C(sp2)-C(sp2) cross coupling reaction catalyzed by a water-stable palladium complex supported onto nanomagnetite particles

Article abstract of DOI:10.1039/c4nj01355g

A water-stable palladium complex supported onto nanomagnetite particles was prepared and characterized. The nanocatalyst showed excellent reusability and activity in aqueous phase processes including the C(sp²)-C(sp²) cross coupling reactions. The advantages of the protocol are its generality, high yields, short reaction time, a cleaner reaction profile, and simplicity.

Full text of DOI:10.1039/c4nj01355g

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Graphical Abstract
O
O
D
O
2
H N
EtO
Si
O
O
TEOS
O
N
N
OEt
Si
SiOEt
3
O
O
O
H N
2
O
O
Si
O
1
2
OEt
Ar
Ar
X
X
Fe@SiO
2
Fe@SiO
2
B(OH)
KX
KHCO
3
OEt
Si
3
O
O
O
(I)
Ar Ar'
(
II)
N
N
O
Ar
Pd
Ar'
Si
O
O
Ar'B(OH) K
3
OEt
Fe@SiO
2
KHCO3
:Pd2+
(III)
2 2 3 2
Ar'B(OH) + K CO + H O
:
Pd0
Water-stable palladium complex supported onto nano magnetite
particles catalyzed C(sp2)-C(sp2) cross coupling reaction
Tahereh Azadbakht, Mohammad Ali Zolfigol,* Reza Azadbakht, Vahid Khakyzadeh, David M
Perrin
A new Palladium nanoparticles-based magnetic catalyst which is stable in water, has been
successfully synthesized, characterized and employed for Suzuki reaction.

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RSCPublishing
PAPER (or FOCUS or PERSPECTIVE)
Water-stable palladium complex supported onto nano
2
2
magnetite particles catalyzed C(sp )-C(sp ) cross
coupling reaction
Cite this: DOI: 10.1039/c3nj00000x
a,b
a
c
Tahereh Azadbakht, Mohammad Ali Zolfigol, * Reza Azadbakht,
d
b
Received 00th XXXXX 2013,
Accepted 00th XXXXX 2013
Vahid Khakyzadeh, David M Perrin
A waterꢀstable palladium complex supported onto nano magnetite particles was prepared and
characterized. The nanocatalyst showed excellent reusabilities and activities in aqueous phase
processes including the C (sp )ꢀC (sp ) cross coupling reaction. The advantages of the protocol
were generality, high yield, short reaction time, cleaner reaction profile, and simplicity.
DOI: 10.1039/c3nj00000x
2
2
www.rsc.org/njc
Introduction
sustainability and “green chemistry” demands. So they have an
advantage of homogenous catalyst to have high activity and
The Heck and Suzuki coupling reactions that are done with
palladiumꢀbased catalysts have shown high efficiency in the
advantage of heterogonous catalyst to have easily recovering
21
and reusing. Fe O nanoparticles is an attractive nanocatalyst
1
–6
3
4
construction of CꢀC bonds. The resulting product are very
important in pharmaceutical applications due to their significant
influences in the synthesis of bioactive compounds and organic
which have attracted many attentions due to their unique
properties such as high surface to volume ratio, low toxicity,
22–24
easily preparation and superparamagnetism.
Fe O ꢀ
3 4
7
–9
products.
Homogeneous catalysts have high activity for
supported nanoparticles can be simply separated, recovered and
reused for reaction and costs and waste can be significantly
coupling and are used for the Heck and Suzuki coupling
reactions, But this kind of catalyst does not have capability to
be easily separated and be reused in subsequent reactions.
Hence they cannot meet the sustainability demands. A
homogenous catalyst is classified in this kind of catalyst, which
lack of capability to be recycled prevents to satisfy the
requirements of “sustainability” and they are not acceptable in
this new approach. In another classification, heterogeneous
catalysts are able to be recycled and recovered but the low
activity that is attributed to their low surface contact does not
allow to be selected as a perfect catalyst. Nanochemistry as a
new area of research give us ability to synthesis the
nanoparticles by scaling down the size and make wide range of
shapes and size with unique property and specification. Many
researchers have been done to synthesis the nanoparticles and
use them as a catalyst.
volume ratio is one of the attractive advantages of
nanoparticles.
