DOI: 10.1002/cctc.

201000062

Cu Nanoparticles in PEG: A New Recyclable Catalytic

System for N-Arylation of Amines with Aryl Halides
Mazaahir Kidwai,*[a] Neeraj Kumar Mishra,[a] Saurav Bhardwaj,[a] Anwar Jahan,[a]
Ajeet Kumar,[b] and Subho Mozumdar[b]
A new protocol for the N-arylation of aryl halides with anilines
using Cu nanoparticles in polyethylene glycol (PEG) as an efficient and reusable catalytic system has been developed. The
reaction did not require any cocatalyst. Various solvents were
screened, and PEG400 provided the best results. The studies
showed that the mechanism of catalytic action is dependent

on the size of the nanoparticles. The Cu nanoparticles and PEG

were recyclable and retained their activity. This newly developed protocol was also found to be suitable for the cross
coupling of N H heterocycles with iodobenzene. The present
methodology offers several advantages, such as excellent
yields, short reaction times, and milder reaction conditions.

Introduction
The N-arylation of NH-containing substrates is important in
organic synthesis because the resultant products, arylamines,
and N-aryl heterocycles are ubiquitous compounds in pharmaceuticals, crop protection chemicals, and material sciences.[14]
Hartwig,[5] Buchwald and co-workers,[6] and Shakespeare[7] have
reported that arylation of amines, amides, and C N bond forming cross-coupling reactions of NH-containing substrates has
emerged as a powerful methodology. Chan et al.,[8] Evans
et al.,[9] Lam et al.,[10] and others[11-13] reported that arylamines
and N-arylheterocycles can be prepared using boronic acids,
cupric acetate [Cu(OAc)2], and Cu0 catalysts under mild conditions compared to that of conventional Ullmann and Goldberg
arylation protocols.[14] The synthetic scope of traditional
Ullmann coupling protocols are greatly limited by its high
reaction temperature (often 120 8C or higher)[1416] and poor
substrate generality. In addition, these reactions often require
the use of stoichiometric amounts of reagents, which on scale,
leads to problems of waste disposal. To overcome all these
drawbacks, considerable attention has been paid to develop
an efficient and recyclable catalytic method for N-arylation.
In this context, polyethylene glycol (PEG) has been used as a
solvent and phase-transfer catalyst (PTC) in organic synthesis.
A number of recent reviews have also covered PEG chemistry
and its applications in biotechnology and medicine,[17] PEGsupported catalysis,[18] PEG-based aqueous biphasic systems
(ABS) as alternative separation media,[19] aqueous two-phase
systems (ATPS) in bioconversion,[20] and its derivatives as solvent and PTC in organic synthesis.[21] The toxicity profile and
environmental burden are available for a range of PEG molecular weights. The preliminary studies have revealed that PEG
could be used as a reaction medium for selective reactions
with easy recyclability.[22-23]
Despite the advantages of homogeneous metal catalysts,
difficulties in recovering the catalyst from the reaction mixture
severely inhibits their wide use in industry. Heterogeneous
catalysis supplies the opportunity for easy separation and

1312

recycling of the catalyst, easy product purification, and

possibly, continuous or multiple processing of compounds.
Thus, the development of improved synthetic methods for
N-arylation remains an active research area.
Metal nanoparticles (NPs)[24, 25] as catalysts in synthetic organic chemistry have gained much interest. Current literature
shows that the application of Cu nanoparticles as catalysts in
organic synthesis has been little explored. Copper nanoparticles are particularly attractive because they are high yielding,
need mild reaction conditions, and are recyclable.[26, 27] Furthermore, the use of copper nanoparticles, in Ullmann and Suzuki
cross coupling reactions[11, 28] are considered ecofriendly.
Heterogeneous metal
nanoparticles
find
excellent
application for various organic transformations.[29, 30] The high
reactivity of metal nanoparticles is due to higher surface
areas than the bulk metal catalyst. This is thought to be due
morphological differences; whereas large size metal catalysts
have only a small percentage of reactive sites on the surface,
smaller size nanoparticles will possess a much higher surface
concentration of such sites. The catalytic activity of Cu nanoparticles was evident when no product was obtained in the
absence of the catalyst.
Considering our previous works in the field of metal nanoparticles[29, 30] and PEG[22] in organic synthesis, we have developed an efficient method for C N bond formation using Cu
nanoparticles as catalyst in PEG with excellent yields. The reaction is effective at 95 8C in PEG in the presence of K2CO3. The
[a] Prof. M. Kidwai, N. K. Mishra, S. Bhardwaj, A. Jahan
Green Chemistry Research Laboratory, Department of Chemistry
University of Delhi, Delhi-110007 (India)
Fax: (+ 91) 11-2766-6235
E-mail: kidwai.chemistry@gmail.com
[b] A. Kumar, Dr. S. Mozumdar
Laboratory for Nanobiotechnology, Department of Chemistry
University of Delhi, Delhi-110007 (India >
Fax: (+ 91) 98-1072-8438

