Preparation of palladium nanoparticles using Euphorbia thymifolia L. leaf extract and evaluation of catalytic activity in the ligand-free Stille and Hiyama cross-coupling reactions in water

Article abstract of DOI:10.1039/c5nj00244c

The synthesis of palladium nanoparticles (Pd NPs) using an aqueous extract of leaves of Euphorbia thymifolia L. and their application in the ligand-free Stille and Hiyama cross-coupling reactions are reported here. Pd NPs were characterized using powder XRD, TEM, FT-IR and UV-vis techniques. The synthesized Pd NPs exhibited excellent catalytic activity and the reactions generated the corresponding products in good to excellent yields. These methods have some advantages, such as efficiency, generality, high yield, elimination of ligand, organic solvent and homogeneous catalysts, cleaner reaction profiles, ease of product isolation and simplicity. The reactions were carried out in a green solvent i.e. water. The catalyst was quantitatively recovered and reused without significant loss in the catalytic activity.

Full text of DOI:10.1039/c5nj00244c

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Preparation of palladium nanoparticles using
Euphorbia thymifolia L. leaf extract and evaluation
of catalytic activity in the ligand-free Stille and
Hiyama cross-coupling reactions in water
Cite this:DOI: 10.1039/c5nj00244c
Mahmoud Nasrollahzadeh,*a S. Mohammad Sajadi,b Ebrahim Honarmanda and
Mehdi Mahamc
The synthesis of palladium nanoparticles (Pd NPs) using an aqueous extract of leaves of Euphorbia
thymifolia L. and their application in the ligand-free Stille and Hiyama cross-coupling reactions are reported
here. Pd NPs were characterized using powder XRD, TEM, FT-IR and UV-vis techniques. The synthesized
Pd NPs exhibited excellent catalytic activity and the reactions generated the corresponding products in
good to excellent yields. These methods have some advantages, such as efficiency, generality, high yield,
elimination of ligand, organic solvent and homogeneous catalysts, cleaner reaction profiles, ease of product
isolation and simplicity. The reactions were carried out in a green solvent i.e. water. The catalyst was
quantitatively recovered and reused without significant loss in the catalytic activity.
Received (in Montpellier, France)
28th January 2015,
Accepted 1st April 2015
DOI: 10.1039/c5nj00244c
www.rsc.org/njc
malignant.3 Earlier reported methods for the synthesis of biaryls
suffered from drawbacks such as the use of expensive, toxic and
Introduction
The importance of biaryls, especially for their applications in moisture-sensitive reagents and stoichiometric amounts of homo-
medicinal chemistry, and the synthesis of herbicides, natural geneous catalysts, harsh reaction conditions, low yields, tedious
products and biologically active molecules and in materials work-ups and environmental pollution caused by the formation of
science, has led to significant research by organic chemists.1 side products.3 Despite the excellent activity of the homogeneous
There are several methods for the synthesis of biaryls in the catalysts, they cannot easily be recovered from the reaction
literature.1b,2 Amongst them, palladium-catalyzed Stille, Suzuki mixture and reused. Therefore, the development of a mild,
and Hiyama cross-coupling reactions are applied for the pre- highly efficient and environmentally benign method for ligand-
paration of both symmetrical and unsymmetrical biaryls.1b,3,4 free Stille and Hiyama cross-coupling reactions in water under
The palladium-catalyzed Stille cross-coupling reactions of organo- heterogeneous conditions has been a major challenge in organic
halides with organotin compounds have been proven to be a synthesis. We recently published the synthesis of biaryls via a
useful and attractive synthetic method for the synthesis of Suzuki cross-coupling reaction of aryl halides with arylboronic
biaryls via C–C bond formation.3a–d The palladium-catalyzed acids in the presence of heterogeneous catalysts.4 Owing to the
cross-coupling of organosilanes with aryl halides and triflates is importance of biaryls in medicinal chemistry and materials
known as the Hiyama reaction.3e–g
science, we next turned our attention to applying new and
In the last two decades, Stille and Hiyama cross-coupling heterogeneous catalysts to the Stille and Hiyama cross-coupling
reactions have generally proceeded under an inert atmosphere reactions.
