Co-Catalyzed Synthesis of N-Sulfonylcarboxamides from Carboxylic Acids and Sulfonyl Azides

Article abstract of DOI:10.1021/acs.joc.8b01300

A Co-catalyzed effective synthesis of N-sulfonylcarboxamides from the reaction of carboxylic acids and organic azides in the presence of isocyanide has been developed. The protocol has the advantages of short time, low temperature, and being oxidant-free, which provides a new and simple approach for the synthesis of N-sulfonylcarboxamides in good to excellent yields with a broad substrate scope.

Full text of DOI:10.1021/acs.joc.8b01300

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Article
Co-Catalyzed Synthesis of N-Sulfonylcarboxamides
from Carboxylic acids and Sulfonyl Azides
Yue Fang, Zheng-Yang Gu, Shun-Yi Wang, Jin-Ming Yang, and Shun-Jun Ji
J. Org. Chem., Just Accepted Manuscript • Publication Date (Web): 29 Jun 2018
Downloaded from http://pubs.acs.org on June 29, 2018
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Co-Catalyzed Synthesis of N-Sulfonylcarboxamides from Carboxylic acids and
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Sulfonyl Azides
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Yue Fang,1,2,3 ZhengꢀYang Gu,2 ShunꢀYi Wang,2 JinꢀMing Yang*,1 and ShunꢀJun Ji*,2
1School of Pharmacy, Yancheng Teachers University, Yancheng, 224051, China
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2Key Laboratory of Organic Synthesis of Jiangsu Province, College of Chemistry, Chemical
Engineering and Materials Science & Collaborative Innovation Center of Suzhou Nano Science and
Technology, Soochow University, Suzhou, 215123, China; Eꢀmail: chemyjm@163.com;
shunjun@suda.edu.cn
3College of Chemical Engineering, Nanjing University of Technology, Nanjing, 210009, China
ABSTRACT: A Coꢀcatalyzed effective synthesis of Nꢀsulfonylcarboxamides from the reaction of
carboxylic acids and organic azides in the presence of isocyanide has been developed. The protocol has
the advantages of short time, low temperature and oxidantsꢀfree, which provids a new and simple
approach for the synthesis of Nꢀsulfonylcarboxamides in good to excellent yields with a broad substrate
scope.
KEYWORDS: cobalt; carboxylic acids; organic azides; Nꢀsulfonylcarboxamides; isocyanide
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INTRODUCTION
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Nꢀsulfonylcarboxamides and their dervatives are an important class of organic active small molecules,
which are widely used in organic synthesis.1 At the same time, their natural activities have aroused great
concerns of chemical workers. For example, I, II and III (LY573636·Na) are effective antitumor
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agents and are widely used in the treatment of colon cancer, lung cancer, breast cancer, ovarian cancer
and prostate cancer.2 SZ4TA2 IV is an inhibitor of BclꢀXL (Scheme 1).3
Scheme 1. Drugs containing N-sulfonylcarboxamides.
In the past few decades, with the increasing demands of Nꢀsulfonylcarboxamides, a series of
strategies to construct these compounds have been developed (Scheme 2).4ꢀ5 Conventionally, synthesis
of Nꢀsulfonyl formamide and its derivatives involve typical methodologies using sulfonamide to react
with carboxylic acid,6 ester,7 acyl chloride,8 and aldehyde.9 However, these protocols suffer from certain
disadvantages such as use of coupling agents/bases, harsh reaction conditions and low yields. In
addition, Manas and coꢀworks reported a new strategy by breaking the C(O)ꢀCHNO2 bond of αꢀ
nitroketone with TsNBr2 to form a new CꢀN bond under the condition of potassium carbonate.10
Unfortunately, this method also has the drawbacks of using stoichiometric bases and low yields.
