2-Aminophenyl diphenylphosphinite as a new ligand for heterogeneous palladium-catalyzed Heck-Mizoroki reactions in water in the absence of any organic co-solvent

Article abstract of DOI:10.1016/j.tet.2009.06.081

In this article, 2-aminophenyl diphenylphosphinite has been introduced as a new ligand for the Heck-Mizoroki reactions of aryl halides with styrene and n-butylacrylate in water in the presence of palladium acetate. This ligand is easily prepared from the reaction of chlorodiphenyl phosphine with 2-aminophenol in high yield. Pre-catalyst [Pd(OAc)₂] in the presence of the ligand produces a black solid mass. The solid catalyst has been recycled for the reaction of bromobenzene with styrene for six runs without appreciable loss of its catalytic activity.

Full text of DOI:10.1016/j.tet.2009.06.081

Tetrahedron 65 (2009) 7079–7084
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
2-Aminophenyl diphenylphosphinite as a new ligand for heterogeneous
palladium-catalyzed Heck–Mizoroki reactions in water in the absence
of any organic co-solvent
*
*
Habib Firouzabadi , Nasser Iranpoor , Mohammad Gholinejad
Department of Chemistry, College of Sciences, Shiraz University, Shiraz 71454, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
In this article, 2-aminophenyl diphenylphosphinite has been introduced as a new ligand for the Heck–
Mizoroki reactions of aryl halides with styrene and n-butylacrylate in water in the presence of palladium
acetate. This ligand is easily prepared from the reaction of chlorodiphenyl phosphine with 2-amino-
phenol in high yield. Pre-catalyst [Pd(OAc)2] in the presence of the ligand produces a black solid mass.
The solid catalyst has been recycled for the reaction of bromobenzene with styrene for six runs without
appreciable loss of its catalytic activity.
Received 8 March 2009
Received in revised form 19 May 2009
Accepted 11 June 2009
Available online 25 June 2009
Keywords:
Heck–Mizoroki coupling reaction
Ó 2009 Elsevier Ltd. All rights reserved.
Aryl halides
Pd(OAc)2
2-Aminophenyl diphenylphosphinite
Water
1. Introduction
accompanied with some drawbacks such as the requirement of
elevated temperatures, employing hazardous organic solvents and
Nowadays, environmental consciousness encourages more en-
vironmentally benign chemical processes. Along this line, in-
dustries have started implementing green chemistry practices such
as waste prevention, using new heterogeneous catalysts and the
use of less toxic solvents and reagents.1 However, disposal of or-
ganic solvents is the major problem in chemical industries which
accounts around 80% of their waste.2,3
Water is considered as an alternative to expensive, flammable
and toxic organic solvents.4,5 Conducting the reactions in aqueous
media is usually accompanied with selectivity that cannot be
attained using organic solvents.5 Furthermore, separation of water
insoluble organic compounds from the aqueous phase could easily
be achieved.6–11
Transition-metal-catalyzed reactions are established as impor-
tant protocols in organic synthesis.12 Among transition metals,
palladium catalysis is an essential tool for C–C bond formation re-
actions. Among basic types of palladium-catalyzed trans-
formations, the Heck–Mizoroki reaction which is the reaction
between aryl halides and olefins occupy a special place.13,14 Like any
other established method, the Heck–Mizoroki reaction is also
using expensive phosphine ligands. Challenging subjects for in-
vestigation in Heck–Mizoroki reactions include shortening of the
reaction times, applying recyclable catalysts that can be isolated
easily from the reaction mixture and improving the low reactivity
of aryl bromides and chlorides.
The Heck–Mizoroki reaction is usually achieved using palladium
complexes with phosphine ligands; however, phosphine-free sys-
tems have also appeared in the literature.15–18 There are some re-
ports on the Heck–Mizoroki reactions conducted in neat water or in
aqueous media using organic co-solvents.19–23 Other reports re-
garding the Heck–Mizoroki reactions include using palladium
nanoparticles,24 microwave-assisted conditions,25 amberlite,26
polymer supported palladium,27 oxime-derived palladacycle,28
C–N-palladacyclic catalyst,29 palladium on carbon,30 and super-
critical conditions31 in aqueous media.