 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ChemCatChem 2010, 2, 1312 1317

Cu Nanoparticles in PEG
heterogeneous Cu nanoparticles catalyst and PEG solvent is
cheap and recyclable with only a slight decrease of its activity.
It is presumed that PEG works not only as the reaction
medium, but it also acts as a capping agent to stabilize the
Cu NP which conjugates with PEG to form a reactive species.[31]

Results and Discussion

Aniline (1.2 mmol) and iodobenzene (1 mmol) were used to
optimize the reaction condition with Cu nanoparticles as
catalyst. The reaction occurred to afford diphenyl amine in
90 % yield when it was stirred for 5 h at 95 8C in the presence
of Cu nanoparticles (10 mol %) and K2CO3 (1.5 mmol) in PEG
(Scheme 1). The structure was elucidated on the basis of
spectral data.

Table 2. Optimization of Cu nanoparticles for N-arylation.[a]

Entry

Cu NP (18  2 nm) [mol %]

t [h]

Yield [%][b]

1
2
3
4

5
10
15
20

5
5
5
5

70
90
85
21

[a] Reaction conditions: aniline (1.2 mmol), aryl iodides (1 mmol), K2CO3
(1.5 mmol), Cu NP (18  2) nm (520 mol %), PEG400 (2 mL); T = 95 8C;
[b] yields of isolated product.

Being a heterogeneous process, the experiment was carried

out to recycle the Cu NP/PEG400 system. After the completion
of the reaction, the solution was cooled to room temperature.
Because the Cu NP/PEG400 system is immiscible with diethyl
ether and the product is soluble in ether, it was extracted with
ether. The insoluble Cu NP/PEG400 phase was reused for three
cycles, and there was an approximately 5 % weight loss of PEG
from cycle to cycle (Figure 1).

Scheme 1. N-Arylation of anilines and iodobenzene using Cu nanoparticles.

To optimize the reaction conditions, various parameters such

as the effect of different solvents and bases were studied on
the N-arylation. Among the solvents screened, dioxane, acetonitrile, toluene, DMF, PEG200, PEG400 and PEG600, we found that
PEG400 provided the best result. The reaction with K2CO3 was
more effective in comparison to KOH (Table 1).

Table 1. Effect of solvents on the Cu NP catalyzed cross-coupling of

aniline with aryl iodide.
Entry

Solvent/base

T [8C]

t [h]

Yield [%][b]

1
2

dioxane/K2CO3
acetonitrile/
K2CO3
toluene/K2CO3
DMF/K2CO3
PEG200/K2CO3
PEG400/K2CO3
PEG600/K2CO3
PEG400/K2CO3
PEG400/KOH
PEG400/KOH

100
100

5
5

0
0

100
100
100
95
100
RT
RT
110

5
5
5
5
5
10
10
5

25
10
86
90
90
0
0
45

3
4
5
6
7
8
9
10

[a] Reaction conditions: aniline (1.2 mmol), aryl iodides (1 mmol), base
(1.5 mmol), Cu NP (18  2) nm (10 mol %), solvent (2 mL); T = 95 8C;
[b] yields of isolated product.