25–27
reduced.
7
In this work we synthesized new Pdꢀcatalyst based on
magnetite Fe O4 nanoparticles. The magnetite nanoparticles
3
(
MNPs) prepared and coated with a layer of silica in order to
avoid the aggregation of nanoparticles to cluster or clumps then
is capped with imineꢀfunctionalized silane and (2ꢀ[2ꢀ(2ꢀ
formylphenoxy) ethoxy] benzaldehyde) dihydroxyariyl
palladium complexes immobilized on magnetite nanoparticles
through a click reaction. We performed the Suzuki coupling
reaction as a model reaction with this new nanocatalyst to test
the activity of nanocatalyst (Scheme 1) and we chose the
environmentallyꢀfriendly solvent for the reaction with good
efficiency and high yields. The catalyst easily separated,
recovered and reused for other reactions.
1
0
1
1
1
2
1
3–19
Providing the high surface area to
Catalyst-Pd (0.2 %)
Water/DMF(1:1)
B(OH)2
+
X
K2CO3 / 100 o
C
This property increases the contact between reactants and
catalyst and can improve the activity of the catalyst, which is
desired parameter in most of the reactions. Some ideal
specifications of catalyst such as high activity, small size and
R
R
X : Cl, Br, I
R : Me, OH, OMe, CN, NO2
2
0
2
2
Scheme 1. C (sp )ꢀC (sp ) cross coupling of phenylboronic acid with aryl
ease to separate by external magnet are achievable by halides in the presence of Pd nanocatalyst.
employing the nanochemistry technology to synthesis the
1
2
Results and discussion
magnetic nanoparticles. This type of catalysts can overcome
2
8
the issue of low activity, and they can be easily recovered, Nanomagnetite particles were prepared by literature method.
separated, and reused in other reactions. They will satisfy the The nanoparticles were coated with a layer of silica with
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ARTICLE
DOI: 10.1039/C4NJ01355G
New Journal of Chemistry
O
O
D
H N
2
O
OEt
OEt
Si
O
O
O
O
O
O
O
Si
O
O
PdCl2
N
N
O
TEOS
SiOEt
3
O
O
N
N
Si
Pd
NH2
Si
Toluene
Under argon
12h
Si
O
EtO
O
O
1
2
OEt
OEt
3
4
5
Figure 1. The synthetic route of nanocatalyst 5.
tetraethyl orthosilicate (TEOS). Silanation of the silicaꢀcoated
magnetite nanoparticles (SMNPs) with 3ꢀaminopropyl in Figure . A broad band near 1000ꢀ1100 cm indicated the
triethoxysilane was performed to obtain compound 3. The silica coated magnetite nanoparticles. The observation of a
compound 3 with dialdehyde of 2ꢀ[2ꢀ(2ꢀformylphenoxy) band at 1635 cm Curve b—4 confirmed C=N double bond.
ethoxy]benzaldehyde (D) sonicated for 10 min to produce The band at 1635 cm due to reaction with Pd shifted to lower
FTꢀIR spectra of compounds (3), (4) and (5) are illustrated
ꢀ1
ꢀ
1
ꢀ
1
ꢀ
1
structure of 4. In last step PdCl added to the reaction to frequency 1625 cm in Curve c—5.
2
demonstrate the nanocatalyst 5. These steps are illustrated in
Figure 1. Transmission electron microcopy (TEM) images of
the catalyst are indicated in Figure 2.
Figure 2. TEM images of nanocatalyst.
Figure 4. FTꢀIR spectra of the compound 3ꢀ5: Curve a— 3; Curve b—4;
Curve c—5.