Palladium in the presence of phosphinite ligands [PPh2(OR)] and
related compounds have also been reported for carbon–carbon
bond formation reactions.33,34 We have also reported an imidazo-
lium-based phosphinite ionic liquid as a medium and a ligand in
the Heck–Mizoroki reaction, dehalogenation and homocoupling of
aryl halides in the presence of PdCl2.32
Now, we report efficient Heck–Mizoroki reaction of various aryl
halides in the presence of an easily prepared 2-aminophenyl
diphenylphosphinite as a ligand in water in the absence of any
organic co-solvent.
* Corresponding authors. Tel.: þ98 711 2284822; fax: þ98 711 2280926.
E-mail addresses: firouzabadi@chem.susc.ac.ir (H. Firouzabadi), iranpoor@
chem.susc.ac.ir (N. Iranpoor).
0040-4020/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2009.06.081

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H. Firouzabadi et al. / Tetrahedron 65 (2009) 7079–7084
2. Results and discussion
The molar ratio of ligand (L) with respect to Pd has been de-
termined by employing the mole ratio method.32 The complex for-
mation between the ligand and Pd(OAc)2 in DMF was in good
harmonywiththeformationofML2 complex as presentedby Figure 2.
Some information about the shape and the size of the catalyst
particles was obtained by SEM images as presented in Figure 3. The
images show that in the presence of Pd(OAc)2 the shape of the
particles have been verified from needle (A) to highly dispersed
spherical form, uniformly sized particles (B) which is characteristic
of Pd(0) complex formation.39
Phosphinites are potential ligands for the formation of com-
plexes with metal ions that can be used as catalysts in organic
synthesis. They are prepared easily from the reaction of commer-
cially available compounds such as PPh2Cl with alcohols or
phenols.34–38
In this study, 2-aminophenyl diphenylphosphinite (L) was
obtained from the reaction of chlorodiphenyl phosphine with
2-aminophenol in 87% yield (Fig. 1).
The formation of the Pd(0) catalyst was also supported by the
XRD of the powder obtained by drying of the aqueous mixture of
Pd(OAc)2 and the ligand at (111),(200),(220) and (311) crystallo-
graphic planes as illustrated in Figure 4.40
H2N
O
P
Figure 1. 2-Aminophenyl diphenylphosphinite (L).
2-Aminophenyl diphenylphosphinite is water and air stable, and
the handling of its palladium complex does not need special pre-
cautions. The formation of active Pd(0) catalyst as a black insoluble
mass was achieved by reacting Pd(OAc)2 with 2-aminophenyl
diphenylphosphinite (L) in water at 80 ꢀC. At the start, the colour of
the heterogeneous mixture was beige, which was changed to a dark
brown colour and finally, a black heterogeneous mass was pro-
duced after a few minutes.
Figure 4. Powder XRD patterns resulted from the evaporation of the aqueous solution
of Pd(OAc)2 and the ligand.
The stability of the ligand towards basic conditions was also
studied. For this purpose, a mixture of 2-aminophenyl diphenyl-
phosphinite (2 mmol) with of NaOH (3 mmol) in H2O (5 mL) was
refluxed for 3 h. After workup of the reaction mixture, the intact
aminophosphinite was isolated over 97% yield.
In order to find a suitable base for the reactions, the reaction of
bromobenzene (1 mmol) as a model compound with styrene
(1.5 mmol), in the presence of Pd(OAc)2 (3 mol %), L (9 mol %) and
different bases was studied. The results indicate that NaOH was the
best base for this reaction (Table 1).
In order to show the benefit of using water as solvent, we
compared the coupling reaction of 4-bromotoluene with styrene in
toluene and water. For this aim, 4-bromotoluene was treated with
styrene in the presence of Pd(OAc)2 (3 mol %) and L (9 mol %) in
toluene and water at 95 ꢀC for 3 h. The reaction which was con-
ducted in water resulted in the isolation of 81% of the product
Figure 2. Mole ratio plot for complex formation between Pd(OAc)2 and 2-amino-
phenyl diphenylphosphinite (L) at 271 nm in relation to lmax of the ligand.
Figure 3. SEM image of L in the absence of Pd(OAc)2 (A) and after addition of Pd(OAc)2 to L (B) (magnification of 5000).