The concentration of catalyst plays a major role in the

synthesis of diphenyl amines derivatives through coupling
reaction. By using the coupling of aniline and aryl iodide as a
model reaction and varying the concentration of Cu nanoparticles, it was found that the optimum reaction rate and
yield could be achieved at the catalyst concentration of
10 mol % (Table 2).
ChemCatChem 2010, 2, 1312 1317

Figure 1. Recycling of Cu NP/PEG400 catalytic system (Table 3, entry 1).

Scope of this novel protocol in N-arylation with other

amines was studied to determine the effect of substitution
pattern on the reaction yield. Substituted amines having electron-donating groups such as 4-methoxy-, 2-methyl-, and 2methoxyaniline (Table 3, entries 2, 6, 7) showed greater reactivity in comparison to electron-withdrawing groups such as 4chloro-, 4-bromo-, and 4-nitroaniline (Table 3, entries 35). The
reaction of aniline was also studied with substituted iodobenzene. When iodobenzene was replaced by bromo- or
chlorobenzene, the yields were comparatively low (Table 3).
We found that this newly developed protocol was also
suitable for the cross-coupling of NH heterocycles with iodobenzene, which gave the corresponding N-arylated products in
excellent yields in which imidazole derivatives required longer
reaction times to complete the reaction (Table 4).

 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemcatchem.org

1313

M. Kidwai et al.

Table 3. Cross-coupling reaction of substituted anilines with aryl halides

using Cu nanoparticles as catalyst.[a]

Table 4. Reaction of NH heterocycles with iodobenzene.[a]

t [h]

Yield [%][b]

89

91

18

69

18

70

26

95

Entry
Entry

t [h] Product

Yield [%][b]

C6H5

90

4-OCH3C6H4 I

5.2

93

4-ClC6H4

91

4-BrC6H4

5.5

82

Substrate

Product

4-NO2C6H4

12

70

2-CH3C6H4

3.5

94

2-OCH3C6H4 I

95

[a] Reaction conditions: NH heterocycles (1.2 mmol), aryl iodides

(1 mmol), K2CO3 (1.5 mmol), Cu NP (18  2) nm (10 mol %), PEG400 (2 mL);
T = 95 8C; [b] yields of isolated product.

C6 H 5

Br 12

81

4-OCH3C6H4 Br 10

90
Table 5. Size screening of Cu nanoparticles in cross-coupling reactions of
aniline and aryl iodide.[a]

10

C6 H 5

Cl 10

60

[a] Reaction conditions: aniline (1.2 mmol), aryl iodides (1 mmol), K2CO3
(1.5 mmol), Cu NP (18  2) nm (10 mol %), PEG400 (2 mL); T = 95 8C;
[b] yields of isolated product.

Effect of particle size on the catalytic efficiency

The size of the Cu nanoparticles plays an important role in
terms of yields and reaction times. Changing the size of
particles resulted in a drop in catalytic activity. Thus studies
show that the mechanism of catalytic action is dependent on
the nanoparticles size (Table 5).
The maximum reaction rate was obtained for an average
particle size of about 20 nm in diameter. With a decrease in
particle size, a trend of decreasing reaction rate has been
found for particles with a diameter of less than 20 nm, whereas
those above this diameter shows a steady decline of reaction
rate with increasing size. It has been postulated that in the
case of particles with an average size less than 20 nm, a downward shift of the Fermi level takes place, with a consequent
increase of band gap energy.[11, 32-35] As a result, the particles require more energy to pump electrons to the adsorbed ions for
the electron transfer reaction. This leads to a reduction in reaction rate when catalyzed by smaller particles. On the other
hand, for nanoparticles > 20 nm in diameter, the change of
Fermi level is not appreciable. As these particles exhibit less

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Entry

Particle size ( 2 nm)

t [h]

Yield [%][b]

1
2
3
4

10
20
30
50

5
3
3.5
6

88
94
90
70

[a] Reaction conditions: aniline (1.2 mmol), aryl iodides (1 mmol), K2CO3
(1.5 mmol), Cu NP (18  2) nm (10 mol %), PEG400 (2 mL); T = 95 8C;
[b] yields of isolated product.

surface area for adsorption with increased particle size, a

decrease in catalytic efficiency results.