Via analysing of TEM of catalyst, we found that more than
7
0% of catalyst size is < 20 nm (Table 1).
Magnetic measurements of the Fe O nanoparticles and
3 4
nanocatalyst with Pd were investigated at room temperature by
using a vibrating sample magnetometer (VSM). Based on
magnetization curves, the saturation of the obtained catalyst
Table 1. Particle size distribution histogram from TEM image.
Entry
Size (nm)
Abundance
І
10ꢀ15
15ꢀ20
35.3
35.3
dropped from 35 emu/g (Fe
This reduction in saturation accounts for the surface coating on
Fe nanoparticles that interact with Pdꢀnanoparticle catalyst
Figure ).
3 4
O ) to 7 emu/g for the catalyst.
II
III
25ꢀ30
32.4
O
3 4
(
The nanocatalyst was analyzed by Energy dispersive xꢀray
EDX) and the outcome was acceptable with expected elements
such as: iron, silicon, oxygen, carbon, nitrogen and palladium.
EDX analysis of the nanocatalyst is shown Figure .
(
a)
b)
3 4
Figure 5. The vibrating sample magnetometer (VSM) of the Fe O (a) in
comparison with catalyst (b).
Inductively coupled plasma optical emission spectroscopy
ICP/OES) analysis of the catalyst found that the weight
(
percentage of Pd to be 3.8 wt% Pd in the catalyst.
Xꢀray photoelectroscopy (XPS) technique was used to
determine the oxidation state of the Pd surface in nanocatalyst.
Figure 3. EDX analysis of the nanocatalyst.
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ARTICLE
The XPS spectrum of Pd is shown in Figure . The binding obtained. It should be noted that the yield of the reaction for
energy showed the doublet peak at 335 ev (3d ) and 340.7 ev aryl bromides bearing an electronꢀwithdrawing group was a
5/2
(
3d ). This result could be attributed to the Pd (0) oxidation little more than electron–releasing group (Table 3, entries 8ꢀ9).
3/2
state. This result is consistent with previously reported values in We try about aryl chloride and unfortunately a low yield was
2
9
literature (Figure ).
observed. We utilized this catalyst in coupling 2ꢀ
naphthylboronic acid as a larger ring and it was successful
(
entries 14ꢀ15).
a
Table 2. Influence of base, solvent and palladium percent in model reaction .
b
Entry Solvent
Base
Pd (%) Time (h) Yield (%)
1
2
3
4
5
6
7
8
9
DMF
K
K
NaOH
NaOAc
Na
CS
2
CO
CO
3
3
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.2
0.1
0.3
0.2
3
3
3
3
3
3
3
3
3
92
92
83
70
71
91
54
61
80
92
80
DMF/H
DMF/H
DMF/H
DMF/H
DMF/H
2
2
2
2
2
O
O
O
O
O
2
2
CO
CO
3
2
3
H
2
O
K
2
K
2
K
2
K
2
K
2
CO
CO
CO
CO
CO
3
3
3
3
3
Toluene
Figure 6. XPS spectra of the catalyst Pd (0).
DMF/H
DMF/H
DMF/H
2
O
O
O
1
1
0
1
2
2
3
1.5
The xꢀray diffraction (XRD) pattern of Silica coated
magnetite nanoparticles Fe O @SiO (Figure a) exhibited XRD
a
Reaction condition bromobenzene (1 mmol), phenylboronoc acid (1.5 mmol),
K CO (2 mmol), solvent (4 mL); Isolated yield
2 3
3
4
2
b
broadened pattern because of its nonꢀcrystalline at 2θ= 20ꢀ29◦
and 30.2, 35.5, 43.3, 53.6, 57.3, 62.79 and 74.2◦ which confirm
Fe O @SiO structure. The XRD pattern of Pdꢀnanocatalyst
Another point and advantage was important about new nano
catalyst and it was its ability to recover and reuse. The reaction
of bromobenzeneas and phenylboronic acid was selected as a
model for this step. When the coupling reaction was done, the
catalyst was separated by an external magnet, washed and
dried.
