Fabrication, characterization and application of nanopolymer supported copper (II) complex as an effective and reusable catalyst for the CN bond cross-coupling reaction of sulfonamides with arylboronic acids in water under aerobic conditions

Article abstract of DOI:10.1016/j.molcata.2014.02.017

This paper reports on the synthesis and use of nanopolymer supported copper (II) complex, as separable catalysts for N-arylation of sulfonamides with arylboronic acids in water. This method has the advantages of high yields, elimination of homogeneous cat

Full text of DOI:10.1016/j.molcata.2014.02.017

Journal of Molecular Catalysis A: Chemical 387 (2014) 123–129
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Journal of Molecular Catalysis A: Chemical
journal homepage: www.elsevier.com/locate/molcata
Fabrication, characterization and application of nanopolymer
supported copper (II) complex as an effective and reusable catalyst for
the C N bond cross-coupling reaction of sulfonamides with
arylboronic acids in water under aerobic conditions
Mahmoud Nasrollahzadeha,∗, Akbar Rostami-Vartoonia, Ali Ehsania, Majid Moghadamb
a Department of Chemistry, Faculty of Science, University of Qom, Qom 37185-359, Iran
b Department of Chemistry, Catalysis Division, University of Isfahan, Isfahan, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
This paper reports on the synthesis and use of nanopolymer supported copper (II) complex, as separable
catalysts for N-arylation of sulfonamides with arylboronic acids in water. This method has the advantages
of high yields, elimination of homogeneous catalysts, green reaction conditions, simple methodology
and easy work up. The catalyst can be recovered and reused several times without significant loss of its
catalytic activity. The catalyst was characterized using the powder XRD, SEM, EDS and FT-IR spectroscopy.
Received 24 October 2013
Received in revised form 13 February 2014
Accepted 16 February 2014
Available online 3 March 2014
Keywords:
© 2014 Elsevier B.V. All rights reserved.
Polymer supported copper (II) complex
N-Arylation, Sulfonamide
Heterogeneous catalyst
1. Introduction
researchers have turned their attention toward the use of less
expensive, less toxic, and more efficient metals to replace Pd.
Sulphonamides are well-documented compounds of synthetic
importance which have been widely used as antibacterial, diuretics,
anticonvulsants, hypoglycaemic, and HIV protease inhibitors [1–3].
Sulphonamides are conventionally synthesized via the reac-
tion of sulfonyl chlorides with excess ammonia in the presence
of a base, or by N-sulfonylation of amines in the presence of
homogeneous and heterogeneous catalysts [4–6]. However, this
methodology, when applied to pharmaceutical manufacturing, suf-
fers from the limitation that both the sulfonyl chloride and aromatic
amine are genotoxic alerting structures, bearing a very low (ppm
level) threshold of residual tolerance in active pharamaceutical
ingredients (API) according to the recent regulatory guidelines. An
alternate route to N-aryl sulfonamides is the palladium-catalyzed
coupling of aryl halides or pseudohalides with primary sulfon-
amides in the presence of expensive, unstable and poisonous
phosphine ligands [7,8]. The toxicity and high cost of palladium
catalysts restrict their use on the industrial applications. Thus,
Recently, several methods have been reported for the N-arylation
of sulfonamides by the correct choice of copper sources, bases,
ligands, and other additives [9–13]. However, most of traditional
Cu-catalyzed reactions suffer from different drawbacks such as
high reaction temperatures, generally 140 ◦C or higher, use of sto-
ichiometric amounts of copper catalysts, long reaction times, use
of toxic polar solvents and expensive ligands, and low yields of
the products that restrict their usage in practical applications.
Thus, it is desirable to develop a more efficient and convenient
method for the copper-catalyzed arylation of sulfonamides in
water.
On the other hand, among various copper catalysts for the
coupling reactions, homogeneous catalysts have been widely inves-
tigated, while less expensive heterogeneous catalysts received
scanter attention. The problem with homogeneous catalysis is the
difficulty to separate the catalyst from the reaction mixture and
the impossibility of reuse it in consecutive reactions. In addi-
tion, homogeneous catalysis might result in unacceptable copper
contamination of the desired isolated product, which is a particu-
larly significant drawback for its application in the pharmaceutical
industry. Thus, the use of heterogeneous Cu catalysts such as
organometallic complexes onto a solid support is often desirable
from the perspective of process development due to their easy
handling, simple recovery, and recycling.
