Cu(OAc)2-catalyzed N-arylation of sulfonamides with arylboronic acids or trimethoxy(phenyl)silane

Article abstract of DOI:10.1080/00397910802638495

Cu(OAc)2-catalyzed C-N bond-formation reaction of sulfonamides with organoboronic acids or trimethoxy(phenyl)silane was achieved in the presence of 20mol% of Cu(OAc)2, providing N-arylation products with yields ranging from moderate to good.

Full text of DOI:10.1080/00397910802638495

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Cu(OAc)2-Catalyzed N-
Arylation of Sulfonamides
with Arylboronic Acids or
Trimethoxy(phenyl)silane
Changduo Pan a , Jiang Cheng a , Huayue Wu a ,
Jinchang Ding a & Miaochang Liu a
a College of Chemistry and Materials Engineering ,
Wenzhou University , Wenzhou, China
Published online: 13 May 2009.
To cite this article: Changduo Pan , Jiang Cheng , Huayue Wu , Jinchang Ding
& Miaochang Liu (2009) Cu(OAc)2-Catalyzed N-Arylation of Sulfonamides with
Arylboronic Acids or Trimethoxy(phenyl)silane, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 39:12,
2082-2092, DOI: 10.1080/00397910802638495
To link to this article: http://dx.doi.org/10.1080/00397910802638495
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Synthetic Communications1, 39: 2082–2092, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910802638495
Cu(OAc)2-Catalyzed N-Arylation of
Sulfonamides with Arylboronic Acids or
Trimethoxy(phenyl)silane
Changduo Pan, Jiang Cheng, Huayue Wu, Jinchang Ding,
and Miaochang Liu
College of Chemistry and Materials Engineering, Wenzhou University,
Wenzhou, China
Abstract: Cu(OAc)2-catalyzed C-N bond-formation reaction of sulfonamides
with organoboronic acids or trimethoxy(phenyl)silane was achieved in the
presence of 20 mol% of Cu(OAc)2, providing N-arylation products with yields
ranging from moderate to good.
Keywords: Arylboronic acids, Cu(OAc)2-catalyzed, sulfonamides, trimethoxy
(phenyl)silane
N-Arylsulfonamides have long been the subjects of pharmaceutical
interest because of their potential biological activities.[1] A large number
of pharmaceutically active compounds contain aryl sulfonamide motifs,[2]
which are employed in the prevention and treatment of bacterial infec-
tions, diabetes mellitus, oedema, hypertension, and gout. Thus, develop-
ing efficient methods to synthesize sulfonamides is a desirable goal.
Recently, the copper-catalyzed N-arylation of sulfonamides with aryl
halides was developed.[3] In 2003, He and Wu studied copper-catalyzed
N-arylation of sulfonamides with aryl halides using microwave heating
at 195 ꢀC.[3d] In 2005, Deng et al. reported copper-catalyzed cross-
coupling of sulfonamides with aryl halides facilitated by amino acid ligands
Received May 7, 2008.
Address correspondence to Miaochang Liu, College of Chemistry and
Materials Engineering, Wenzhou University, Wenzhou 325027, China. E-mail:
mcl_wzu@yahoo.com.cn
2082