H. Firouzabadi et al. / Tetrahedron 65 (2009) 7079–7084
7081
Table 1
The results of the reaction of bromobenzene with styrene in the presence of
different bases using Pd(OAc)2 and the ligand
Table 3
Heck–Mizoroki coupling of different aryl halides with styrene in water in the
presence of the ligand and NaOH as base
Ph
Br
Pd(OAc)2 (3 mol%)
+
Ph
L (9 mol%), Base
Ph
Pd(OAc)2 (2-3 mol%)
X
H2O (1.5 mL), 80 °C
L (6-9 mol%)
+
Ph
NaOH (2 eq), H2O (1.5 mL)
80 or 95 °C
R
Entry
Base
Time (h)
Isolated yield%
R
1
2
3
4
5
6
7
0
24
0.75
18
18
7
0
83
70
60
78
54
45
X = I, Br, Cl
NaOH
K2CO3
K3PO4
CS2CO3
Et3N
Entry
Ar–X
Pd(OAc)2
Time
(h)
Isolated
yield%
ProductRef.
(mol %), [T ꢀC]
14
14
I
DBU
1
2
3
4
2, [80]
2, [80]
3, [80]
3, [95]
0.4
2
85
1a41
I
while, for the similar reaction in toluene, only 20% of the desired
product was isolated.
The benefit of using 2-aminophenyl diphenylphosphinite ligand
in comparison with Ph3P and under ligand-free conditions has also
been disclosed upon the reaction of 4-bromotoluene with styrene
in water. The results are presented in Table 2.
86 (15)a
84 (10)a
81 (trace)a
1b42
1a41
1c43
MeO
Br
0.75
3
Br
Br
Table 2
Comparison of the reaction of 4-bromotoulene with styrene in the presence of 2-
aminophenyl diphenylphosphinite, Ph3P and ligand-free conditions in water
Me
Cl
Ph
5
6
3, [95]
3, [95]
5
9
79
1d44
Br
Pd(OAc)2 (3 mol%)
H2O (1.5 mL), 95 °C
NaOH (2 eq.), Ligand
+
Ph
Me
Me
Me
84b
1e41
Br
Entry
Ligand
Time (h)
Yield%
1
2
3
Ligand-free
PPh3
L
5
4
3
Trace
30
81
Br
Br
7
3, [95]
3.5
90 (38)a,c
1f41
NC
Then, the optimized conditions were applied in Heck–Mizoroki
reactions of structurally different aryl halides. The amount of the
Pd(OAc)2 varies from 2 to 3 mol % and the nature of the aryl halides
determines the temperature requirement for the reaction.
8
3, [95]
3, [95]
3, [95]
5
16
15
90c
1g42
1h42
1kd
O2N
N
Br
Br
9
85 (35)a
Most of the reactions proceeded at two different temperatures,
80 and 95 ꢀC and in some cases, in a sealed tube at 130 ꢀC. The
amount of the aminophosphinite ligand (L) varies from 6 to
9 mol % (Table 3). However, iodobenzene, 4-iodoanisole, bromo-
benzene and 3-bromothiophene reacted with styrene at 80 ꢀC to
give the desired trans-alkenes in 85%, 86%, 84% and 85% isolated
yields respectively (Table 3, entries 1, 2, 3, 11). Homo-coupled
products were also obtained in 5–8% isolated yields. The reaction
of the other aryl bromides with styrene were performed at 95 ꢀC to
give their corresponding trans-stilbenes in the appropriate re-
action times in high to excellent yields (Table 3). In these reactions,
the corresponding homo-coupled products were also isolated in
5–8% yields.
The reaction of aryl chlorides with styrene is usually sluggish
with low yields. We have also studied this reaction in the presence
of 2-aminophenyl diphenylphosphinite (L, 9 mol %) with Pd(OAc)2
(3 mol %) in water at 95 ꢀC using aryl chlorides and styrene. The
desired trans-stilbenes were isolated in 40–45% yields after 10–24 h
(Table 3, entries 12–14). These low yielding reactions forced us to
study similar reactions in a sealed-tube at higher temperatures in
water. For this purpose, chlorobenzene, 4-chlorotoluene and
4-chloronitrobenzene were reacted with styrene in the presence of
Pd(OAc)2 (3 mol %) and L (9 mol %) in water in a sealed tube at
130 ꢀC for about 20 h (Table 3). Reaction of chlorobenzene and
4-chlorotoluene was successful and the corresponding products
N
10
85c
N
Br
11
3, [80]
1
85
1l45
S
Cl
12
13
3, [95]
3, [95]
10
20
45 (85)e
42 (80)e
1a41
Cl
Cl
1c43
Me
14
3, [95]
24
40c (68)c,e
1g42
O2N
a
Yields in parenthesis show the reactions conducted in the absence of ligand.