Chang’s group reported the first chemoselective ruthenium(II) porphyrin catalyzed amidation of a wide
range of aldehydes with PhI=NTs as the nitrogen source.11 Apart from these, Ashfeld’s team reported
the method for the synthesis of Nꢀsulfonyl formamide and its derivatives from carboxylic acid and azide
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in the presence of chlorophosphite and triethylamine.12 However, the chlorophosphite was airꢀ and
moistureꢀsensitive and a high reaction temperature was required. Recently, our group devoted to
developing the insertion reactions of isocyanides to construct nitrogenꢀcontaining organic molecules.13
During the coupling reaction of carboxylic acid, azide compound and tertꢀbutyl isocyanide,
accidentally, we found that benzoic acid and TsN3 formed Nꢀtosylbenzamide in the presence of tertꢀ
butyl isocyanide and cobalt catalyst. Herein, we report a Coꢀcatalyzed effective synthesis of Nꢀ
sulfonylcarboxamides through the reaction of carboxylic acids and organic azides in the presence of
isocyanide.
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ref 12
R1COOH
R2SO2N3
+
O
O
CIP(OET)2
Et3N
R1
ref 9a
H
R1
ref 8
Cl
O
O
O
O
SO2R2
NO2
ref 10
R1
N
R1
R1
O
R1
H
ref 7a
NTs
[Co]
O
This
work
R1
tBu-NC
R1COOH
ref 6
H
ref 11
R1COOH
R2SO2N3
+
Scheme 2. Methods for the synthesis of N-sulfonylcarboxamides.
RESULTS AND DISCUSSION
Initially, we chose the modle reaction of benzoic acid 1a with TsN3 2a and tertꢀbutyl isocyanide
catalyzed by 5 mol % Co2(CO)8 in MeCN at 80 °C for 4 h. Gratifyingly, the desired product 3aa was
observed in 96% isolated yield (Table 1, entry 1). The structure of 3aa was confirmed by NMR, IR and
HRMS. As we expected, no desired product could be detected in the absence of cobalt catalyst or tertꢀ
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butyl isocyanide (Table 1, entry 2). Then, we screened different cobalt catalysts, such as CoC2O4,
CoCl2·6H2O, Co(acac)2, Co(OAc)2 and CoBr2·H2O, but the yield is not higher than the model reaction
(Table 1, entries 3ꢀ7). The reaction efficiency decreased when other isonitrile was applied instead of
tertꢀbutyl isocyanide (Table 1, entries 8ꢀ12). Decreasing the temperature did not have a benefical effect
on the reaction (Table 1, entries 13ꢀ15).
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Table 1. Optimization of the reaction conditionsa
entry
variations from the standard conditions
yield (%)b
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standard condition
without catalyst/ligand
CoC2O4, instead of Co2(CO)8
96
trace
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CoCl2·6H2O, instead of Co2(CO)8
68
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Co(acac)2, instead of Co2(CO)8
74
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Co(OAc)2, instead of Co2(CO)8
87
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CoBr2·H2O, instead of Co2(CO)8
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2ꢀisocyanoꢀ1,3ꢀdimethylbenzene, instead of tertꢀbutyl isocyanide
ethyl 4ꢀisocyanobenzoate, instead of tertꢀbutyl isocyanide
2ꢀisocyanoꢀ2,4,4ꢀtrimethylpentane, instead of tertꢀbutyl isocyanide
cyclohexyl isocyanide, instead of tertꢀbutyl isocyanide
nꢀbutylisocyanide, instead of tertꢀbutyl isocyanide
20 ℃instead of 80 ℃
77
55
trace
75
93
48
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63
85
40 ℃instead of 80 ℃
60 ℃instead of 80 ℃
aReaction conditions: 1a (0.5 mmol), 2a (0.75 mmol), catalyst (5 mol %), solvent (4 mL), 4 h. bIsolated yield.