Abbreviations:
XRD, X-ray powder diffraction; SEM, scanning electron
microscopy; EDS, Energy Dispersion X-ray Spectroscopy; FT-IR spectroscopy,
Fourier transform infrared spectroscopy; NMR, Nuclear Magnetic Resonance.
∗
Corresponding author. Tel.: +98 25 32103595; fax: +98 25 32850953.
E-mail address: mahmoudnasr81@gmail.com (M. Nasrollahzadeh).
http://dx.doi.org/10.1016/j.molcata.2014.02.017
1381-1169/© 2014 Elsevier B.V. All rights reserved.

124
M. Nasrollahzadeh et al. / Journal of Molecular Catalysis A: Chemical 387 (2014) 123–129
were performed with a Philips powder diffractometer type PW
1373 goniometer. It was equipped with a graphite monochromator
˚
crystal. The X-ray wavelength was 1.5405 A and the diffraction pat-
terns were recorded in the 2ꢀ range (10–60) with scanning speed
of 2◦/min. Morphology and particle dispersion was investigated
by scanning electron microscopy (SEM) (Cam scan MV2300). The
chemical composition of the prepared nanostructures was mea-
sured by EDS performed in SEM.
Scheme 1. Possible structure for the polystyrene-anchored Cu(II) tetrazole com-
plex.
2.2. Preparation of 5-phenyl-1H-tetrazole
5-Phenyl-1H-tetrazole was prepared according to the literature
[15].
Scheme 2. N-Arylation of sulfonamides with arylboronic acids.
2.3. Preparation of nanopolystyrene-anchored Cu(II) tetrazole
complex 2
The growth of tetrazoles chemistry over the last 30 years has
been significant [14–16], mainly as a result of the roles played
by tetrazoles in coordination chemistry as ligands and in organic
synthesis as an effective substrate [17,18]. We recently published
synthesis of various tetrazoles and their application in coordination
chemistry [14–18]. In addition, polystyrene is one of the most popu-
lar polymeric supports used in synthetic organic chemistry because
of its inexpensiveness, ready availability, mechanical robustness,
chemical inertness, and facile functionalization [19].
In the course of our researches on the synthesis of tetrazoles
and applications of heterogeneous catalysts [14–18,20–22], herein
we report synthesis and characterization of the nanopolystyrene-
anchored Cu(II) tetrazole complex [PS-tet-Cu(II)] (2) (Scheme 1)
and its application as a novel and stable heterogeneous catalyst
for the N-arylation of sulfonamides with arylboronic acids in water
under aerobic conditions (Scheme 2).
The reaction was carried out in a round-bottomed flask of
250 mL capacity. To the mixture of chloromethylated polystyrene
(2.0 g, 1.25 mmol/g of Cl) in 50 mL of DMF, 5-phenyl-1H-tetrazole
(5.0 mmol) and K2CO3 (5.0 mmol) was added. The mixture was
stirred at 100 ◦C for 24 h. Then, reaction mixture was filtrated,
washed with DMF, dried in vacuo for 12 h. Phenyltetrazole-
functionalized polymer 1 (1.0 g) was treated with CuCl2·2H2O
(0.5 g) in ethanol (50 mL) and the mixture stirred under reflux
conditions for 24 h. The resulting bright green colored polymer,
impregnated with the metal complex, was filtered, washed with
ethanol and dried at 60 ◦C to give PS-tet-Cu(II) 2 (Scheme 3).
2.4. General experimental procedure for the N-arylation of
sulfonamides
To
a mixture of PS-tet-Cu(II) 2 (0.05 g) and arylboronic
2. Experimental
acid (0.7 mmol) in water (5 mL), K2CO3 (1 mmol), sulfonamide
(0.7 mmol) and water (5 mL) was added and the mixture was vig-
orously stirred for the appropriate times under reflux conditions.
After completion (as monitored by TLC), the catalyst was filtered
and the reaction mixture was cooled to room temperature. The
resulting product was filtered and purified by recrystallization
using ethyl acetate and n-hexane to afford N-arylated product. All
compounds were compared with the corresponding compounds
prepared by the reported procedure [4,23–40]. All compounds were
known and were characterized by spectral analysis or melting
points. 1H NMR data of some compounds are given below.