CꢂN Bond Formation
2083
in dimethylformamide (DMF) at 135 ꢀC.[3c] Although much progress had
been made in the copper-catalyzed N-arylation of sulfonamides with aryl
halides, the procedures usually required drastic reaction conditions.
Lately, much attention has been paid to the development of transi-
tion-metal-catalyzed N-arylation of sulfonamides through the reaction
of sulfonamides with nucleophilic arylmetal reagents. In 2001, Lam et al.
first reported the Cu(OAc)2-catalyzed N-arylation of sulfonamides with
phenylboronic acid using an organic base in CH2Cl2.[4] Later, Lan et al.
described N-arylation of sulfonamides with phenylboronic acid employ-
ing an equivalent of Cu(OAc)2 ꢁ H2O.[5] Very recently, Kantam et al.
reported the synthesis of N-arylsulfonamides with phenylboronic acid
in ionic liquids.[6] Mild reaction conditions and short reaction times are
important features of their methods. However, N-arylation of sulfon-
amides with arylboronic acids was not systematically studied. Moreover,
a transformation employing trimethoxy(phenyl)silane in place of
arylboronic acids has not been reported before. Herein, we report
systematic N-arylation of sulfonamides with arylboronic acids and
trimethoxy(phenyl)silane.
We initially studied the reaction of 4-methylbenzenesulfonamide with
phenylboronic acid in dry isopropanol as a model reaction in the presence
of 20 mol% of Cu(OAc)2 and 1 equiv. of various inorganic bases. The results
are summarized in Table 1. These results revealed that the bases had dramatic
Table 1. Effect of base and solvent on Cu(OAc)2-catalyzed N-arylation of
sulfonamides with arylboronic acids
Entry
Base
Solvent
Isolated yielda (%)
1
2
3
4
5
6
7
8
9
10
K2CO3
K2CO3
K2CO3
K2CO3
K2CO3
Cs2CO3
K3PO4
MgO
Ethanol
CH2Cl2
THF
1,4-Dioxane
Isopropanol
Isopropanol
Isopropanol
Isopropanol
Isopropanol
Isopropanol
51
36
43
55
65
30
45
30
35
32
Na2CO3
NaOH
aReaction conditions: 4-methylbenzenesulfonamide (0.2 mmol), phenylboronic
acid (0.3 mmol), base (0.3 mmol), solvent (2 mL), 90 ꢀC, 12 h.

2084
C. Pan et al.
effects on N-arylation of sulfonamides. Among the bases screened, the
inorganic base K2CO3 gave the best result, and the N-arylation product
was isolated in 65% yield. Then we turned our attention to the screening of
solvents, and isopropanol was determined to be the best one.
Under the optimal reaction conditions (Table 1, entry 5), a series of
sulfonamides and arylboronic acids were tested, and the results are
summarized in Table 2.
All the substrates ran smoothly in the procedure, and the products
were isolated with yields ranging from moderate to good (Table 2).
Both electron-rich and electron-deficient sulfonamides coupled effi-
ciently with arylboronic acids. In our system, generally the electron-
deficient arylboronic acids delivered the products with greater yields
(Table 2, entries 3 and 4), than the electron-rich analogs (Table 2,
entries 1 and 2). For example, 3ab was isolated in only 63% yield,
whereas 3ac and 3ad were formed in 85% and 81% yields, respectively
(Table 2, entries 2–4).
Having successfully studied N-arylation of sulfonamides with aryl-
boronic acids, we next tested the feasibility for the cross-coupling
between sulfonamides and trimethoxy(phenyl)silane, which has attracted
much attention as a viable option to these processes because of its low
cost, easy availability, nontoxic by-products, and stability under many
reaction conditions.[7]
We applied this catalytic system to the N-arylation of sulfonamides
with trimethoxy(phenyl)silane, replacing the base (K2CO3) with
TBAF ꢁ 3H2O as the additive. To our delight, the reaction ran smoothly
in the procedure, whereas the yields were slightly less than those of the
N-arylation of sulfonamides with arylboronic acids. The results are
shown in Scheme 1.
In summary, we systematically developed N-arylation of sulfona-
mides with arylboronic acids. Compared with the previous results,[4–6]
the present coupling reaction gave greater yields. Moreover, we devel-
oped N-arylation of sulfonamides with trimethoxy(phenyl)silane.
Scheme 1. N-Arylation reaction of sulfonamides with phenyltrimethoxysilane.

CꢂN Bond Formation
2085
Table 2. Cu(OAc)2-catalyzed N-arylation reaction of sulfonamides with
arylboronic acidsa
Entry
1
Sulfonamide 1
Arylboronic acid 2
Isolated yield (%)
65
2
3
4
5
1a
1a
1a
63
85
81
62
2a
6
7
1b
1b
2c
2d
73
72
8
1b
70
9
2a
69
10
11
1c
1c
2b
2d
68
70
12
2b
62
13
1d
2c
73
(Continued )