3
4
2
exhibited at 2θ= 40.1, 46.65, 68.1, 82.08 which confirm Pd (0)
3
0
structure (Figure b).
Table 3. Investigations of the scope of substrates in the Pdꢀcatalyzed
2
2
a
C (sp )ꢀC (sp ) cross coupling reaction .
Time Yield
Entry Aryl halides
Aryl boronic acids
b
(
h)
(%)
92
92
89
94
92
91
1
2
3
4
5
6
iodobenzene
phenylboronic acid
phenylboronic acid
phenylboronic acid
phenylboronic acid
phenylboronic acid
phenylboronic acid
1
1ꢀiodoꢀ4ꢀmethylbenzene
4ꢀiodophenol
1
1
1ꢀiodoꢀ4ꢀmethoxybenzene
bromobenzene
1
3
3 4 2
Figure 7. XRD patterns of (a) Fe O @SiO (b) SMNPsꢀsupportedꢀ(D)ꢀPd.
1ꢀbromoꢀ4ꢀmethylbenzene
3
Catalyst Suzuki reaction. We setup a Suzuki reaction to prove
the activity of the new synthesized catalyst (structure (5)),
where the reaction of bromobenzene with phenylboronic acid
was performed as the model reaction. In the first experiment,
the coupling reaction was done in the presence of DMF solvent,
1ꢀbromoꢀ4ꢀ
methoxybenzene
7
phenylboronic acid
3
93
8
9
1ꢀbromoꢀ4ꢀnitrobenzene
4ꢀbromobenzonitrile
1ꢀbromoꢀ2ꢀmethylbenzene
iodobenzene
phenylboronic acid
3
3
3
1
3
6
3
3
93
94
86
95
94
11
90
82
phenylboronic acid
1
0
1
2
3
phenylboronic acid
1
1
1
4ꢀnitrophenylboronic acid
4ꢀnitrophenylboronic acid
phenylboronic acid
o
K CO base and 0.2% catalyst loading at 100 C for 3 hours
2
3
bromobenzene
(
obtained yield was 92%). Different solvents such as
chlorobenzene
H O/DMF, water and toluene were investigated in these
2
14
15
iodobenzene
naphthalenꢀ2ꢀylboronic acid
naphthalenꢀ2ꢀylboronic acid
reactions. The greatest yield was observed with water/DMF
1ꢀiodoꢀ4ꢀmethoxybenzene
a
(
1:1) as shown in Table 2. By testing different bases such as
2 3
Reaction condition bromobenzene (1 mmol), phenylboronoc acid (1.5 mmol), K CO (2
o
b
2
mmol), DMF/H O (4 mL, v/v=1:1), Pd catalyst (0.2 mol%), 100 C; Isolated yield
NaOH, NaOAc, Na CO and CS CO , decreasing in yield was
2
3
2
3
observed (Table 2) and for catalyst loading, the highest yield
was obtained in the presence of 0.2% catalyst (Table 2).
A schematic representation of the proposed catalytic route
for Suzuki reaction has been presented in Scheme 2. Firstly, the
arylhalide reacts with the active palladium catalyst (oxidative
addition) to produce Pd(II) intermediate (II). In continues, aryl
moiety of phenyl boronic acid exchange with halide onto
surface of catalyst (III) and finally, the III undergo reductive
elimination to produce expected product.
The obtained optimized reaction conditions are presented in
Table 2. The reactions were also investigated with various aryl
halides and arylboronic acids at the determined optimized
conditions and the results are summarized in Table 2. We used
aryl iodide to test the catalytic activity of the Pd nanoparticles
catalyst. The time of reaction for aryl iodide was shorter than
aryl bromides (1 h) and very good to excellent yields were
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Ar
comparison of their spectral data with those in the authentic
samples.