2.1. Instruments and reagents
All reagents were purchased from the Merck and Aldrich
chemical companies and used without further purification.
Chloromethylated polystyrene (4–5% Cl and 2% cross-linked with
divinylbenzene) was purchased from Merck. CuCl2·2H2O was pro-
cured from Merck and used without further purification. Products
were characterized by different spectroscopic methods (FT-IR and
1H NMR spectra), elemental analysis (CHN) and melting points.
The NMR spectra were recorded in CDCl3. 1H NMR spectra were
recorded on a Bruker Avance DRX 90 MHz instrument. The chem-
ical shifts (ı) are reported in ppm relative to the TMS as internal
standard. J values are given in Hz. IR (KBr) spectra were recorded on
a Perkin-Elmer 781 spectrophotometer. Melting points were taken
in open capillary tubes with a BUCHI 510 melting point appara-
tus and were uncorrected. The elemental analysis was performed
using Heraeus CHN-O-Rapid analyzer. TLC was performed on silica
gel polygram SIL G/UV 254 plates. X-ray diffraction measurements
2.5. Spectral data of some compounds
2.5.1. N-p-Tolyl-benzenesulfonamide (Table 2, entry 2)
FT-IR (KBr, cm−1): 3261, 3064, 2921, 1914, 1511, 1448, 1392,
1330, 1300, 1221, 1161, 1092, 1022, 914, 814, 754, 724, 687, 641,
578, 526, 503; 1H NMR (90 MHz, CDCl3): ıH 7.83–6.97 (m, 10H),
2.22 (s, 3H).
Scheme 3. Preparation of copper tetrazole-supported complex.

M. Nasrollahzadeh et al. / Journal of Molecular Catalysis A: Chemical 387 (2014) 123–129
125
2.5.2. N-(4-Methoxyphenyl)benzenesulfonamide (Table 2, entry
3)
2.5.11. 4-Methyl-N-(4-chlorophenyl)benzenesulfonamide
(Table 2, entry 14)
FT-IR (KBr, cm−1): 3259, 3065, 3005, 2935, 2837, 1610, 1510,
FT-IR (KBr, cm−1): 3264, 1593, 1481, 1454, 1395, 1334, 1272,
1166, 1090, 1053, 902, 749, 707, 673, 632, 564, 533, 436; 1H NMR
(90 MHz, CDCl3): ıH 7.64–7.10 (m, 9H), 2.35 (s, 3H).
1447, 1395, 1329, 1288, 1250, 1219, 1161, 1091, 1031, 910, 827,
755, 724, 688, 639, 580, 519; 1H NMR (90 MHz, CDCl3): ıH 7.76–6.65
(m, 10H), 3.70 (s, 3H).
2.5.3. 4-Chloro-N-phenyl-benzenesulfonamide (Table 2, entry 4)
FT-IR (KBr, cm−1): 3260, 3090, 2966, 2897, 2835, 1598, 1480,
1414, 1397, 1343, 1322, 1301, 1283, 1222, 1162, 1093, 1031, 1013,
922, 827, 757, 695, 672, 623, 556, 507, 482; 1H NMR (90 MHz,
CDCl3): ıH 7.78–7.08 (m, 10H).
2.5.12. 4-Methyl-N-pyridin-3-yl-benzenesulfonamide (Table 2,
entry 15)
FT-IR (KBr, cm−1): 3482, 3335, 3083, 1631, 1598, 1525, 1494,
1345, 1220, 1177, 1008, 911, 842, 761, 737, 632, 571, 555, 497; 1
NMR (90 MHz, CDCl3): ıH 7.69–7.25 (m, 9H), 2.37 (s, 3H).
H
2.5.4. 4-Chloro-N-(4-methoxyphenyl)-benzenesulfonamide
(Table 2, entry 5)
3. Results and discussion
FT-IR (KBr, cm−1): 3248, 3092, 3016, 2985, 2965, 2840, 11611,
1581, 1508, 1471, 1461, 1444, 1395, 1335, 1288, 1250, 1217, 1174,
1159, 1031, 1011, 940, 907, 828, 777, 757, 705, 682, 624, 583, 540,
517; 1H NMR (90 MHz, CDCl3): ıH 7.65 (d, J = 8.6 Hz, 2H), 7.38 (d,
J = 8.6 Hz, 2H), 6.98 (d, J = 8.3, 2H), 6.78 (d, J = 8.3 Hz, 2H), 6.55 (br,
NH, 1H), 3.75 (s, 3H).