2086
C. Pan et al.
Table 2. Continued
Entry
Sulfonamide 1
Arylboronic acid 2
Isolated yield (%)
14
15
1d
2d
2a
70
63
16
17
18
1e
1e
1e
2c
2d
2e
75
75
70
aAll reactions were run with sulfonamides (0.2 mmol), arylboronic acids
(0.3 mmol), Cu(OAc)2 (7.4 mg, 20 mol%), and K2CO3 (0.3 mmol) in 2 mL dry
isopropanol at 90 ꢀC in a sealed tube for 12 h.
EXPERIMENTAL
General
All reactions and manipulations were conducted under an air atmosphere.
Column chromatography was performed using EM silica gel 60 (300–400
mesh); 1H NMR and 13C NMR were recorded on a 300-MHz spectrometer.
Chemical shifts were reported in parts per million (ppm) downfield from tet-
ramethylsilane (TMS) with the solvent resonance as the internal standard.
Typical Experimental Procedure for the N-Arylation of Sulfonamides
with Arylboronic Acids or Trimethoxy(phenyl)silane
Under an air atmosphere, a reaction tube was charged with sulfonamides
(0.2 mmol), arylboronic acids or trimethoxy(phenyl)silane (0.3 mmol),
Cu(OAc)2 (7.4 mg, 20 mol%), i-PrOH (2 mL), and K2CO3 (41.4 mg,
0.3 mmol) or TBAF ꢁ 3H2O (94.5 mg, 0.3 mmol). After the mixture was
heated at 90 ꢀC for 12 h, the solvent was evaporated under reduced pres-
sure, and the residue was purified by flash-column chromatography on
silica gel to give the product.
Characterization Data of All the Products
N-Phenyl-4-methylbenzenesulfonamide (3aa)[3c]
1H NMR (CDCl3, 300 MHz): d 7.72–7.65 (m, 2H), 7.24–7.21 (m,
4H), 7.13–7.06 (m, 3H), 6.56 (s, 1H), 2.38 (s, 3H). 13C NMR

CꢂN Bond Formation
2087
(CDCl3, 75 MHz): d 143.9, 136.6, 135.9, 129.6, 129.3, 127.3, 125.2,
121.4, 21.5.
N-(4-Methoxyphenyl)-4-methylbenzenesulfonamide (3ab)[3c]
1H NMR (CDCl3, 300 MHz): d 7.57 (d, J ¼ 8.3 Hz, 2H), 7.21 (d,
J ¼ 8.0 Hz, 2H), 6.96 (d, J ¼ 8.7 Hz, 2H), 6.76 (d, J ¼ 8.7 Hz, 2H), 6.28
(s, 1H), 3.76 (s, 3H), 2.39 (s, 3H). 13C NMR (CDCl3, 75 MHz): d
157.9, 143.6, 135.9, 129.5, 128.7, 127.3, 125.6, 114.4, 55.4, 21.5.
N-(4-Chlorophenyl)-4-methylbenzenesulfonamide (3ac)[8]
1H NMR (CDCl3, 300 MHz): d 7.68 (d, J ¼ 8.3 Hz, 2H), 7.51 (s, 1H),
7.24–7.16 (m, 4H), 7.04 (d, J ¼ 8.7 Hz, 2H), 2.37 (s, 3H). 13C NMR
(CDCl3, 75 MHz): d 144.2, 135.6, 135.2, 130.7, 129.8, 129.4, 127.2,
122.8, 21.5.
N-(4-Fluorophenyl)-4-methylbenzenesulfonamide (3ad)[8]
1H NMR (CDCl3, 300 MHz): d 7.62 (d, J ¼ 8.3 Hz, 2H), 7.23 (d,
J ¼ 8.5 Hz, 2H), 7.09–7.02 (m, 3H), 6.94–6.88 (m, 2H), 2.38 (s, 3H). 13C
NMR (CDCl3, 75 MHz): d 162.2, 158.9, 144.0, 135.6, 132.3, 129.7,
127.3, 124.6, 124.4, 116.2, 115.9, 21.5.
N-Phenyl-3,5-dichlorobenzenesulfonamide (3ba)[9]
1H NMR (CDCl3, 300 MHz): d 7.63 (s, 2H), 7.50 (s, 1H), 7.33–7.30
(m, 2H), 7.22–7.17 (m, 1H), 7.10–7.07 (m, 2H), 6.88 (s, 1H). 13C
NMR (CDCl3, 75 MHz): d 146.5, 140.7, 140.1, 137.8, 134.4, 131.1,
130.3, 127.0.
N-(4-Chlorophenyl)-3,5-dichlorobenzenesulfonamide (3bc)
IR (KBr, cmꢂ1): 3431, 3273, 1567, 1485, 1397, 1337, 1169, 805. Mp: 131–
1
134 ꢀC. H NMR (CDCl3, 300 MHz): d 7.63 (s, 2H), 7.54–7.53 (m, 1H),
7.29–7.28 (m, 2H), 7.03 (d, J ¼ 8.7 Hz, 2H), 6.85 (s, 1H). 13C NMR
(CDCl3, 75 MHz): d 140.9, 138.6, 138.0, 136.8, 134.5, 130.3, 128.4. MS
(ESI): m=z 335 (Mþ). Anal. Calcd. for C12H8Cl3NO2S: C, 42.82; H,
2.40; N, 4.16. Found: C, 42.84; H, 2.34; N, 4.10.