B(OH)
KX
KHCO
3
3
Ar
X
X
Fe@SiO
2
Fe@SiO
2
OEt
Si
Characterization methods
O
O
O
(I)
(
II)
N
N
O
O
Ar
Ar'B(OH)
3
K
Pd
Ar'
The structure of the new magnetite nanocatalyst was
characterized by FTꢀIR, XRD, UVꢀVIS, EDX, TEM, XPS and
VSM analysis. FTIRꢀspectra was recorded by Perkin Elmer PEꢀ
1600ꢀFTIR. Pd content of the catalyst was determined by
inductively coupled plasma (ICP) ICPꢀOES. Xꢀray
photoelectron spectroscopy (XPS) was carried out by Dual
Si
Ar Ar'
O
KHCO
3
OEt
Fe@SiO
2
2 2 3 2
Ar'B(OH) + K CO + H O
Pd0
:Pd2+
:
(III)
Scheme 2. Proposed catalytic cycle for Suzuki crossꢀcoupling reaction.
Subsequent to drying, directly used in next similar coupling anode (Mg and Al K alpha) achromatic Xꢀray source. The size
reaction. Employing the catalyst in coupling reaction and of the magnetite nanoparticles was measured by using
recycling was performed for five times and TEM images of it transmission electron microscope (Hitachi H 7600 TEM). Xꢀray
was taken (Error! Reference source not found.). TEM images diffraction (XRD) measurement was performed by Xꢀray
showed that not only catalyst structure was stable but also the diffractometer ITAL STRUCTURES model APD2000 with
yield of reaction after each time was acceptable.
applying Cu Kα radiation, in at 2θ range of 5° to 90°. Magnetic
measurement of materials was investigated with a vibrating
sample magnetometer (VSM ꢀ 4 inch, Daghigh Meghnatis
Kashan Co., Kashan, Iran) at room temperature.
Catalyst preparation
At first magnetic nanoparticles Fe O4 and Fe O @SiO
2
3
3
4
were synthesized according to the procedure previously
3
1
reported in literature.
Silanation of the silica- coated magnetite nanoparticles. Initially
Silica coated magnetic nanoparticles put under vacuum to dry.
2
g of dry particles was dispersed in 100 mL dry toluene and 30
min was sonicated. 7.5 mL (32.04 mmol) of (3ꢀaminopropyl)
triethoxysilane was added dropwise to the suspended solid
nanoparticles under mechanical stirring. The reaction was
refluxed at 115 °C for 20 h. After refluxing, the nanoparticles
were cooled down and then separated by a magnet. The
nanoparticles were then washed three times with anhydrous
methanol and then dried under vacuum. Next, a back titration
was performed to determine the concentration of amines, which
was measured to be 0.048ꢀ0.502 mmol/g.
Figure 8. TEM images of nanocatalyst after five times recycling.
Reusability of the Pd magnetically separable nanocatalyst is
shown in Error! Reference source not found.
. An
insignificant decrease in the catalytic activity was observed
after sixteen reactions for example yield of reaction in tenth run
was roughly 80 %. Metal leaching of the catalyst was studied
before and after the reaction by ICPꢀOES analysis. The Pd
content was found to be 3.8 % wt and 3.48 % wt before and
after the five reactions series respectively, which was verified
to imply insignificant Pd leaching. Turnover frequency (TOF)
General Procedure for the Preparation of the 2[2(2formylphenoxy)
ethoxy]benzaldehyde (D) on silica- coated magnetite nanoparticles (
SMNPs-supported- D). 3 g of material (3) were suspended in 50
mL of dry methanol, and after sonication for 15 min, 10 mL (10
mmol) of 2ꢀ[2ꢀ(2ꢀformylphenoxy) ethoxy]benzaldehyde were
added and the mixture was heated at 50 °C for 2 days. After
cooling to room temperature, the particles were separated
magnetically, washed 3 times with dry methanol, and dried
under a vacuum for 24 h to give SMNPsꢀsupportedꢀD.
ꢀ
1
of catalyst was determined (153.33 h for first reaction and 103
ꢀ
1
h for sixteen reactions).