GC yields, n-octane was used as an internal standard.
The reaction of high melting point substrates was preformed in the presence of
b
c
TBAB (15 mol %) in order to facilitate the solubility of the substrate.
d
Spectroscopic data are given in Experimental section.
Yields in the parenthesis show the reactions conducted in sealed tubes at 130 ꢀC.
e

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H. Firouzabadi et al. / Tetrahedron 65 (2009) 7079–7084
Table 4
were obtained in 85 and 80% isolated yields respectively. However,
the reaction of 4-chloronitrobenzene did not proceed to comple-
tion and the desired product was isolated in 68% yield.
Isolation of the heterogeneous catalyst was easily performed by
filtration or centrifugation. The isolated catalyst was washed with
diethyl ether and dried in air. The resulting isolated catalyst was
used for the reaction of bromobenzene with styrene for six runs to
afford trans-stilbene in 79–83% isolated yields (Table 4).
Recycling of the catalyst for the reaction of bromobenzene with styrene
Ph
Br
Pd(OAc)2 (3 mol%)
+
NaOH (2 eq.), L (9 mol%)
H2O (1.5 mL), 80 °C
Ph
Run
Time (h)
Isolated yield%
Finally, the reaction of n-butyl acrylate with different aryl
halides was investigated. In these reactions iodobenzene and
4-iodoanisole were treated with n-butyl acrylate in the presence
of Pd(OAc)2 (2 mol %), Cs2CO3 as a base and the ligand L (6 mol %)
at 80 ꢀC. The reactions proceeded smoothly with the formation of
trans-isomers in 85% and 89% isolated yields respectively (Table 5,
1
2
3
4
5
6
1
1
1
1
1
1
83
83
81
80
80
79
Table 5
Heck–Mizoroki reactions of different aryl halides with n-butyl acrylate in water
O
Pd(OAc)2 (2-3 mol%)
L (6-9 mol%)
Cs2CO3(2 eq), H2O (1.5 mL)
80 or 95 °C
X
O
O
+
O
R
R
X = I, Br
2a-2l
Entry
1
Ar–X
Pd(OAc)2
Time
(h)
Isolated yield%
ProductRef.
(mol %), [T ꢀC]
I
2, [80]
2
85
89
86
80
2a41
I
2
3
4
2, [80]
3, [80]
3, [95]
5
4
2b41
2a41
2c46
MeO
Br
Br
20
Me
Cl
Br
5
6
3, [95]
3, [95]
10
24
72
2d43
Me
76a
2e41
Br
Br
Br
7
8
9
3, [95]
3, [95]
3, [95]
5
6
86b
88b
80
2f41
2g42
2h41
NC
O2N
N
Br
Br
22
N
10
3, [95]
3, [80]
20
5
75b
73
2kc
N
Br
11
2l41
S
a
GC yield, n-octane has been used as an internal standard.
For the solid and high melting point substrates, the reactions were preformed in TBAB (15 mol %) in order to facilitate their solubility.
Spectroscopic data of these products are given in Experimental section.
b
c

H. Firouzabadi et al. / Tetrahedron 65 (2009) 7079–7084
7083
entries 1, 2). The corresponding homo-coupled products were also
isolated in less than 10% yields. In these reactions, n-butyl acrylate
cannot tolerate strong basic conditions such as NaOH solutions;
therefore, the reactions were performed in the presence of
a weaker base such as Cs2CO3. Aryl bromides were also reacted
with n-butyl acrylate with the molar ratios of aryl bromides,
n-butyl acrylate, Pd(OAc)2 (3 mol %) and the ligand L (9 mol %) in
water at 80 ꢀC and 95 ꢀC. The reactions proceeded smoothly and
the desired products were isolated in 72–88% yields (Table 5). The
reaction of aryl chlorides with n-butyl acrylate in the presence of
Pd(OAc)2, L and Cs2CO3 at 95 ꢀC failed completely in water and the
starting materials were isolated intact after prolonged reaction
times.
Calcd for %C: 73.71, %H: 5.49, %N: 4.77; found: %C: 73.43, %H: 5.07,
%N: 4.14. m/z (Mþ): 293.