in a toxic organic solvent and in the presence of toxic and
Recently, noble metal nanoparticle (NMNPs)-based hetero-
expensive phosphine ligands, and a stoichiometric amount of geneous catalysts have attracted much attention of scientists
homogeneous palladium catalysts, such as Pd(PPh3)4, PdCl2(PPh3)2 worldwide, since they exhibit unique surface properties, high-
and PdCl2(MeCN)2, which are economically and environmentally specific surface areas and high catalytic activities.5 In particular,
Pd NPs emerged as one of the most useful heterogeneous catalysts
a Department of Chemistry, Faculty of Science, University of Qom, PO Box 37185-359,
Qom, Iran. E-mail: mahmoudnasr81@gmail.com; Fax: +98 253 32103595;
Tel: +98 253 32850953
b Department of Petroleum Geoscience, Faculty of Science, Soran University,
PO Box 624, Soran, Kurdistan Regional Government, Iraq
c Department of Chemistry, Aliabad Katoul Branch, Islamic Azad University,
Aliabad Katoul, Iran
due to their numerous applications in palladium-catalyzed reac-
tions such as Sonogashira coupling,6a hydrogenation,6b the Suzuki
reaction,4c the Heck reaction,7 C–N coupling8 and in the oxidation
of hydrocarbon.9
There are several and various chemical and physical methods
for the preparation of Pd NPs. Unfortunately, most of these have
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several disadvantages such as the use of hazardous and expensive cross-coupling reactions in water. To the best of our knowledge,
organic solvents, toxic and hazardous reducing agents, surfactants, there are no other reports on the preparation of MNPs by
organic ligands, polymers, and dendrimers and the need for high Euphorbia thymifolia L. leaf extract (Scheme 1).
temperatures and pressures.10 As a result, these drawbacks have
limited the large-scale application of Pd NPs in industry. There-
fore, the preparation of Pd NPs with suitable catalytic activity is still
a challenge for the development of environmentally friendly,
In this work, we report a successful and totally green method
sustainable, simple, rapid, easy to control and energy-efficient
Results and discussion
for the synthesis and characterization of Pd NPs by using the
extract of leaves of Euphorbia thymifolia L. as a reducing and
methods.
Quite recently, we reported the green synthesis of various
stabilizing agent without using any synthetic reagent or toxic
metal nanoparticles (MNPs) using plant extracts and tree gums
chemicals. These extracts contain several easily oxidizable
under mild conditions and investigated their good catalytic
efficiency in organic reactions.6,11 The advantages of the present
functional groups (e.g. –OH) that can act as reducing agents
for the reduction of PdII to Pd0 and the formation of Pd NPs.
method are a simple reaction setup, very mild reaction condi-
Moreover, we have developed a simple, efficient and inexpensive
tions, cost effectiveness, and avoidance of using non-green
catalytic method for ligand-free Stille and Hiyama cross-coupling
solvents and dangerous chemicals. Moreover, compatibility with
reactions in water.
biomedical and pharmaceutical applications is a benefit of this
method.12
Characterization of green-synthesized Pd NPs using the leaf
extract of Euphorbia thymifolia L.
Euphorbia thymifolia L., from the family of Euphorbiaceae, is
a small, slender and annual prostrate herb. The leaves of the
plant are opposite, very small, 3–6 mm long, obliquely oblong The UV spectrum of the extract (Fig. 1) shows bonds at lmax
or elliptic-oblong. A survey of the literature reported on the 380 nm (bond I) due to the transition localized within the ring
plant revealed the presence of some reducing phytochemicals, of cinnamoyl system, whereas the one centered at 280 nm
especially potent antioxidant tannins, such as hydrolysable (bond II) is for absorbance of the ring related to the benzoyl
tannins, gallotannins, ellagitannins, isomallotinic acid, valoneaic system. They are related to the p - p* transitions and these
acid, hexahydroxydiphenic acid, dehydrohexahydroxydiphenic absorbent bonds demonstrate the presence of polyphenolics.