With the optimized reaction conditions in hand, we first investigated the scope of various carboxylic
acids (Table 2). The reactions of benzoic acids bearing electronꢀdonating groups (ꢀMe, ꢀOMe)
proceeded smoothly to furnish 3ba-3ea in 71ꢀ98% yields. The halogen substituted benzoic acids (ꢀF, ꢀ
Cl, ꢀBr, ꢀI) also showed good reactivities, and the desired products 3fa-ma could be obtained in 76ꢀ85%
yields. Notably, 3na could be isolated in 70% yield when 4ꢀ(trifluoromethyl)benzoic acid was subjected
to the reaction with 2a. To our delight, both cinnamic acid and cyclobutanecarboxylic acid were also
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well tolerated during this transformation to generate the products 3oa and 3pa in good yields. The
reactions of heteroaromatic carboxylic acids such as furanꢀ3ꢀcarboxylic acid and thiopheneꢀ2ꢀcarboxylic
acid with 2a also resulted in the corresponding products 3qa and 3ra in 91% and 93% yields,
respectively. Unfortunately, some biologically active amino acids such as Dꢀhomoserine and Lꢀproline
failed to give the targeted products.
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Table 2. Substrate scope of carboxylic acidsa,b
aReaction conditions: 1 (0.5 mmol), 2a (0.75 mmol), Co2(CO)8 (5 mol %), MeCN (4 mL), 4 h. bIsolated yield.
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We next investigated the scope of various sulfonyl azides (Table 3). It was gratifying to observe that
paraꢀsubstituted benzenesulfonyl azides bearing electronꢀdonating groups (ꢀH, ꢀOMe) exhibited an
excellent reactivity under the reaction conditions to afford the desired products 3ab-ac in 89ꢀ93%
yields. When halide substituted 4ꢀbromobenzenesulfonyl azide and 4ꢀiodobenzenesulfonyl azide
reacted with 1a, the desired products 3ae-af could be formed in 80ꢀ94% yields. Electronꢀwithdrawing
group (ꢀCN) was well tolerated in the reaction (3ad). Besides, the naphthaleneꢀ2ꢀsulfonyl azide was also
proven to be a good candidate for the reaction, the corresponding product 3ag was afforded in 93%
yield. In particular, acceptable yields were obtained when alkylsulfonyl azides, such as butaneꢀ1ꢀ
sulfonyl azide, propaneꢀ1ꢀsulfonyl azide and ethanesulfonyl azide, were subjected to the reaction (3ah-
aj).
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Table 3. Substrate scope of azidesa,b
aReaction conditions: 1 (0.5 mmol), 2a (0.75 mmol), Co2(CO)8 (5 mol %), MeCN (4 mL), 4 h. bIsolated yield.
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In addition, our procedure could also be applied in the preparation of LY573636 (3sk; Scheme 3),
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which was a marketing drug and used as antitumor agent. The gram scale reaction of 1s and 2k afforded
LY573636 in 60% yield under the optimized conditions.
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Scheme 3. Synthesis of LY573636.
According to the literatures and our previous work, a plausible mechanism was proposed in Scheme
4.14 First, Co2(CO)8 reacts with MeCN to give intermediate A via ligand exchange. Subsequently, A
reacts with isocyanide molecules to furnish Co complex B. The reaction of B and sulfonyl azide leads to
intermediate C. The dissociation of N2 from the intermediate C generates the Co(I)ꢀnitrene intermediate
D, which undergoes coupling reaction between the nitrene moiety with the coordinated isocyanide
ligand to produce intermediate F. Carboxylic acid attacks F to result in the intermediate G. Then, G is
further transformed to intermediate H. Subsequently sulfonylcarboxamide 3 is formed by releasing tertꢀ
butyl isocyanate 3’ which could be detected by LCꢀMS.
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Scheme 4. A plausible mechanism.
In summary, we have developed a Coꢀcatalyzed facile synthesis of sulfonyl azides with carboxylic
acids to form Nꢀsulfonylcarboxamides. This protocol is easy to handle and has no use for bases and
oxidants. A wide range of Nꢀsulfonylcarboxamides can be obtained in good to excellent yields with
good compatibility of functional groups.