General Procedure to Preparation of Palladium Catalyst. 1 g of dry
nanoparticles from the final step and 15 mL dry toluene was
sonicated. Then, PdCl (0.6 mmol, 0.1 g) in 15 mL toluene was
2
added and the mixture was refluxed for 12 h under argon. The
resulting product containing an external magnet was separated,
subjected to a water wash (1×10 mL), methanol wash (3×10
mL) and then dried under vacuum.
Figure 9. Reusability of the Pd magnetically separable nanocatalyst in
sixteen reactions.
Experimental section
General procedure for Suzuki reaction. A mixture of aryl halide (1
Materials. All chemicals were purchased from Merck or Fluka
Chemical Companies. The known products were identified by
mmol), arylboronic acid (1.5 mmol), K CO3 (2.0 mmol),
2
4
| J. Name., 2012, 00, 1-3
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DMF/H O as solvent (4.0 mL, v/v=1:1) and the catalyst was 10. F. Cozzi, Adv. Synth. Catal., 2006, 348, 1367–1390.
2
1
1. W. Teunissen, A. A. Bol, and J. W. Geus, Catal. Today, 1999,
48, 329–336.
2. S. Shylesh, V. Schünemann, and W. R. Thiel, Angew. Chem. Int.
Ed. Engl., 2010, 49, 3428–59.
added to a round bottom flask. The mixture of reaction was
stirred at 100 C, in an air atmosphere for the required time to
complete the reaction. When the reaction was completed, the
o
1
reaction was cooled and added 25 mL Et O to the solution, the
2
13. Z. Wang, P. Xiao, B. Shen, and N. He, Colloids Surfaces A
Physicochem. Eng. Asp., 2006, 276, 116–121.
organic phase was washed with water (2×10 mL) and
evaporated the solvent. The residual of reaction was purified by 14. A. Schätz, M. Hager, and O. Reiser, Adv. Funct. Mater., 2009,
1
9, 2109–2115.
flash chromatography to provide the pure coupling product.
The catalyst separated magnetically by using external magnet.
The catalyst was washed with H O, Et O and recovered.
1
1
1
5. S. Wittmann, A. Schätz, R. N. Grass, W. J. Stark, and O. Reiser,
Angew. Chem. Int. Ed. Engl., 2010, 49, 1867–70.
6. J. Mondal, T. Sen, and A. Bhaumik, Dalton Trans., 2012, 41,
2
2
6
173–81.
Conclusions
7. X. Jin, K. Zhang, J. Sun, J. Wang, Z. Dong, and R. Li, Catal.
Commun., 2012, 26, 199–203.
18. A. R. MoosaviꢀZare, M. A. Zolfigol, V. Khakyzadeh, C.
Böttcher, M. H. Beyzavi, A. Zare, A. Hasaninejad, and R.
Luque, J. Mater. Chem. A, 2014, 2, 770.
9. M. A. Zolfigol, A. R. MoosaviꢀZare, P. Moosavi, V.
Khakyzadeh, and A. Zare, Comptes Rendus Chim., 2013, 16,
962–966.
A novel, efficient, costꢀeffective, operationally simple and
2
2
ecocompatible protocol for the C (sp )ꢀC (sp ) cross coupling
reaction under ambient atmosphere in aqueous medium has
been developed using waterꢀstable palladium complex
supported onto nano magnetite particles as an efficient,
recyclable and stable heterogeneous catalyst. The salient
1
features of the proposed methodology include generality, high 20. M. A. Zolfigol, V. Khakyzadeh, A. R. MoosaviꢀZare, A.
Rostami, A. Zare, N. Iranpoor, M. H. Beyzavi, and R. Luque,
Green Chem., 2013, 15, 2132.
1. J. M. Campelo, D. Luna, R. Luque, J. M. Marinas, and A. a
Romero, ChemSusChem, 2009, 2, 18–45.
efficiency and simplicity, which lead to short reaction times,
high yields, a cleaner reaction profile and easy recyclability of
the heterogeneous catalyst by a magnet.