acid and gallic acid.13
The UV-vis spectrum of green-synthesized Pd NPs using
Through this study we used the leaves of Euphorbia thymifolia Euphorbia thymifolia L. leaf extract (Fig. 1) showed significant
L. for the green synthesis of Pd NPs without using any harmful changes in the absorbance maxima due to surface plasmon
reducing or capping agents. As an extension of our continuing resonance, demonstrating the formation of Pd NPs. Also, the
interest in stabilized nanosized catalysts and their applications progression of the reaction and the formation of palladium
in organic synthesis,6,11 we herein report the first investigation nanoparticles were controlled by UV-vis spectroscopy. The yellow
of the green synthesis of Pd NPs for ligand-free Stille and Hiyama color of the PdII solution immediately changed to dark brown
Scheme 1 The new strategy for ligand-free Stille and Hiyama cross-coupling reactions.
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Fig. 3 FT-IR spectrum of green-synthesized Pd NPs.
Fig. 1 (A) UV-vis spectrum of the leaf extract of Euphorbia thymifolia L.;
(B) UV-vis spectrum of the green-synthesized Pd NPs using the leaf extract
of Euphorbia thymifolia L.
Fig. 2 FT-IR spectrum of aqueous extract of leaves of Euphorbia thymifolia L.
(lmax 260–320 nm), indicating the reduction of PdII to Pd0 and
the formation of Pd NPs as characterized by UV-vis spectrum.
FT-IR analysis was carried out to identify the possible
biomolecules responsible for the reduction of Pd nanoparticles
and capping of the bioreduced Pd nanoparticles synthesized by
the leaf extract. The FT-IR spectrum of the crude extract (Fig. 2)
depicted some peaks at 3500 to 3000, 1700 and 1580, and 1350
to 1100 cmÀ1, which represent free OH in the molecule and OH
groups that form hydrogen bonds, and carbonyl group (CQO),
stretching CQC aromatic ring and C–OH stretching vibrations,
respectively. These peaks suggest the presence of phenolics in
the plant leaf extract. The presence of phenolics in the extract
Scheme 2 Mechanism of Pd NP green synthesis; oxidation of the polyol
by metal ions to a,b-unsaturated carbonyl groups.
could be responsible for the reduction of metal ions and the present in the Euphorbia thymifolia L. leaf extract were not only
formation of the corresponding metal nanoparticles.
responsible for the reduction of PdII but also function as capping
Furthermore, the FT-IR spectra of Pd NPs show demonstra- ligands to the surfaces of the Pd NPs, as confirmed by FT-IR
tive differences in the shape and location of signals, indicating spectroscopy.
the interaction between PdCl2 and the involved sites of phyto-
The crystallinity of green-synthesized Pd NPs from the leaf
chemicals for the production of nanoparticles (Fig. 3). The extract of Euphorbia thymifolia L. was confirmed by XRD and the
peaks at 3300, 1720, 1522, 1381 and 1174 cmÀ1 represent the powder diffraction pattern is presented in Fig. 4. The presence of
OH functional groups, carbonyl group (CQO), stretching CQC Pd was confirmed with powder XRD measurements. In the XRD
aromatic ring and C–OH stretching vibrations, respectively. analysis, the planes (111), (200), (220) and (311) can be indexed
Polyphenolics could be adsorbed on the surface of metal to the face centered cubic (fcc) structure of Pd. The result is
nanoparticles, possibly through p-electron interaction in the similar to the reported data.4c,6a The intense reflection at 40.571
absence of other strong ligating agents. In fact, the p-electrons (111), in comparison with the other planes, may indicate the
in a Red–Ox system can transfer to the free orbital of a metal preferred growth direction of the nanocrystals. A few additional
ion and convert that to the free metal. A mechanism of polyol sharp unassigned peaks between 10.01 and 32.01 2y were also
oxidation is shown in Scheme 2. These are in agreement with observed. These were attributed to the crystallization of other
our previous findings.6,11 The polyphenolic and flavonoidic groups bioorganic compounds on the surfaces of the Pd NPs.