Conclusions
In conclusion, we have developed a mild and efficient method
for amination using Cu nanoparticles in PEG as environmentally benign solvent. The catalyst and solvent were recovered and
they retained their activity. In comparison to other transition
metal catalyst systems, this protocol is simple and avoids the
use of expensive metal catalysts or additives. To the best of
our knowledge, this is the first catalytic system for the N-arylation of NH-containing substrates. Further studies to elucidate
the mechanism of this catalytic system and to extend this
process to other reactions is ongoing in our laboratory.

 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

ChemCatChem 2010, 2, 1312 1317

Cu Nanoparticles in PEG

Experimental Section
The materials were purchased from SigmaAldrich and Merck and
were used without any further purification. All reactions and purity
of diphenyl amines were monitored by thin layer chromatography
(TLC) using aluminum plates coated with silica gel (Merck) using
hexane/ethylacetate (80:20) as an eluent. The isolated products
were further purified by column chromatography using silica gel G
(particle size 1040 microns, 300 mesh) purchased from Spectrochem Pvt. Ltd. Mumbai, India. Melting points were determined on
Buchi 530. 1H NMR spectra were recorded on a Bruker Avance
Spectrospin 300 (300 MHz). All NMR samples were run in CDCl3
and chemical shifts were expressed as ppm relative to internal
Me4Si. The size and morphology of Cu nanoparticles were characterized by using a transmission electron microscope (TEM, FEI
Philips Morgagni 268D model, ac voltage of 100 kV with a magnification of up to 2, 80 000  ) and a quasi elastic light scattering
instrument (QELS, photocor-FC, Model-1135P). The metallic nature
of the particles was confirmed by using a UV spectrophotometer
(Shimadzu).

the water content parameter W0 (defined as the molar ratio of

molar concentration of water to surfactant concentration, W0 =
[H2O]/[surfactant], the size of the nanoparticles could be controlled. The sizes of the Cu nanoparticles prepared at W0 = 5 were
confirmed as 1418 nm through quasi elastic light scattering
(QELS) data (Figure 2 a) and TEM measurements (Figure 2 b). The

Preparation of Cu nanoparticles
A chemical method involving reduction of Cu2 + ions to Cu0 in a
reverse micellar system was employed to prepare the copper
nanoparticles (Scheme 2).[3638] Poly(oxyethylene) (tetra methyl

Scheme 2. Preparative procedure of Cu nanoparticles.

butyl) phenyl ether, commercially known as Triton X-100 (TX-100)

was used as the surfactant with cyclohexane as the solvent continuous phase, hexanol as cosurfactant and aqueous solution of salts
as dispersed phase (water core in which particle formation occurs).
The reverse micelles were prepared by dissolving TX-100 in cyclohexane (usually 0.080.15 m of TX-100 solution). A typical preparative method is as follows: To a set volume of 100 mL (0.1 m TX-100
solutions in cyclohexane), CuSO4 aqueous solution (900 mL, 2 % w/
v) and hexanol (quantity substituent, q.s.) were added to prepare
an optically clear reverse micellar solution (RM-1). To another solution of 0.1 m TX-100 in cyclohexane (100 mL), N2H2 solution (5 %
aqueous solution) and hexanol (q.s.) were added to obtain RM-2.
To the prepared reverse micellar solution of CuSO4 aqueous solution (2 % w/v) (RM-1), another reverse micellar N2H2 solution (5 %
aqueous solution) (RM-2) was added dropwise with constant stirring under the nitrogen atmosphere. In the presence of nitrogen
atmosphere, the resulting solution was allowed to stir for three
hours to complete the Ostwald ripening (particle growth). The
copper nanoparticles were extracted by adding absolute ethanol
to the reverse micellar solution containing Cu nanoparticles followed by centrifugation at 30004000 rpm for 10 min. By varying
ChemCatChem 2010, 2, 1312 1317

Figure 2. a) QELS data of Cu nanoparticles: Plot of population distribution in

percentile versus size distribution in nanometers; b) TEM image of Cu nanoparticles.

Cu nanoparticles prepared were round in shape and brown in

color (colloidal state). TEM photographs (Figure 2 b) confirmed the
sizes of copper nanoparticles used in the experiment. The metallic
nature of the Cu0 nanoparticles was confirmed by a characteristic
UV absorption of particles dispersed in cyclohexane (Figure 3).

