11OF3: C, 61.11;
h, 5.13. Found: C, 60.87; H, 5.32%.
1-(4-Nitrophenyl)pentan-3-one: Oil.9 IR (film): ν (cm−1) 2970,
1
1705, 1602, 1515, 1338, 1106, 855; H NMR (400 MHz, CDCl3):
δ 8.13 (d, J = 8.4 Hz, 2H), 7.36 (d, J = 8.4 Hz, 2H), 3.02 (t, J = 7.4 Hz,
2H), 2.80 (t, J = 7.4 Hz, 2H), 2.44 (q, J = 7.4 Hz, 2H), 1.06 (t, J =
7.4 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 209.6, 149.2, 146.4,
129.3, 123.7, 42.9, 36.1, 29.4, 7.7.
1-(2-Methoxyphenyl)pentan-2-one: Oil. IR (film): ν (cm−1) 2976,
1714, 1602, 1495, 1362, 1244, 1221, 1029, 756; 1H NMR (400 MHz,
CDCl3): δ 7.21–7.12 (m, 2H), 6.89–6.83 (m, 2H), 3.82 (s, 3H), 2.88
(t, J = 7.6 Hz, 2H), 2.70 (t, J = 7.6 Hz, 2H), 2.42 (q, J = 7.2 Hz, 2H),
1.05 (t, J = 7.2 Hz, 3H); 13C NMR (100 MHz, CDCl3): δ 211.5, 157.4,
130.0, 129.4, 127.4, 120.5, 110.2, 55.2, 42.3, 36.0, 25.1, 7.8. Anal.
Calcd for C12H16O2: C, 74.97; H, 8.39. Found: C, 74.69; H, 8.16%.
31 C.-J. Liu, S.-G. Li, W.-Q. Pang and C.-M. Che, Chem. Commun., 1997,
65.
32 P.C. Mehnert, D.W. Weaver and J.Y. Ying, J. Am. Chem. Soc., 1998, 120,
12289.
33 H. Yang, G. Zhang, X. Hong and Y. Zhu, J. Mol. Catal. A: Chem., 2004,
210, 143.
34 C. Gonzalez-Arellano, A. Corma, M. Iglesias and F. Sanchez, Adv. Synth.
Catal., 2004, 346, 1758.
35 F. Alonso, I.P. Beletskaya and M. Yus, Tetrahedron, 2005, 61, 11771.
36 H.E.B. Lempers and R.A. Sheldon, J. Catal., 1998, 175, 62.
37 M.H. Lim and A. Stein, Chem. Mater., 1999, 11, 3285.
We thank the National Natural Science Foundation of China
(20862008) for financial support.

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