3.1. Characterization of catalyst
The catalyst was characterized using the powder XRD, SEM, EDS
and FT-IR spectroscopy.
Formation of PS-tet-Cu(II) 2 was confirmed by FT-IR spec-
tra. The FT-IR spectrum of the chloromethylated polystyrene
was compared with the polymer-supported tetrazole ligand and
nanopolymer-supported [PS-tet-Cu(II)] catalyst in order to con-
firm the coordination of the metal atom with the tetrazole ligand.
FT-IR spectra of the polymer supported ligand and copper cat-
alyst are given in Fig. 1. As shown in Fig. 1A, the sharp C–Cl
peak (due to CH2Cl groups) at 670 cm−1 and the strong peak at
1265 cm−1 corresponding to the H–C–Cl wagging modes in the
starting polymer practically disappeared after introduction of the
tetrazole ligand on the polymer. The stretching vibrations of the
2.5.5. 4-Chloro-N-p-tolyl-benzenesulfonamide (Table 2, entry 6)
FT-IR (KBr, cm−1): 3273, 3087, 3033, 2964, 2926, 2857, 1915,
1583, 1510, 1473, 1434, 1395, 1336, 1276, 1223, 1163, 1088, 1040,
1014, 966, 942, 908, 828, 812, 770, 754, 706, 660, 575, 530, 480,
428; 1H NMR (90 MHz, CDCl3): ıH 7.77–7.14 (m, 9H), 2.27 (s, 3H).
2.5.6. 4-Chloro-N-(2-chlorophenyl)-benzenesulfonamide
(Table 2, entry 7)
FT-IR (KBr, cm−1): 3255, 3087, 1582, 1480, 1453, 1397, 1341,
1278, 1223, 1177, 1086, 1054, 1038, 1012, 942, 909, 832, 753, 692,
722, 642, 625, 556, 482, 448; 1H NMR (90 MHz, CDCl3): ıH 7.75–7.04
(m, 9H).
N
N double bonds appear at 1448 cm−1 for polystyrene-tetrazole
ligand (Fig. 1A) and complex (Fig. 1B). Some of the extra peaks
present in the complex compared to ligand prove the coordina-
tion of metal atom. The functionalized beads exhibited a band at
1655 cm−1 due to stretching vibrations of the C N double bond,
which was shifted to 1600 cm−1 in the anchored beads, indicat-
ing that the nitrogen atoms of the tetrazole is coordinated to
copper. This suggests that the ligand acts as chelating agent coordi-
nated through ‘N’ atom. The IR spectrum of PS-tet-Cu(II) 2 showed
a band around 408 cm−1 due to the Cu N stretching vibrations
(Fig. 1B).
2.5.7. N-(4-Bromophenyl)-4-chlorobenzenesulfonamide (Table 2,
entry 8)
FT-IR (KBr, cm−1): 3237, 3090, 2906, 2840, 1584, 1486, 1452,
1386, 1328, 1292, 1276, 1229, 1181, 1163, 1116, 1092, 1073, 1009,
915, 844, 825, 752, 711, 675, 633, 570, 496, 480, 436; 1H NMR
(90 MHz, CDCl3): ıH 7.74–6.90 (m, 9H).
Scanning electron micrograph (SEM) was recorded to under-
stand the morphological changes occurring on the surface of the
polymer. As expected, the pure polystyrene bead had a smooth
and flat surface [41], while the anchored complex showed rough-
ening of the top layer (Fig. 2). On the other hand, after metal
loading on the surface of the polymer, a change in morphol-
ogy of the polymer surface is observed and the smooth and flat
surface of the polymer shows a slight roughening on complexa-
tion.
The presence of polystyrene and copper was confirmed with
powder XRD measurements. The powder X-ray diffraction pattern
of the complex is shown in Fig. 3. Polystyrene exhibits broad peaks
at about of 2ꢀ = 19.0◦ and 22.7◦ [42]. Peaks at 38.2◦ and 46.5◦ are
attributed to Cu.