2088
C. Pan et al.
N-(4-Fluorophenyl)-3,5-dichlorobenzenesulfonamide (3bd)
IR (KBr, cmꢂ1): 3285, 3078, 1572, 1507, 1471, 1349, 1169, 803. Mp: 103–
1
105 ꢀC. H NMR (CDCl3, 300 MHz): d 7.59 (s, 2H), 7.54–7.53 (m, 1H),
7.09–6.97 (m, 4H), 6.75 (s, 1H). 13C NMR (CDCl3, 75 MHz): d 162.8,
159.5, 141.4, 136.1, 133.1, 131.1, 125.6, 125.5, 125.3, 117.2, 116.6,
116.3. MS (ESI): m=z 320 (Mþ). Anal. calcd. for C12H8Cl2FNO2S: C,
45.02; H, 2.52; N, 4.37. Found: C, 45.10; H, 2.50; N, 4.33.
N-(4-(Trifluoromethyl)phenyl)-3,5-dichlorobenzenesulfonamide (3be)[10]
1H NMR (CDCl3, 300 MHz): d 7.69 (s, 2H), 7.58–7.55 (m, 3H), 7.20
(d, J ¼ 8.6 Hz, 2H), 7.08 (s, 1H). 13C NMR (CDCl3, 75 MHz): d
141.4, 138.8, 136.4, 136.3, 133.6, 133.5, 126.97, 126.93, 126.87, 125.5,
120.3, 120.3.
N-Phenyl-4-(trifluoromethyl)benzenesulfonamide (3ca)[11]
1H NMR (CDCl3, 300 MHz): d 7.90 (d, J ¼ 8.2 Hz, 2H), 7.70 (d,
J ¼ 8.3 Hz, 2H), 7.29–7.24 (m, 2H), 7.18–7.08 (m, 4H). 13C NMR
(CDCl3, 75 MHz): d 142.4, 135.7, 134.9, 134.4, 129.5, 127.7, 126.3,
126.2, 126.1, 126.0, 124.8, 121.9, 121.2.
N-(4-Methoxyphenyl)-4-(trifluoromethyl)benzenesulfonamide (3cb)
IR (KBr, cmꢂ1): 3248, 2963, 2843, 1609, 1508, 1442, 1337, 1169. Mp:
1
141–143 ꢀC. H NMR (CDCl3, 300 MHz): d 7.82 (d, J ¼ 8.2 Hz, 2H),
7.70 (d, J ¼ 8.2 Hz, 2H), 6.98 (d, J ¼ 8.7 Hz, 2H), 6.78 (d, J ¼ 8.7 Hz,
2H), 6.52 (s, 1H), 3.77 (s, 3H). 13C NMR (CDCl3, 75 MHz): d 158.4,
158.3, 142.4, 134.7, 134.3, 127.9, 126.0, 125.94, 125.83, 124.9, 121.3,
114.6, 55.4. MS (ESI): m=z 331 (Mþ). Anal. calcd. for
C14H12Cl2F3NO3S: C, 50.75; H, 3.65; N, 4.23. Found: C, 50.83; H,
3.60; N, 4.18.
N-(4-Fluorophenyl)-4-(trifluoromethyl)benzenesulfonamide (3cd)
IR (KBr, cmꢂ1): 3265, 1605, 1507, 1444, 1337, 1156. Mp: 126–128 ꢀC. 1H
NMR (CDCl3, 300 MHz): d 7.84 (d, J ¼ 8.2 Hz, 2H), 7.72 (d, J ¼ 8.2 Hz,
2H), 7.07–6.95 (m, 4H), 6.59 (s, 1H). 13C NMR (CDCl3, 75 MHz): d
162.7, 159.4, 142.2, 131.4, 127.7, 126.3, 126.2, 125.3, 125.2, 116.6,
116.3. MS (ESI): m=z 319 (Mþ). Anal. calcd. for C13H9F4NO2S: C,
48.90; H, 2.84; N, 4.39. Found: C, 49.02; H, 2.80; N, 4.33.