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Table 1 Optimization of the reaction conditions in the Hiyama cross-
coupling reaction of bromobenzene with phenyltrimethoxysilanea
Entry
Pd NPs (mol%)
Base
Time (h)
Yieldb (%)
1
2
3
4
5
6
7
8
9
1.0
1.0
1.0
1.0
1.0
1.0
1.0
0.5
1.5
NaOAc
CsF
K3PO4
DBU
K2CO3
NEt3
NaOH
NaOH
NaOH
8
8
8
8
8
8
3
3
3
Trace
Trace
Trace
Trace
23
28
96
63
96
a
Reaction conditions: 1.0 equiv. of bromobenzene, 1.5 equiv. of
phenyltrimethoxysilane, 1.0 mol% of catalyst, 2.0 equiv. of base and
b
water (4.0 mL), 90 1C. Isolated yield.
Fig. 4 XRD powder pattern of green-synthesized Pd NPs.
reactions (entry 8). Increasing the amount of Pd NPs showed no
substantial improvement in the reaction yield (entry 9).
After finding the optimized reaction conditions, the scope of
the protocol was subsequently extended to a range of substi-
tuted aryl bromides and arylsiloxanes as substrates and the
results are summarized in Table 2. Aryl bromides with electron-
withdrawing or electron-donating groups afforded the coupling
products in good to excellent yields. In addition, the steric
hindrance of the substituent did not influence the product
yield (Table 2, entries 4 and 7). The reaction of bromobenzene
Table 2 Hiyama cross-coupling reaction of different aryl bromides with
arylsiloxanesa
Fig. 5 TEM image of green synthesized Pd NPs.
Entry
Aryl bromide
ArSi(OR)3
Time (h)
Yieldb (%)
Particle morphology and size of Pd NPs were studied by
transmission electron microscopy (TEM). The image obtained
by TEM confirmed the formation of Pd NPs using the aqueous
extract of leaves of Euphorbia thymifolia L. (Fig. 5). Particle sizes
ranged from 20 to 30 nm and the particle shape was spherical.
The presence of some larger particles could be attributed to the
aggregation or overlapping of smaller particles.
1
2
3
3
3
3
96 (93)c
94
95
4
3
94
5
6
3
3
93
93
Evaluation of the catalytic activity of Pd NPs for the Hiyama
cross-coupling reaction
The catalytic activity of the Pd NPs was investigated for the Hiyama
cross-coupling reaction in water under aerobic conditions.
7
3
93
Bromobenzene and phenyltrimethoxysilane were used as
model substrates in order to optimize the reaction conditions
(Table 1). Different bases were also tested in this reaction
system. As shown in Table 1, the base has a significant role
on the reaction; NaOH was found to be quite successful for the
transformation. Thus, the optimized reaction condition was
found to be 1.0 mmol of bromobenzene, 1.5 mmol of phenyl-
trimethoxysilane, 1.0 mol% of Pd NPs and 2.0 mmol of NaOH
in H2O as solvent at 90 1C for 3 h under aerobic conditions
(entry 7). The use of lower catalyst loadings resulted in incomplete
8
9
3
4
96
87
10
11
4
4
95
0
a
Reaction conditions: 1.0 equiv. of aryl bromide, 1.5 equiv. of arylsiloxane,
1.0 mol% of catalyst and 2.0 equiv. of NaOH and water (4.0 mL), 90 1C.
b
c
Yields are after work-up. Yield after the 5th cycle.
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provided the desired cross-coupling products in high yields.
The best result was obtained with bromobenzene (1.0 mmol),
tributylphenylstannane (1.2 mmol), Pd NPs (1.0 mol%), K2CO3
(2.0 mmol), and water at 90 1C, which gave the product in a
good yield (91%).