General procedure for the synthesis of diphenyl amines

In a 50 mL round bottom flask, substituted anilines (1.2 mmol), aryl
halides (1 mmol), and K2CO3 (1.5 mmol) in PEG (2 mL) were stirred
under a nitrogen atmosphere and Cu nanoparticles (10 mol % 18 

 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.chemcatchem.org

1315

M. Kidwai et al.
7.23 (t, J = 7.95 Hz, 1 H), 6.986.93 (m, 3 H), 4.26 (s, 1 H), 2.38 ppm
(s, 3 H). 13C NMR (100 MHz, CDCl3): d = 145.46, 142.79, 132.34,
128.72, 127.46, 124.68, 120.34, 119.21, 117.48, 22.53 ppm.
N-(2-methoxyphenyl)aniline (Table 3, entry 7): Yellowish oil, 1H NMR
(300 MHz, CDCl3): d = 7.387.32 (m, 3 H), 7.217.18 (m, 2 H), 7.07
7.04 (t, J = 8.2 Hz, CDCl3), 6.846.78 (m, 3 H), 4.32 (s, 1 H), 3.39 ppm
(s, 3 H), 13C NMR (100 MHz, CDCl3): d = 147.73, 142.28, 132.36,
129.12, 120.89, 118.20, 117.35, 115.26, 56.43 ppm.
N-phenylpyrrole: (Table 4, entry 1): Light yellow solid, m.p. 60
62 8C; 1H NMR (300 MHz, CDCl3): d = 7.867.83 (d, J = 8.6 Hz, 2 H),
7.447.32 (m, 3 H), 7.217.18 (m, 2 H), 6.406.36 ppm (m, 2 H).
13
C NMR (100 MHz, CDCl3): d = 142.63, 130.42, 129.73, 127.64,
125.74, 120.72, 118.46, 110.51 ppm.
Figure 3. UV spectrum for characterizing the metallic nature of the Cu nanoparticles.

2 nm) were added. The reaction mixture was allowed to be stirred

at 95 8C for the appropriate time (Table 3). The extent of reaction
was monitored using TLC. After completion of the reaction, the
mixture was cooled and extracted with diethyl ether and the ether
layer was washed with brine solution, and then dried with anhydrous sodium sulfate. Cu NP/PEG400 system being insoluble in ether
was recovered. The solvent was removed in vacuo, the crude reaction mixture was purified by silica gel column chromatography
using 10 % ethyl acetate and 90 % petroleum ether as an eluent to
yield the diphenyl amines. The recovered Cu NP/PEG400 catalytic
system can be reused for consecutive runs. The structures of all
the products were unambiguously established on the basis of their
spectral analysis (1H NMR and 13C NMR spectral data). All the
products are known compounds; those synthesized by novel
routes were elucidated by comparison with existing literature.
N-phenylaniline (Table 3, entry 1): Yellow solid, m.p. 5253 8C.
H NMR (300 MHz, CDCl3): d = 7.547.50 (m, 4 H), 7.297.26 (d, J =
8.7 Hz, 4 H), 6.916.82 (m, 2 H), 5.49 ppm (s, 1 H). 13CNMR (100 MHz,
CDCl3): d = 118.04, 121.24, 129.54, 143.28 ppm.