CꢂN Bond Formation
2089
N-(4-Methoxyphenyl)-4-chlorobenzenesulfonamide (3db)[11]
1H NMR (CDCl3, 300 MHz): d 7.62 (d, J ¼ 8.7 Hz, 2H), 7.40 (d,
J ¼ 8.7 Hz, 2H), 6.96 (d, J ¼ 8.7 Hz, 2H), 6.77 (d, J ¼ 8.7 Hz, 2H), 6.39
(s, 1H). 13C NMR (CDCl3, 75 MHz): d 158.3, 139.4, 129.2, 128.7,
128.2, 125.8, 114.5, 55.4.
N-(4-Chlorophenyl)-4-chlorobenzenesulfonamide (3dc)[11]
1H NMR (CDCl3, 300 MHz): d 7.70 (d, J ¼ 8.7 Hz, 2H), 7.42 (d,
J ¼ 8.7 Hz, 2H), 7.20 (d, J ¼ 8.7 Hz, 2H), 7.09 (s, 1H), 7.02 (d, J ¼ 8.7 Hz,
2H). 13C NMR (CDCl3, 75 MHz): d 139.9, 136.9, 134.5, 131.5, 129.6,
129.5, 128.6, 123.3.
N-(4-Fluorophenyl)-4-Chlorobenzenesulfonamide (3dd)[12]
1H NMR (CDCl3, 300 MHz): d 7.66 (d, J ¼ 8.6 Hz, 2H), 7.42
(d, J ¼ 8.6 Hz, 2H), 7.07–7.03 (m, 2H), 6.98–6.92 (m, 3H). 13C NMR
(CDCl3, 75 MHz): d 159.3, 139.7, 137.0, 131.7, 129.4, 128.7, 125.1,
124.9, 116.4, 116.1.
N-Phenylbenzenesulfonamide (3ea)[3c]
1H NMR (CDCl3, 300 MHz): d 7.81–7.77 (m, 2H), 7.53–7.51 (m, 1H),
7.46–7.43 (m, 2H), 7.26–7.21 (m, 2H), 7.10–7.07 (m, 4H). 13C NMR
(CDCl3, 75 MHz): d 138.8, 136.3, 133.0, 129.3, 129.0, 127.2, 125.4,
121.7.
N-(4-Chlorophenyl)benzenesulfonamide (3ec)[13]
1H NMR (CDCl3, 300 MHz): d 7.76 (d, J ¼ 7.6 Hz, 2H), 7.59–7.43
(m, 3H), 7.20 (d, J ¼ 8.7 Hz, 2H), 7.01 (d, J ¼ 8.6 Hz, 2H), 6.85 (s, 1H).
13C NMR (CDCl3, 75 MHz): d 138.5, 134.9, 133.2, 131.0, 129.4, 129.1,
127.2, 122.9.
N-(4-Fluorophenyl)benzenesulfonamide (3ed)[12]
1H NMR (CDCl3, 300 MHz): d 7.75–7.72 (m, 2H), 7.55–7.44 (m, 3H),
7.06–6.95 (m, 2H), 6.94–9.92 (m, 3H). 13C NMR (CDCl3, 75 MHz): d
162.4, 138.6, 133.1, 132.1, 132.0, 129.0, 127.2, 124.8, 124.7, 116.3,
115.9.