Scheme 3
or 4-bromotoluene with phenyltriethoxysilane afforded the
corresponding cross-coupling product in good to excellent
yields (Table 2, entries 9 and 10). Also, in the presence of
phenyltrimethylsilane, the desired product was not obtained
(Table 2, entry 11).
Under the optimized experimental conditions, the reaction
of aryl bromides containing electron-withdrawing or electron-
donating groups with different organostannanes produced the
desired cross-coupling products in good to excellent yields
under ligand-free and aerobic conditions (Table 3).
Compared with the literature on the Stille and Hiyama cross-
coupling reactions,14,15 notable features of our method are:
ꢀ The reaction system is clean and simple;
Evaluation of the catalytic activity of Pd NPs for the Stille cross-
coupling reaction
The optimization of the reaction conditions for a model Stille
cross-coupling reaction as shown in Scheme 3 was done with
respect to catalyst loading, reaction time and base used in the
reaction.
As a model reaction, initially the reaction of bromobenzene
(1.0 mmol) with tributylphenylstannane (1.2 mmol) was inves-
tigated in water in the presence of various bases (K2CO3, NaOAc
and CsF) at 90 1C. Among the different bases examined, K2CO3
ꢀ A green synthesis of Pd NPs in water without using any
harmful reducing or capping agents;
ꢀ The use of a plant extract as an economic and effective
bioreductant represents an interesting, fast and clean synthetic
route for the large-scale synthesis of efficient and low-cost Pd
NP catalysts which potentially can be applied for future catalytic
applications in other reactions;
ꢀ Toxic organic solvents are not needed;
ꢀ Toxic ligands and fluoride sources14c,d are not needed;
ꢀ The Stille and Hiyama cross-coupling reactions were per-
formed in water under aerobic conditions;
Table 3 Stille cross-coupling reaction of different aryl bromides with
organostannanea
ꢀ The catalyst can be easily recovered and reused without
any modification and with no significant loss of activity;
ꢀ The yields of the products are very high.
Entry
Aryl bromide
Organostannane
Time (h)
Yieldb (%)
To show the advantages of the proposed method in compar-
ison with other reported methods, we summarize some of the
results for the Stille and Hiyama cross-coupling reactions in
Tables 4 and 5, which show that green-synthesized Pd NPs are
equally or more efficient catalysts with respect to reaction time
and yield than previously reported ones.
1
2
3
4
3
3
3
3
91
93
90
93
Catalyst recyclability
The recyclable of the catalyst is economically important in
industry. The stability and high recyclability are important
properties for evaluating the performance of the green synthe-
sis of Pd NPs. As shown in Table 6, the recovered Pd NPs
exhibited almost constant catalytic activity for at least five runs
in the Stille cross-coupling reaction of bromobenzene with
tributylphenylstannane. Moreover, after completion of the reac-
tion, the catalyst was easily separated by centrifugation, washed
with ethanol and deionized water, and finally dried in an oven
for the next run of the Stille cross-coupling reaction by charging
with the same substrates (Table 6). This result suggests that the
5
3
94
6
7
3
3
94
95
8
9
4
8
89
84
a
Reaction conditions: aryl bromide (1.0 mmol), organostannane
(1.2 mmol), Pd NPs (1.0 mol%), K2CO3 (2.0 mmol) and water (4.0 mL),
b
aerobic conditions, 90 1C. Isolated yield.
Table 4 Pd NP-catalyzed Hiyama cross-coupling reaction between 4-bromoacetophenone and phenyltrimethoxysilane compared to reported methods
Entry
Reaction conditions
Yielda (%)
Ref.