EXPERIMENTAL SECTION
General Experimental Information. Unless otherwise stated, all reagents were purchased from commercial suppliers and used without
further purification. Analytical thinꢀlayer chromatography (TLC) was performed on silica gel, visualized by irradiation with UV light. For
column chromatography, 200ꢀ300 mesh silica gel was used. All reactions were carried out in oil bath and using undistilled solvent, without
the need of precautions to exclude air and moisture unless otherwise noted. IR spectra were recorded on a BRUKER VERTEX 70
spectrophotometer. H NMR and 13C NMR spectra were recorded on a BRUKER 400 MHz (1H NMR) or 300 MHz (1H NMR) and 101
1
MHz (13C NMR) or 75 MHz (13C NMR) spectrometer using CDCl3 or DMSOꢀd6 as solvent. High resolution mass spectra were obtained
using BRUKER micrOTOFꢀQ III instrument with ESI source.
General procedure for N-Sulfonylcarboxamides 3
A mixture of carboxylic acids 1 (0.5 mmol), sulfonyl azides 2 (0.75 mmol), and Co2(CO)8 (5 mol%) were added into a flask and stirred at
80 C in 4 mL of MeCN. Then, the tertꢀbutyl isocyanide (100 µL) was added into. Then the mixture was vigorously stirred under reflux
conditions monitored by TLC analysis (about 4h). After removing the solvents in vacuo, the residue was directly purified by flash column
chromatography by using ethyl acetate (EA) and petroleum ether (PE) ( EA/PE = 10 : 1 ~ 2 : 1) as eluents to afford pure product 3.
o
Nꢀtosylbenzamide (3aa). White solid (132 mg, 96%). IR 3306, 1699, 1450, 1419, 1163, 1158, 839, 707, 658 cmꢀ1. H NMR (400 MHz,
Chloroformꢀd) δ 8.03 (d, J = 8.3 Hz, 2H), 7.83 (d, J = 7.5 Hz, 2H), 7.49 (t, J = 7.4 Hz, 1H), 7.35 (t, J = 7.7 Hz, 2H), 7.29 (d, J = 8.1 Hz,
2H), 2.39 (s, 3H). 13C NMR (101 MHz, Chloroformꢀd) δ 165.1, 145.1, 135.7, 133.4, 131.3, 129.6, 128.8, 128.6, 128.1, 21.7. HRMS (ESI)
m/z: calcd. for C14H13NO3NaS [M+Na]+ 298.0514, found: 298.0518.
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4ꢀmethylꢀNꢀtosylbenzamide (3ba). White solid (139 mg, 96%). IR 3296, 1696, 1392, 1153, 841, 657 cmꢀ1. 1H NMR (400 MHz, DMSOꢀd6)
δ 12.39 (s, 1H), 7.85 (dt, J = 48.7, 9.9 Hz, 4H), 7.53 – 7.18 (m, 4H), 2.40 (s, 6H).13C NMR (101 MHz, DMSOꢀd6) δ 165.2, 144.1, 143.6,
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136.7, 129.5, 129.1, 128.8, 128.4, 127.7, 21.1. HRMS (ESI) m/z: calcd. for C15H16NO3S [M+H]+ 290.0851, found: 290.0861.
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3ꢀmethylꢀNꢀtosylbenzamide (3ca). White solid (142 mg, 98%). IR 3292, 1696, 1394, 1151, 1078, 872, 661 cmꢀ1. 1H NMR (400 MHz,
Chloroformꢀd) δ 9.79 (s, 1H), 8.04 (d, J = 8.0 Hz, 2H), 7.69 – 7.56 (m, 2H), 7.42 – 7.25 (m, 4H), 2.40 (s, 3H), 2.29 (s, 3H). 13C NMR (101
MHz, CDCl3) δ 165.1, 145.1, 138.6, 135.6, 134.1, 131.1, 129.6, 128.6, 128.5, 126.3, 125.1, 21.64, 21.13 ppm. HRMS (ESI) m/z: calcd. for
C15H16NO3S [M+H]+ 290.0851, found: 290.0856.