4.3. General experimental procedure for the Heck–Mizoroki
reaction
In a conical flask (5 mL), a mixture of Pd(OAc)2 (7 mg, 0.03 mmol)
and L (26 mg, 0.09 mmol) in distilled water (1.5 mL) was prepared
and heated at 80 ꢀC for 10 min with steering to give an insoluble
black material. To the resulting black material, aryl halide (1 mmol),
styrene (0.17 mL, 1.5 mmol) or n-butyl acrylate (0.21 mL, 1.5 mmol)
and NaOH (80 mg, 2 mmol) were added at 80 or 95 ꢀC. Stirring was
continued until the consumption of the starting materials (GC and
TLC). The resulting heterogeneous mixture was extracted with ethyl
acetate or diethyl ether (6ꢂ1 mL). The organic phase was separated
and dried over anhydrous Na2SO4 and evaporated. The resulting
crude product was purified by flash chromatography to give the
desired pure coupling products in high to excellent isolated yields
(Tables 3 and 5).
3. Conclusions
In this study, for the first time, we have introduced 2-amino-
phenyl diphenylphosphinite (L) as a ligand for Heck–Mizoroki re-
actions in water in the absence of an organic co-solvent.
Aryl iodides and bromides were reacted efficiently with styrene
and n-butylacrylate at 80 and 95 ꢀC in the presence of the catalyst
in water. However, the reaction of less reactive aryl chlorides with
styrene was conducted in a sealed tube at 130 ꢀC. The procedure is
easy and does not require special precautions. All the reactions
were conducted in the air in water without the use of an organic co-
solvent. The solid catalyst was simply isolated by filtration or cen-
trifugation and was recycled smoothly for several runs without
appreciable loss of its catalytic activity.
4.3.1.
Table 3, entry 5; 1H NMR (250 MHz, CDCl3)
11H). 13C NMR (62.9 MHz, CDCl3)
(ppm): 136.9, 135.8, 133.1, 129.3,
b
-4-Chlorophenyl styrene44
d
(ppm): 7.5–7.23 (m,
d
128.8, 128.7, 127.8, 127.6, 127.3, 126.5.
4.3.2. 5-Styryl-pyrimidine
Table 3, entry10; beige solid powder, mp: 68–70 ꢀC. 1H NMR
(250 MHz, CDCl3)
d (ppm): 9.01 (s, 1H), 8.79 (s, 2H), 7.45–7.48 (d,
2H, J¼7.2), 7.23–7.48 (m, 3H), 7.17 (d, 1H, J¼16.5), 6.92 (d, 1H,
J¼16.5). 13C NMR (62.9 MHz, CDCl3)
d (ppm): 157.1, 154.2, 135.9,
4. Experimental
4.1. General
132.7, 130.9, 128.8, 128.6, 126.8, 121.0. IR (cmꢁ1): 3041.1, 1634.1,
1556.5, 1414.1, 1186.4, 961.0, 718.7, 694.2, 633.5. Anal. Calcd for
%C: 79.10, %H: 5.53, %N: 15.37; found: %C: 79.04, %H: 5.51, %N:
15.45.
IR spectra were run on a Perkin–Elmer 781 spectrophotometer.
The 1H NMR and 13C NMR spectra were recorded on a Bruker
Avance DPX 250 MHz Spectrometer in CDCl3 or DMSO-d6 solvents
using TMS as an internal standard. 31P NMR spectra were recorded
at 90 MHz in DMSO-d6 solvent using TMS as an internal standard.
4.3.3. 3-p-Tolyl-butyl acrylate46
Table 5, entry 4; 1H NMR (250 MHz, CDCl3)
d (ppm): 7.57 (d, 1H,
J¼16.0), 7.33 (d, 2H, J¼8.0), 7.09 (d, 2H, J¼8.0), 6.31 (d, 1H, J¼16.0),
4.12 (t, 2H, J¼6.7), 2.28 (s, 3H), 1.60 (m, 2H), 1.35 (m, 2H), 0.88 (t, 3H,
J¼7.2).
Chemical shifts were reported in ppm (d), and coupling constants
(J), in Hz. Mass spectra were obtained at 70 eV. The reaction
monitoring were carried out on silica gel analytical sheets or by GC
analysis using a 3-m length column packed with DC-200 stationary
phase. Scanning electron micrographs were obtained by SEM (SEM,
XL-30 FEG SEM, Philips, at 20 kV). X-ray diffractions were obtained
using XRD, D8, Avance, Bruker, axs.