1
2
3
4
5
Pd NPs (1.0 mol%)/PEG, NaOH, 90 1C, 2 h
Pd/C (2.0 mol%), NaOH, H2O, 100 1C, 4 h
Pd2(dba)3 (1.0 mol%), pyrazole-tethered phosphine ligand, TBAF, 1,4-dioxane, 55 1C, 10 h
SiO2@Fe3O4–Pd (0.5 mol%), TBAF, THF, 60 1C, N2, 10 h
Pd NPs (1.0 mol%)/extract, NaOH, H2O, 90 1C, 3 h
98
92
85
85
96
14a
14e
14 f
14b
This work
a
Isolated yield.
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Table 5 Pd NP-catalyzed Stille cross-coupling reaction between bromobenzene and tributylphenylstannane compared to reported methods
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Entry
Reaction conditions
Yielda (%)
Ref.
1
2
3
4
5
6
Pd@Fe3O4 (0.5 mol%), CsF, 1,4-dioxane, 100–110 1C, 15 h
Pd NPs (0.02 equiv.)/PEG, K2CO3, H2O, 80 1C, 2 h
Pd/Fe3O4 (1.5 mol%), CsF, dioxane, 100 1C, 16 h
Pd NPs (2.5 mol%), THeptAB,b 90 1C, 16 h
Pd(OAc)2 (3.0 mol%)/Dabco, Bu4NF, dioxane, 80 1C, 20 h
Pd NPs (1.0 mol%)/extract, K2CO3, H2O, 90 1C, 3 h
87
90
86
86
93
91
4b
15c
15e
15f
15g
This work
a
b
Isolated yield. Tetraheptylammonium bromide.
Table 6 Reusability of nanocatalysta
The element analyses (C, H, N) were obtained from a Carlo
ERBA Model EA 1108 analyzer carried out on a PerkinElmer
240c analyzer. TLC was performed on silica gel polygram SIL
G/UV 254 plates. X-ray diffraction (XRD) measurements were
carried out using a Philips powder diffractometer type PW 1373
goniometer (Cu Ka = 1.5406 Å). The scanning rate was 21 minÀ1
in the 2y range from 10 to 801. Transmission electron micro-
scopy (TEM) was recorded on a Zeiss-EM10C-80 KV. UV-visible
spectral analysis was recorded on a double-beam spectrophoto-
meter (Hitachi, U-2900) to ensure the formation of nanoparticles.
Entry
Yieldb (%)
Recovery of catalyst (%)
1
2
3
4
5
91
91
90
89
88
99
99
98
97
96
a
Reaction conditions: bromobenzene (1.0 mmol), tributylphenylstannane
(1.2 mmol), K2CO3 (2.0 mmol), Pd NPs (1.0 mol%), water (4.0 mL), 90 1C.
b
Isolated yield.
nanocatalyst is stable during the Stille cross-coupling reaction.
The reusability of the catalyst was also studied for the Hiyama
cross-coupling (Table 2, entry 1). The recovered catalyst could
be added to fresh substrates under identical conditions for five
runs without a noticeable drop in the product yield and its
catalytic activity.
Preparation of the extract of leaves of Euphorbia thymifolia L.
50 g of dried powdered leaves of Euphorbia thymifolia L. was
added to 250 mL double distilled water in a 500 mL flask and
well mixed on a magnetic heating stirrer at 70 1C for 30 min.
The extract obtained was centrifuged at 6500 rpm, then filtered
and filtrate was kept in the refrigerator for further use.
Conclusion
Preparation of Pd NPs using the Euphorbia thymifolia L. leaf
extract
A novel, environmentally friendly and simple one-step method
to synthesize stable Pd NPs is reported here. The extract of
leaves of Euphorbia thymifolia L. was used as both reducing and
stabilizing agents at a moderate temperature (70 1C) in water
and under aerobic conditions. The present method is a more
efficient and more rapid synthesis process compared with
chemical and physical methods for the synthesis of Pd NPs.
The catalytic activity of Pd NPs was tested for the ligand-free
Stille and Hiyama cross-coupling reactions in water. A variety of
biaryls are efficiently synthesized using the stable Pd NPs in
good to excellent yield. The catalyst was quantitatively recovered
and reused without any appreciable loss in the particle size and
reactivity.