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2ꢀmethylꢀNꢀtosylbenzamid (3da). White solid (140 mg, 97%). IR 3260, 1710, 1595, 1407, 1291, 1164, 1068, 840, 737, 665 cmꢀ1. 1H NMR
(400 MHz, Chloroformꢀd) δ 7.98 (d, J = 7.9 Hz, 2H), 7.36 (dd, J = 27.4, 7.8 Hz, 4H), 7.16 (d, J = 8.0 Hz, 2H), 2.43 (s, 3H), 2.32 (s, 3H).
13C NMR (101 MHz, Chloroformꢀd) δ 166.8, 145.1, 138.0, 135.7, 132.3, 131.7, 131.6, 129.6, 128.5, 127.5, 125.9, 21.8, 20.1. HRMS (ESI)
m/z: calcd. for C15H16NO3S [M+H]+ 290.0851, found: 290.0854.
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4ꢀmethoxyꢀNꢀtosylbenzamide (3ea). White solid (108 mg, 71%). IR 3227, 1667, 1436, 1254, 1162, 1022, 837, 763 cmꢀ1. 1H NMR (400
MHz, DMSOꢀd6) δ 12.28 (s, 1H), 7.89 (t, J = 8.6 Hz, 4H), 7.44 (d, J = 7.8 Hz, 2H), 7.02 (d, J = 8.6 Hz, 2H), 3.82 (s, 3H), 2.40 (s, 3H). 13
C
NMR (101 MHz, DMSOꢀd6) δ 164.6, 163.2, 144.1, 136.8, 130.6, 129.5, 127.7, 123.5, 113.9, 55.6, 38.9, 21.1. HRMS (ESI) m/z: calcd. for
C15H16NO4S [M+H]+ 306.0800, found: 306.0809.
4ꢀchloroꢀNꢀtosylbenzamide (3fa). White solid (124 mg, 80%). IR 3354, 1701, 1590, 1336, 1131, 1076, 810, 755, 662 cmꢀ1. 1H NMR (400
MHz, DMSOꢀd6) δ 7.89 (d, J = 8.1 Hz, 2H), 7.82 (d, J = 7.8 Hz, 2H), 7.47 (d, J = 8.1 Hz, 2H), 7.33 (d, J = 7.9 Hz, 2H), 2.36 (s, 3H). 13
C
NMR (101 MHz, DMSOꢀd6) δ 166.3, 142.1, 139.6, 136.6, 133.9, 130.3, 128.9, 128.1, 127.4, 21.0. HRMS (ESI) m/z: calcd. for
C14H13ClNO3S [M+H]+ 310.0305, found: 310.0311.
4ꢀbromoꢀNꢀtosylbenzamide (3ga). White solid (135 mg, 76%). IR 3211, 1699, 1586, 1435, 1330, 1162, 1071, 829, 751, 660 cmꢀ1. 1H NMR
(400 MHz, DMSOꢀd6) δ 12.60 (s, 1H), 7.90 (d, 2H), 7.81 (d, 2H), 7.70 (d, 2H), 7.44 (d, J = 8.1 Hz, 2H), 2.40 (s, 3H). 13C NMR (101 MHz,
DMSOꢀd6) δ 164.7, 144.2, 136.7, 131.6, 130.9, 130.4, 129.5, 127.8, 127.2, 21.1. HRMS (ESI) m/z: calcd. for C14H13BrNO3S [M+H]+
353.9800, found: 353.9797.