We used Energy Dispersive X-ray Spectroscopy (EDS) to deter-
mine chemical composition of catalyst. The presence of metals
along with oxygen and chlorine can be further surmised by EDS
data which suggests the immobilization of the metal complex on
the surface of the polymer matrix. In the EDS spectrum of catalyst
(Fig. 4), peaks related to C, Cu, Cl and O were observed. EDS results
show that Cu concentration is about 3.07 wt%. The excess oxygen
is due to physical absorption of oxygen from environment during
sample preparation.
2.5.8. N-(4-Methoxyphenyl)-4-methylbenzenesulfonamide
(Table 2, entry 10)
FT-IR (KBr, cm−1): 3269, 3011, 2963, 2839, 1611, 1598, 1509,
1466, 1441, 1396, 1334, 1289, 1253, 1218, 1183, 1105, 1090, 1029,
937, 911, 843, 824, 811, 772, 711, 679, 639, 615, 555; 1H NMR
(90 MHz, CDCl3): ıH 7.58–6.75 (m, 9H), 3.72 (s, 3H), 2.34 (s, 3H).
2.5.9. 4-Methyl-N-o-tolyl-benzenesulfonamide (Table 2, entry
12)
FT-IR (KBr, cm−1): 3279, 3268, 1631, 1600, 1489, 1396, 1331,
1307, 1295, 1160, 1091, 1018, 948, 904, 816, 781, 715, 678, 600,
570; 1H NMR (90 MHz, CDCl3): ıH 7.63 (d, J = 7.8 Hz, 2H), 7.23–7.04
(m, 6H), 6.87 (br, NH, 1H), 2.36 (s, 3H), 2.02 (s, 3H).
2.5.10.
4-Methyl-N-(3-trifluoromethylphenyl)benzenesulfonamide
(Table 2, entry 13)
FT-IR (KBr, cm−1): 3232, 3034, 2933, 1597, 1502, 1412, 1331,
1267, 1170, 1128, 1088, 933, 899, 797, 701, 668, 563; 1H NMR
(90 MHz, CDCl3): ıH 8.11 (br, NH, 1H), 7.80–7.30 (m, 8H), 2.31 (s,
3H).

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M. Nasrollahzadeh et al. / Journal of Molecular Catalysis A: Chemical 387 (2014) 123–129
Fig. 1. FT-IR spectra of: (A) polystyrene-tetrazole ligand (B) supported Cu-tetrazole complex.
3.2. Activity of nanopolystyrene-anchored Cu(II) tetrazole
complex 2 for the N-arylation of sulfonamides
The catalytic activity of complex
2 was studied for the
N-arylation of sulfonamides in water at reflux under aerobic con-
ditions. Reaction conditions were optimized for the N-arylation
of p-toluenesulfonamide using phenylboronic acid as a substrate
and PS-tet-Cu(II) as heterogeneous catalysts in the presence
of water and various bases under reflux conditions (Table 1).
Table 1
Optimization of reaction conditions in N-arylation of p-toluenesulfonamide with
phenylboronic acid.a
Entry
PS-tet-Cu(II) (g)
Base
Yieldb (%)
1
2
3
4
5
6
7
0
K2CO3
K2CO3
K3PO4
Na2CO3
Cs2CO3
K2CO3
K2CO3
0
95
76
81
90
95
80
0.05
0.05
0.05
0.05
0.09
0.03
a
Reaction condition: PhB(OH)2 (0.7 mmol), sulfonamide (0.7 mmol), base
(1.0 mmol), catalyst (0.05 g), H2O (10 mL), reflux, 1 h.
Fig. 2. Typical SEM image of PS-tet-Cu(II).
b
Isolated yield.

M. Nasrollahzadeh et al. / Journal of Molecular Catalysis A: Chemical 387 (2014) 123–129
127
Fig. 3. XRD pattern of PS-tet-Cu(II).
Reaction without catalyst did not give any product (Table 1, entry
1). However, addition of the PS-tet-Cu(II) to the mixture has rapidly
increased the N-arylation of sulfonamides in high yields. Our exper-
iments showed that the base was necessary for the N-arylation
of sulfonamides. Among the selected bases, K2CO3 acted as the
most effective one (Table 1, entry 2). The effect of catalyst load-
ing was probed. Catalyst loads of 0.05 g were typically required
to achieve quantitative conversion with most substrates. No sig-
nificant improvement on the yield was observed using higher
amounts of the catalyst (Table 1, entry 6). The use of lower cat-
alyst loadings resulted in incomplete reactions (Table 1, entry 7).