In a typical synthesis of Pd NPs, 15 mL of the extract of the
plant leaves was added dropwise to 50 mL of a 0.003 M aqueous
solution of PdCl2 with constant stirring at 80 1C. Reduction of
the palladium ions (PdII) to palladium (Pd0) was completed
after around 20 min via monitoring the UV-vis spectrum of the
solution. The color of the reaction mixtures gradually changed
over 20 min at 80 1C and indicated the formation of palladium
nanoparticles. Then the colored solution of palladium nano-
particles was centrifuged at 7000 rpm for 45 min to complete
the precipitation and separation.
General procedure for the Hiyama cross-coupling reaction
In a 25 mL round bottom flask, a solution of Pd NPs (1.0 mol%)
was added to aryl bromide (1.0 mmol), arylsiloxane (1.5 mmol)
and NaOH (2 mmol) in water (4.0 mL). The mixture was
magnetically stirred in a pre-heated oil bath at 90 1C for the
Experimental
Reagents and methods
High-purity chemical reagents were purchased from the Merck appropriate time (Table 2). After completion of the reaction (as
and Aldrich chemical companies. All materials were of com- monitored by TLC), the mixture was allowed to cool, extracted
mercial reagent grade. Melting points were determined in open with diethyl ether and washed with water. The ethereal phase
capillaries using a BUCHI 510 melting-point apparatus and are was separated, evaporated under reduced pressure and the
uncorrected. 1H NMR and 13C NMR spectra were recorded on a residue was purified by flash chromatography on silica gel to
Bruker Avance DRX-400 spectrometer at 400 and 100 MHz, obtain the desired cross-coupling product. All the products are
respectively. FT-IR spectra were recorded on a Nicolet 370 FT/IR known compounds and the spectral data and melting points
spectrometer (Thermo Nicolet, USA) using pressed KBr pellets. were identical to those reported in the literature.14
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S. M. Sajadi, A. Rostami-Vartooni and M. Khalaj, RSC Adv.,
2014, 4, 43477; ( f ) M. Nasrollahzadeh, B. Jaleh and
A. Ehsani, New J. Chem., 2015, 39, 1148; (g) P. Fakhri,
M. Nasrollahzadeh and B. Jaleh, RSC Adv., 2014, 4, 48691.
5 S. Wei, Z. Dong, Z. Ma, J. Sun and J. Ma, Catal. Commun.,
2013, 30, 40.
6 (a) M. Nasrollahzadeh, M. Maham and M. M. Tohidi, J. Mol.
Catal. A: Chem., 2014, 391, 83; (b) M. Nasrollahzadeh,
New J. Chem., 2014, 38, 5544.
7 C. Vincenzo, N. Angelo, M. Antonio, D. Antonia and I. Patrizia,
Organometallics, 2003, 22, 4193.
8 V. Kogan, Z. Aizenshtat, R. Popovitz-Biro and R. Neumann,
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General procedure for the Stille cross-coupling reaction
To a stirred solution of 1.0 mmol of aryl bromide in 4 mL of
water, 1.2 mmol of organostannane, 2.0 mmol of K2CO3 and
1.0 mol% of Pd NPs were added and the mixture was heated on
an oil bath at 90 1C for the appropriate time. After completion
of the reaction (as monitored by TLC), the mixture was allowed
to cool, extracted with diethyl ether and washed with water. The
ethereal phase was separated, evaporated under reduced pressure
and the residue was purified by flash chromatography on silica
gel to obtain the desired cross-coupling product. All the products
are known compounds and the spectral data and melting points
were identical to those reported in the literature.15
9 Y. Nishihata, J. Mizuki, T. Akao, H. Tanaka, M. Uenishi,
M. Kimura, T. Okamoto and N. Hamada, Nature, 2002,
418, 164.
Acknowledgements
We gratefully acknowledge the Iranian Nano Council and
University of Qom for support of this work.
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