2ꢀfluoroꢀNꢀtosylbenzamide (3ha). White solid (125 mg, 85%). IR 3321, 1702, 1613, 1426, 1346, 1164, 1080, 804, 751, 660 cmꢀ1. 1H NMR
(400 MHz, DMSOꢀd6) δ 12.60 (s, 1H), 7.91 (d, J = 8.0 Hz, 2H), 7.62 – 7.54 (m, 2H), 7.47 (d, J = 8.0 Hz, 2H), 7.34 – 7.27 (m, 2H), 2.41 (s,
3H).13C NMR (101 MHz, DMSOꢀd6) δ 163.0, 159.4 (d, J = 337.3 Hz), 144.4, 136.5, 134.2 (d, J = 11.1 Hz), 130.3 (d, J = 2.0 Hz), 129.6,
127.7, 124.6 (d, J = 4.1 Hz), 121.8 (d, J = 18.2 Hz), 116.4 (d, J = 28.3 Hz), 21.1 ppm. HRMS (ESI) m/z: calcd. for C14H13FNO3S [M+H]+
294.0600, found: 294.0606.
3ꢀchloroꢀNꢀtosylbenzamide (3ia). White solid (125 mg, 81%). IR 3290, 1698, 1511, 1363, 1128, 916, 809, 743, 669 cmꢀ1. 1H NMR (400
MHz, DMSOꢀd6) δ 7.99 – 7.65 (m, 4H), 7.54 – 7.34 (m, 2H), 7.25 (d, J = 7.9 Hz, 2H), 2.34 (s, 3H). 13C NMR (101 MHz, DMSOꢀd6) δ
166.9, 141.3, 140.9, 139.4, 132.6, 130.6, 129.8, 128.5, 128.1, 127.1, 126.9, 21.0. HRMS (ESI) m/z: calcd. for C14H13ClNO3S [M+H]+
310.0305, found: 310.0300.
3ꢀbromoꢀNꢀtosylbenzamide (3ja). White solid (147 mg, 83%). IR 3417, 1590, 1556, 1510, 1342, 1222, 1070, 911, 740, 663 cmꢀ1. 1H NMR
(400 MHz, DMSOꢀd6) δ 8.04 (s, 1H), 7.86 (d, J = 7.7 Hz, 1H), 7.72 (d, J = 7.8 Hz, 2H), 7.56 (d, J = 7.9 Hz, 1H), 7.28 (t, J = 7.8 Hz, 1H),
7.19 (d, J = 7.8 Hz, 2H), 2.31 (s, 3H). 13C NMR (101 MHz, DMSOꢀd6) δ 167.9, 143.0, 141.7, 139.7, 132.6 131.1, 129.9, 128.2, 127.2,
126.9, 121.0, 20.9. HRMS (ESI) m/z: calcd. for C14H12BrNO3NaS [M+Na]+ 375.9619, found: 375.9626.
3ꢀiodoꢀNꢀtosylbenzamide (3ka). White solid (171 mg, 85%). IR 3266, 1705, 1677, 1430, 1233, 1159, 1072, 841, 810, 659 cmꢀ1. 1H NMR
(300 MHz, DMSOꢀd6) δ 12.60 (s, 1H), 8.23 (s, 1H), 7.87 (s, 4H), 7.41 (s, 2H), 7.27 (s, 1H), 2.38 (s, 3H). 13C NMR (75 MHz, DMSOꢀd6) δ
164.6, 143.5, 141.0, 137.5, 136.7, 134.8, 130.5, 129.3, 127.7, 127.6, 94.5, 21.0. HRMS (ESI) m/z: calcd. for C14H12INO3NaS [M+Na]+
423.9480, found: 423.9491.
2ꢀchloroꢀNꢀtosylbenzamide (3la). White solid (124 mg, 80%). IR 3247, 1670, 1595, 1418, 1339, 1173, 1086, 892, 753, 659 cmꢀ1. 1H NMR
(400 MHz, DMSOꢀd6) δ 12.72 (s, 1H), 7.90 (d, J = 7.9 Hz, 2H), 7.55 – 7.37 (m, 6H), 2.42 (s, 3H). 13C NMR (101 MHz, DMSOꢀd6) δ
164.9, 144.4, 136.3, 133.9, 132.2, 129.9, 129.9, 129.6, 129.0, 127.7, 127.3, 21.1. HRMS (ESI) m/z: calcd. for C14H13ClNO3S [M+H]+
310.0305, found: 310.0313.