2090
C. Pan et al.
N-(4-(Trifluoromethyl)phenyl)benzenesulfonamide (3ee)[14]
1H NMR (CDCl3, 300 MHz): d 7.86 (d, J ¼ 7.5 Hz, 2H), 7.58–7.56
(m, 1H), 7.51–7.46 (m, 4H), 7.37 (s, 1H), 7.20 (d, J ¼ 8.5 Hz, 2H).
13C NMR (CDCl3, 75 MHz): d 139.7, 138.6, 133.5, 129.3, 127.1, 126.7,
126.67, 126.62, 126.5, 125.6, 122.0, 119.8.
ACKNOWLEDGMENTS
We thank the National Natural Science Foundation of China
(No. 20504023) and the Science and Technology Projects of Zhejiang
Province (No. 2006C31030) for financial support.
REFERENCES
1. (a) Harter, W. G.; Albrect, H.; Brady, K.; Caprathe, B.; Dunbar, J.; Gilmore,
J.; Hays, S.; Kostlan, C. R.; Lunney, B.; Walker, N. The design and synthesis
of sulfonamides as caspase-1 inhibitors. Bioorg. Med. Chem. Lett. 2004, 14,
809–812; (b) Reddy, N. S. M.; Mallireddigari, R.; Cosenza, K. G.; Bell, S.
C.; Reddy, E. P.; Reddy, M. V. R. Synthesis of new coumarin 3-(N-aryl)
sulfonamides and their anticancer activity. Bioorg. Med. Chem. Lett. 2004,
14, 4093–4097; (c) Stranix, B. R.; Lavallee, J. F.; Sevigny, G.; Yelle, J.;
Perron, V.; Leberre, N.; Herbart, D.; Wu, J. J. Lysine sulfonamides as novel
HIV-protease inhibitors: Ne-Acyl aromatic a-amino acids. Bioorg. Med.
Chem. Lett. 2006, 16, 3459–3462.
2. (a) Koehler, N. K. U.; Yang, C. Y.; Varady, J.; Lu, Y.; Wu, X. W.; Liu, M.;
Yin, D.; Bartels, M.; Xu, B. Y.; Roller, P. P.; Long, Y. Q.; Li, P.; Kattah, M.;
Cohn, M. L.; Moran, K.; Tilley, E.; Richert, J. R.; Wang, S. Structure-based
discovery of nonpeptidic small organic compounds to block the cell response
to myelin basic protein. J. Med. Chem. 2004, 47, 4989–4997; (b) Cole, D. C.;
Lennox, W. J.; Lombardi, S.; Ellingboe, J. W.; Bernotas, R. C.; Tawa, G. J.;
Mazandarani, H.; Smith, D. L.; Zhang, G.; Coupet, J.; Schechter, L. E.
Discovery of 5-arylsulfonamido-3-(pyrrolidin-2-ylmethyl)-1H-indole deriva-
tives as potent, selective 5-HT6 receptor agonists and antagonists. J. Med.
Chem. 2005, 48, 353–356; (c) Banerjee, M.; Poddar, A.; Mitra, G.; Surolia,
A.; Owa, T.; Bhattacharyya, B. Sulfonamide drugs binding to the colchicine
site of tubulin: Thermodynamic analysis of the drug-tubulin interactions by
isothermal titration calorimetry. J. Med. Chem. 2005, 48, 547–555.
3. (a) Deng, W.; Liu, L.; Guo, Q. X. Recent progress in copper-catalyzed cross-
coupling reactions. Chin. J. Org. Chem. 2004, 24, 150–165; (b) Kunz, K.;
Scholz, U.; Ganzer, D. Renaissance of Ullmann and Goldberg reactions—
Progress in copper-catalyzed C-N, C-O, and C-S coupling. Synlett 2003, 2428–
2439; (c) Deng, W.; Liu, L.; Zhang, C.; Liu, M.; Guo, Q. X. Copper-catalyzed