4.3.4. 3-Pyrimidin-5-yl-butyl acrylate
Table 5, entry 10; light yellow coloured viscous oil. 1H NMR
(250 MHz, CDCl3)
d (ppm): 9.14 (s, 1H), 8.79 (s, 2H), 7.54 (d, 1H,
J¼16.2), 6.55 (d, 1H, J¼16.2), 4.15 (t, 2H, J¼6.7), 1.56–1.64 (m, 2H),
1.39–1.31 (m, 2H), 0.88 (t, 3H, J¼7.2). 13C NMR (62.9 MHz, CDCl3)
d
(ppm): 165.6, 159.0, 155.5, 137.0, 128.2, 122.3, 64.8, 30.5, 19.0, 13.6.
4.2. Preparation of 2-aminophenyl diphenylphosphinite (L)
IR (cmꢁ1): 3164.5, 3002.6, 2944.2, 2627.7, 2410.1, 2292.7, 1716.3,
1175.5, 1039.2, 918.3, 749.1. Anal. Calcd for %C: 64.06, %H: 6.84, %N:
13.58; found: %C: 63.94, %H: 6.75, %N: 13.43.
To a flask (50 mL) containing of t-BuOH (15 mL), was added
potassium (43 mg, 11 mmol) at room temperature and stirred
slowly until the potassium was completely consumed. To the
resulting solution, 2-aminophenol (1.1 g, 10 mmol) was added and
stirred for 30 min. To the resulting black colour solution, chloro-
diphenylphosphine (1.9 mL, 10 mmol) was added drop wise with
steering in a period of 15 min at room temperature. Then, the re-
action mixture was stirred for 10 h. To the resulting heterogeneous
light brown mixture, water (30 mL) was added and filtered. The
filter cake was washed with diethyl ether (15 mL) and dried under
vacuum at room temperature. 2-Aminophenyl diphenylphosphinite
was isolated as a beige solid compound in 87% yield, mp: 155–
4.4. Recycling of the catalyst for the reaction of
bromobenzene with styrene
Bromobenzene (0.1 mL, 1 mmol) was reacted with styrene
(0.17 mL, 1.5 mmol) in distilled water (1.5 mL) in the presence of
Pd(OAc)2 (7 mg, 0.03 mmol), L (26 mg, 0.09 mmol) and NaOH
(80 mg, 2 mmol) at 80 ꢀC. After completion of the reaction (GC),
work up of the reaction mixture was continued as stated in the
preceding general procedure. The black solid material (the catalyst)
was isolated by centrifugation. Then, the isolated black catalyst was
washed with diethyl ether and dried in air. The resulting solid
catalyst was charged into another batch of the similar reaction. This
was repeated for 6 runs to complete the reaction in 1 h. Isolation of
the coupled product was performed as discussed in the preceding
158 ꢀC. 1H NMR (250 MHz, DMSO-d6)
7.53–7.47 (m, 6H), 6.93–6.37 (m, 4H). 13C NMR (62.9 MHz, CDCl3)
(ppm): 147.7, 133.5, 131.9, 131.5, 131.4, 128.7, 122.5, 120.3, 119.1,
115.5. IR (cmꢁ1): 3355, 3267, 3047, 1504, 1434, 1280, 1218, 1110, 921,
867, 817, 694, 509, 455. 31P NMR (DMSO-d6):
(ppm)¼22.400. Anal.
d (ppm): 7.86–7.78 (m, 4H),
d
d

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Acknowledgements
The authors are grateful to Shiraz University Research Council
and TWAS Chapter of Iran Based at ISMO for the partial support of
this work. We are also grateful to Dr. Ali Afzali Ardakani and Farhad
Nowrouzi for their encouragements. Our thanks also go to Omran
Moradloo and Soghra Farahi for their technical assistance.
23. Amengual, R.; Genin, E.; Michelet, V.; Savignac, M.; Genet, J. P. Adv. Synth. Catal.
2002, 344, 393–398.
Supplementary data
24. Qiao, K.; Sugimura, R.; Bao, Q.; Tomida, D.; Yokoyama, C. Catal. Commun. 2008,
9, 2470–2474.
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NMR spectra of products are available as a supplementary data.
Supplementary data associated with this article can be found in the
online version, at doi:10.1016/j.tet.2009.06.081.
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