N-(p-methoxyphenyl)aniline (Table 3, entry 2): Pale yellow solid,

m.p. 103 8C, 1H NMR (300 MHz, CDCl3): d = 7.857.82 (d, J = 7.5 Hz,
2 H), 7.487.36 (m, 5 H), 6.816.63 (m, 5 H), 4.30 (s, 1 H), 3.41 ppm (s,
3 H). 13C NMR (100 MHz, CDCl3): d = 151.45, 146.32, 132.28, 129.10,
123.41, 119.10, 52.23 ppm.
N-(p-chlorophenyl)aniline (Table 3, entry 3): Pale yellow solid,
m.p. 7172 8C; 1H NMR (300 MHz, CDCl3): d = 7.707.67 (d, 7.95 Hz,
2 H), 7.407.38 (t, J = 7.68 Hz, 2 H), 7.117.05 (m, 3 H), 6.596.57 (d,
J = 8.59 Hz, 2 H), 5.58 ppm (s, 1 H). 13C NMR (100 MHz, CDCl3): d =
146.55, 141.24, 131.76, 122.83, 120.11, 116.40 ppm.
N-(p-Bromophenyl)aniline (Table 3, entry 4): Light yellow solid,
m.p. 86 8C. 1H NMR (300 MHz, CDCl3): d = 7.727.69 (d, 7.94 Hz, 2 H),
7.367.31 (t, J = 8.60 Hz, 2 H), 7.067.01 (m, 3 H), 6.926.88 (d, J =
8.6 Hz, 2 H), 5.67 ppm (s, 1 H), 13C NMR (100 MHz, CDCl3): d =
147.28, 143.43, 129.83, 129.46, 127.04, 118.21, 114.32 ppm.
N-(p-Nitrophenyl)aniline (Table 3, entry 5): Yellow solid, m.p. 130 8C;
H NMR (300 MHz, CDCl3): d = 8.088.05 (d, J = 9.0 Hz, 2 H), 7.26
7.23 (t, J = 8.25 Hz, 2 H), 7.207.12 (m, 3 H), 6.646.61 (d, J = 8.79 Hz,
2 H), 4.40 ppm (s, 1 H). 13C NMR (100 MHz, CDCl3): d = 150.24,
138.45, 137.12, 128.27, 127.56, 124.71, 123.42, 115.0 ppm.

N-(2-methylphenyl)aniline (Table 3, entry 6): Brownish solid,

m.p. 40 8C; 1H NMR (300 MHz, CDCl3): d = 7.657.58 (m, 5 H), 7.28

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www.chemcatchem.org

N-phenylindole: (Table 4, entry 2): Colorless solid, m.p. 6062 8C;

H NMR (300 MHz, CDCl3): d = 7.667.64 (d, J = 7.8 Hz, 1 H), 7.51
7.48 (m, 3 H), 7.367.34 (m, 2 H), 7.287.23 (m, 3 H), 6.78 ppm (s,
1 H). 13C NMR (100 MHz, CDCl3): d = 139.85, 134.97, 129.67, 129.41,
128.07, 127.43, 123.94, 121.30, 112.76, 105.23 ppm.

N-phenylimidazole: (Table 4, entry 3): Colorless solid, m.p. 6062 8C;

H NMR (300 MHz, CDCl3): d = 7.85 (s, 1 H), 7.547.51 (m, 2 H), 7.32
7.30 (m, 3 H), 7.27 (s, 1 H), 7.18 ppm (s, 1 H). 13C NMR (100 MHz,
CDCl3): d = 138.41, 135.76, 129.16, 128.16, 127.17, 120.66, 119.54,
110.83 ppm.
1

N-(phenyl)-5-methyl-imidazole: (Table 4, entry 4): Yellowish oil,

1
H NMR (300 MHz, CDCl3): d = 7.427.36 (m, 5 H), 7.247.22 (m, 3 H),
6.91 (s, 1 H), 6.84 ppm (s, 1 H). 13C NMR (100 MHz, CDCl3): d =
128.93, 128.27, 126.32, 125.68, 119.86, 12.92 ppm.
N-(phenyl)-5-methyl-imidazole: (Table 4, entry 5): Pale yellow solid,
m.p. 98 8C, 1H NMR (300 MHz, CDCl3): d = 8.09 (s, 1 H), 7.747.40 (m,
6 H), 7.267.22 ppm (m, 2 H). 13C NMR (100 MHz, CDCl3): d = 146.36,
132.28, 127.30, 124.30, 124.17, 122.33, 120.63, 112.46 ppm.

Acknowledgements
Neeraj Kumar Mishra, S. Bhardwaj, and Anwar Jahan thank
C.S.I.R. and U.G.C., New Delhi, India for grant of the Junior and
Senior Research Fellowships.
Keywords: amines copper cross-couplings heterogeneous
catalysis nanoparticles
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Received: March 9, 2010

Revised: April 20, 2010
Published online on July 21, 2010

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