Due to its shortcoming of difficult recovery, homogeneous cat-
alysts could not be considered as economic and green catalysts
even if displayed good catalytic capacity. We then used the opti-
mal reaction conditions (catalyst (0.05 g), sulfonamide (0.7 mmol),
arylboronic acid (0.7 mmol) and K2CO3 (1.0 mmol)) for N-arylation
of sulfonamides with different arylboronic acids under reflux con-
ditions for the appropriate times and the results are shown in
Table 2.
the yield of desired products. Apart from arylboronic acids we also
tested 3-pyridinylboronic acid as a heteroaryl boronic acid (Table 2,
entry 15).
To show the advantages of proposed method in comparison
with other reported methods, we summarized some of results for
N-arylation of p-toluenesulfonamide and benzenesulfonamide in
Table 3, which shows that PS-tet-Cu(II) is more efficient catalyst
with respect to reaction time and yield than previously reported
ones. Reported methods for the N-arylation of sulfonamides usu-
ally suffer from certain disadvantages such as environmentally
unpleasant use of huge organic solvents, harsh reaction conditions,
long reaction times, low yields of the products, use of ligand and the
use of the excess of homogeneous copper catalyst which cannot be
easily recovered causing the waste generation or pollution. While in
our proposed method there is no catalyst residue after completion
of the reaction which is very important from both the economi-
cal and environmental points of view. The use of the PS-tet-Cu(II)
catalyst represents an interesting and clean synthetic route with-
out application of toxic organic solvents. Reactions took place with
easy operations and cost of the process, risk reduction and high
yields.
A series of sulfonamides were converted into the correspond-
ing N-arylsulfonamides with arylboronic acids containing both
electron-releasing and electron-withdrawing groups by the PS-tet-
Cu(II) in high yields under reflux conditions in water (Table 2).
The present procedure did not show any remarkable difference in
After removal of the solvent and purification, the products were
characterized by melting points, IR and NMR. Appearance of the two
sharp absorption bands for SO2 stretching bands in the IR spectrum
confirmed formation of the N-arylsulfonamides.
3.3. Catalyst recyclability
The reusability of the catalysts is one of the most important ben-
efits and makes them useful for commercial applications. From an
economic point of view, the stability and sustained activity of the
catalysts are of great importance. Thus the recovery and reusabil-
ity of the PS-tet-Cu(II) catalyst was examined by applying it to the
C
N coupling of p-toluenesulfonamide with phenylboronic acid.
After the first run completed, the PS-tet-Cu(II) catalyst was sepa-
rated, washed with deionized water and ethanol alternately and
dried in a hot air oven at 100 ◦C for 2 h. Then the recovered catalyst
was reused directly in the next run of the reaction. The results show
that no loss of catalyst activity was found even after five cycles in
the PS-tet-Cu(II) catalyst system (Table 4). The XRD spectrum of
reused catalyst after five recycles match that of the fresh catalyst,
which also indicates the preservation of structural and catalytic
activity.
Fig. 4. EDS spectrum of PS-tet-Cu(II).

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M. Nasrollahzadeh et al. / Journal of Molecular Catalysis A: Chemical 387 (2014) 123–129
Table 2
Formation of N-arylsulfonamides from arylboronic acids in water.a
Entry
1
Substrate
Product
Time (h)
1
Yieldb (%)
95
M.p. (◦C) (Reported) [Ref.]
111–113 (111–112) [24]
2
3
4
5
6
1.5
1.5
2
92
92
80
84
81
117–119 (117–119) [26]
92–94 (88–89) [29]
102–104 (–) [38]
2
140–144 (–) [28]
2
84–86 (–) [Commercial]
7
2
80
79–82 (79–81) [26]
8
9
2
80
95
90
89
166–170 (166–170) [Commercial]
102–104 (102–103) [33]
113–114 (114) [34]
1
10
11
1.5
1.5
115–117 (117) [34]
12
1.5
83
107–109 (107–109) [10]
13
14
1
1
1
93
93
91
94–96 (94–95.5) [36]
119–122 (119–122) [4]
191–193 (190.5–191.5) [40]
15
a
Reaction conditions: arylboronic acid (0.7 mmol), sulfonamide (0.7 mmol), K2CO3 (1.0 mmol), PS-tet-Cu(II) (0.05 g), H2O (10 mL), reflux conditions.