CꢂN Bond Formation
2091
cross-coupling of sulfonamides with aryl iodides and bromides facilitated by
amino acid ligands. Tetrahedron Lett. 2005, 46, 7295–7298; (d) He, H.; Wu, Y.
J. Copper-catalyzed N-arylation of sulfonamides with aryl bromides and iodides
using microwave heating. Tetrahedron Lett. 2003, 44, 3385–3386.
4. Lam, P. Y. S.; Vincent, G.; Clark, C. G.; Deudon, S.; Jadhav, P. K. Copper-
catalyzed general C-N and C-O bond cross-coupling with arylboronic acid.
Tetrahedron Lett. 2001, 42, 3415–3418.
5. Lan, J. B.; Zhang, G. L.; Yu, X. Q.; You, J. S.; Chen, L.; Yan, M.; Xie, R. G.
A simple copper salt catalyzed N-arylation of amines, amides, imides, and
sulfonamides with arylboronic acids. Synlett 2004, 1095–1097.
6. Kantam, M. L.; Neelima, B.; Reddy, C. V.; Neeraja, V. N-Arylation of
imidazoles, imides, amines, amides and sulfonamides with boronic acids using
a recyclable Cu(OAc)2ꢁH2O=[bmim][BF4] system. J. Mol. Catal. A: Chem.
2006, 249, 201–206.
7. (a) Gouda, K.; Hagiwara, E.; Hatanaka, Y.; Hiyama, T. Cross-coupling
reactions of aryl chlorides with organochlorosilanes: Highly effective meth-
ods for arylation or alkenylation of aryl chlorides. J. Org. Chem. 1996, 61,
7232–7233; (b) Pilcher, A. S.; DeShong, P. Utilization of tetrabutylammo-
nium triphenyldifluorosilicate as a fluoride source for silicon-carbon bond
cleavage. J. Org. Chem. 1996, 61, 6901–6905; (c) Mowery, M. E.; DeShong,
P. Synthesis of unsymmetrical biaryls by palladium-catalyzed cross coupling
reactions of arenes with tetrabutylammonium triphenyldifluorosilicate, a
hypervalent silicon reagent. J. Org. Chem. 1999, 64, 3266–3270; (d) Denmark,
S. E.; Wu, Z. Synthesis of unsymmetrical biaryls from arylsilacyclobutanes.
Org. Lett. 1999, 1, 1495–1498; (e) Li, J. H.; Deng, C. L.; Liu, W. J.; Xie,
Y. X. Pd(OAc)2=DABCO as an inexpensive and efficient catalytic system
for Hiyama cross-coupling reactions of aryl halides with aryltrimethoxysi-
lanes. Synthesis 2005, 3039–3044; (f) Li, J. H.; Deng, C. L.; Xie, Y. X.
Improved procedure for palladium-catalyzed Hiyama cross-coupling reaction
of aryl halides with aryltrimethoxysilanes under solvent-free conditions.
Synthesis 2006, 969–974; (g) Mino, T.; Shirae, Y.; Saito, T.; Sakamoto, M.;
Fujita, T. Palladium-catalyzed Sonogashira and Hiyama reactions using
phosphine-free hydrazone ligands. J. Org. Chem. 2006, 71, 9499–9502; (h)
Shi, S. Y.; Zhang, Y. H. Pd(OAc)2-catalyzed fluoride-free cross-coupling
reactions of arylsiloxanes with aryl bromides in aqueous medium. J. Org.
Chem. 2007, 72, 5927–5930.
8. Park, K. K.; Lee, J. J.; Ryu, J. Photo–Fries rearrangement of N-arylsulfona-
mides to aminoaryl sulfone derivatives. Tetrahedron 2003, 59, 7651–7659.
9. Somasekhara, S.; Dighe, V. S.; Suthar, G. K.; Dighe, N. K.; Mukherjee, S. L.
Chlorobenzenesulfonamides and some related benzothiadiazines. Indian J.
Chem. 1968, 6, 19–23.
10. Hirohumi, N.; Satoshi, G.; Keizaburo, M.; Seiichi, W.; Hilsashi, T. Prepara-
tion of N-phenylbenzenesulfonamide derivatives as insecticides, miticides, and
nematocides. WO Patent 9700857, 1997; Chem. Abstr. 1997, 126, 143975.
11. Fuwa, H.; Hiromoto, K.; Takahashi, Y.; Yokoshima, S.; Kan, T.;
Fukuyama, T.; Iwatsubo, T.; Tomita, T.; Natsugari, H. Synthesis of biotiny-

2092
C. Pan et al.
lated photoaffinity probes based on arylsulfonamide c-secretase inhibitors.
Bioorg. Med. Chem. Lett. 2006, 16, 4184–4189.
12. Thakur, M.; Thakur, A.; Khadikarc, P. V.; Supurand, C. T. QSAR study on
`
pKa vis-a-vis physiological activity of sulfonamides: A dominating role of
surface tension (inverse steric parameter). Bioorg. Med. Chem. Lett. 2005,
15, 203–209.
13. Chandrasekhar, S.; Narsihmulu, C. Direct conversion of azides to carba-
mates and sulfonamides using Fe=NH4Cl: Effect of sonication. Tetrahedron
Lett. 2000, 41, 7969–7972.
14. Sharma, A. K.; Das, S. K. Microwave-induced rapid access to aromatic and
heteroaromatic sulfonamides under solvent-free conditions without using
external base. Synth. Commun. 2004, 34, 3807–3819.