2
2
2. Y.ꢀS. Lin and C. L. Haynes, Chem. Mater., 2009, 21, 3979–
Acknowledgements
3
986.
The authors gratefully acknowledge the BuꢀAli Sina and 23. Y. Deng, Y. Cai, Z. Sun, J. Liu, C. Liu, J. Wei, W. Li, C. Liu, Y.
Wang, and D. Zhao, J. Am. Chem. Soc., 2010, 132, 8466–73.
Payame Noor, University Research Council, University of
British Columbia and Centre of Excellence in Development of
Environmentally Friendly Methods for Chemical Synthesis
2
2
2
2
4. L. M. Rossi, I. M. Nangoi, and N. J. S. Costa, Inorg. Chem.,
009, 48, 4640–2.
2
5. Y. Liao, L. He, J. Huang, J. Zhang, L. Zhuang, H. Shen, and C.ꢀ
Y. Su, ACS Appl. Mater. Interfaces, 2010, 2, 2333–8.
6. M. Yus, R. Cano, and D. J. Ram, Tetrahedron, 2011, 67, 5432–
(
CEDEFMCS), for providing support to this work.
5
436.
7. Q. Du, W. Zhang, H. Ma, J. Zheng, B. Zhou, and Y. Li,
Tetrahedron, 2012, 68, 3577–3584.
Faculty of Chemistry, BuꢀAli Sina University, Hamedan, Iran, Eꢀmail: 28. S. Qu, H. Yang, D. Ren, S. Kan, G. Zou, D. Li, and M. Li, J.
Notes
a,
zolfi@basu.ac.ir.
Colloid Interface Sci., 1999, 215, 190–192.
b
29. A. KhalafiꢀNezhad and F. Panahi, Green Chem., 2011, 13, 2408.
30. S. Navaladian, B. Viswanathan, T. K. Varadarajan, and R. P.
Viswanath, Nanoscale Res. Lett., 2008, 4, 181–186.
1. N. Koukabi, E. Kolvari, A. Khazaei, M. A. Zolfigol, B.
ShirmardiꢀShaghasemi, and H. R. Khavasi, Chem. Commun.
Chemistry Department, 2036 Main Mall, UBC, Vancouver, BC, Canada
c
Department of chemistry, Payame Noor University, Tehran, Iran.
d
Institut für Organische Chemie, AlbertꢀLudwigsꢀUniversitat, 79104
3
Freiburg, Germany, Eꢀmail: mr.khakyzadeh@yahoo.com.
(Camb)., 2011, 47, 9230–2.
References
1
. P. D. Stevens, J. Fan, H. M. R. Gardimalla, M. Yen, and Y. Gao,
Org. Lett., 2005, 7, 2085–8.
2
3
. M. Zhu and G. Diao, J. phisical Chem., 2011, 24743–24749.
. M. Ghotbinejad, A. R. Khosropour, I. MohammadpoorꢀBaltork,
M. Moghadam, S. Tangestaninejad, and V. Mirkhani, J. Mol.
Catal. A Chem., 2014, 385, 78–84.
4
5
6
. Y.ꢀQ. Zhang, X.ꢀW. Wei, and R. Yu, Catal. Letters, 2010, 135,
2
56–262.
. J. Wang, B. Xu, H. Sun, and G. Song, Tetrahedron Lett., 2013,
4, 238–241.
5
. A. Taher, J.ꢀB. Kim, J.ꢀY. Jung, W.ꢀS. Ahn, and M.ꢀJ. Jin,
Synlett, 2009, 2477–2482.
7
8
. N. Miyaura and A. Suzuki, Chem. Rev, 1995, 2457–2483.
. A. F. Littke and G. C. Fu, Angew. Chem. Int. Ed. Engl., 2002,
4
1, 4176–211.
9
. H. Yang, Y. Wang, Y. Qin, Y. Chong, Q. Yang, G. Li, L. Zhang,
and W. Li, Green Chem., 2011, 13, 1352.
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