Yields are after work-up.
b
Table 3
Comparison present methodology with other reported methods in the N-arylation of different sulfonamides.
Entry
Sulfonamide
Conditions
Yielda (%) [Reference]
1
2
3
4
5
6
7
8
9
p-TolSO2NH2
p-TolSO2NH2
p-TolSO2NH2
p-TolSO2NH2
p-TolSO2NH2
p-TolSO2NH2
PhSO2NH2
PhSO2NH2
PhSO2NH2
PhSO2NH2
PhSO2NH2
CuI, PhI, NMGb, K3PO4, DMF, N2, 100 ◦C, 24 h
CuI, PhBr, MW, K2CO3, NMPc, 195 ◦C, 3 h
95 [10]
70 [13]
93 [25]
16 [43]
79 [This work]
95 [This work]
94 [10]
90 [13]
91 [25]
CuI, PhI, N,Nꢀ-DMEDAd, KF/Al2O3, Dioxane, Ar, 100–110 ◦C, 9 h
CuI, PhBr, Cs2CO3, DMF, air, 130 ◦C, 24 h
Tet-Cu(II)e, PhB(OH)2, K2CO3, H2O, reflux, 1 h
PS-tet-Cu(II), PhB(OH)2, K2CO3, H2O, reflux, 1 h
CuI, PhI, NMGb, K3PO4, DMF, N2, 100 ◦C, 24 h
CuI, PhI, MW, K2CO3, NMPc, 195 ◦C, 3 h
CuI, PhI, N,Nꢀ-DMEDAd, KF/Al2O3, Dioxane, Ar, 100–110 ◦C, 9 h
CuI, PhBr, Cs2CO3, DMF, air, 130 ◦C, 24 h
10
11
12
86 [43]
30 [27]
95 [This work]
Cu(OAc)2·H2O, PhB(OH)2, [bmim][BF4], 70 ◦C, 6 h
PS-tet-Cu(II), PhB(OH)2, K2CO3, H2O, reflux, 1 h
PhSO2NH2
a
Yields are after work-up.
N-Methylglycine as ligand.
b
c
N-Methylpyrrolidinone.
d
e
N,Nꢀ-Dimethylethylenediamine as ligand.
Reaction conditions: arylboronic acid (0.7 mmol), sulfonamide (0.7 mmol), K2CO3 (1.0 mmol), Tet-Cu(II) (2.0 mol%), H2O (10 mL), reflux conditions.

M. Nasrollahzadeh et al. / Journal of Molecular Catalysis A: Chemical 387 (2014) 123–129
129
Table 4
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13001.
Recycle of PS-tet-Cu(II) for the reaction of p-toluenesulfonamide with phenylboronic
acid.a
Entry
Cycle
Yieldb (%)
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1
2
3
4
5
6
Fresh
94
94
95
93
92
92
1st recycle
2nd recycle
3rd recycle
4th recycle
5th recycle
a
Reaction were carried out with 0.7 mmol of p-toluenesulfonamide, 0.7 mmol of
phenylboronic acid, 0.05 g of catalyst and 1.0 mmol of K2CO3 in 10.0 mL H2O under
reflux conditions for 1 h.
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2795.
b
Yields are after work-up.
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Mater. Chem. C 1 (2013) 1337.
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Adv. 3 (2013) 6323.
4. Conclusions
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17.
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In conclusion we have developed an efficient and simple pro-
tocol for the preparation of PS-tet-Cu(II) as a heterogeneous and
reusable catalyst. The catalyst was characterized by SEM, XRD, EDS
and FT-IR spectroscopy and exhibited good activities in coupling
reactions of arylboronic acids with sulfonamides. The reactions
generated the corresponding N-arylsulfonamides in good to excel-
lent yields and were applicable to various sulfonamides and a
variety of arylboronic acids. This method has the advantages of high
yields, elimination of homogeneous catalysts, green reaction con-
ditions, simple methodology and easy work up. In addition, this
methodology offers the competitiveness of recyclability of the cat-
alyst without significant loss of catalytic activity, and the catalyst
could be easily recovered and reused for at least 5 cycles, thus
making this procedure environmentally more acceptable.
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Acknowledgment
We gratefully acknowledge from the Iranian Nano Council and
University of Qom for the support of this work.
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