2ꢀbromoꢀNꢀtosylbenzamide (3ma). White solid (140 mg, 79%). IR 3248, 1697, 1590, 1415, 1339, 1171, 890, 659 cmꢀ1. 1H NMR (400
MHz, DMSOꢀd6) δ 12.69 (s, 1H), 7.89 (d, J = 7.9 Hz, 2H), 7.65 (d, J = 7.4 Hz, 1H), 7.47 (d, J = 8.0 Hz, 2H), 7.42 (d, J = 7.1 Hz, 3H), 2.42
(s, 3H). 13C NMR (101 MHz, DMSOꢀd6) δ 165.6, 144.5, 136.2, 136.0, 133.0, 132.2, 129.6, 129.0, 127.8, 127.7 118.6, 21.1. HRMS (ESI)
m/z: calcd. for C14H12BrNO3NaS [M+Na]+ 375.9619, found: 375.9607.
Nꢀtosylꢀ4ꢀ(trifluoromethyl)benzamide (3na). White solid (120 mg, 70%). IR 3229, 2960, 1702, 1438, 1321, 1159, 1068, 887, 834, 660
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cmꢀ1. H NMR (400 MHz, Chloroformꢀd) δ 8.02 (s, 1H), 7.96 (s, 1H), 7.63 (s, 2H), 7.33 (s, 2H), 2.42 (s, 3H). 13C NMR (101 MHz,
DMSOꢀd6) δ 164.6 , 144.3, 136.6, 135.6, 132.8, 132.4, 129.6, 129.3, 127.8, 125.5, 21.1. HRMS (ESI) m/z: calcd. for C15H13F3NO3S
[M+H]+ 344.0568, found: 344.0575.
Nꢀtosylcinnamamide (3oa). White solid (130 mg, 86%). IR 3236, 3065, 2928, 1692, 1627, 1425, 1083, 989, 863, 660 cmꢀ1. 1H NMR (400
MHz, DMSOꢀd6) δ 7.88 (d, J = 8.2 Hz, 2H), 7.65 – 7.52 (m, 3H), 7.49 – 7.37 (m, 5H), 6.62 (d, J = 15.9 Hz, 1H), 2.40 (s, 3H). 13C NMR
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(101 MHz, DMSOꢀd6) δ 163.5, 144.1, 143.6, 136.7, 133.9, 130.6 , 129.5, 129.0, 128.1 , 127.7, 119.2, 21.1. HRMS (ESI) m/z: calcd. for
C16H15NO3NaS [M+Na]+ 324.0670, found: 324.0664.
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Nꢀtosylcyclobutanecarboxamide (3pa). White solid (94 mg, 74%). IR 3250, 1724, 1595, 1433, 1322, 1171, 1132, 1044, 865, 658 cmꢀ1. 1H
NMR (400 MHz, DMSOꢀd6) δ 11.87 (s, 1H), 7.79 (d, J = 7.9 Hz, 2H), 7.42 (d, J = 7.9 Hz, 2H), 3.08 (t, J = 8.4 Hz, 1H), 2.40 (s, 3H), 2.04
– 1.95 (m, 4H), 1.85 (q, J = 9.2, 8.8 Hz, 1H), 1.68 (s, 1H). 13C NMR (101 MHz, DMSOꢀd6) δ 172.9, 144.1, 136.6, 129.5, 127.5, 38.5, 23.9,
21.1, 17.4. HRMS (ESI) m/z: calcd. for C12H16NO3S [M+H]+ 254.0851, found: 254.0858.
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Nꢀtosylfuranꢀ3ꢀcarboxamide (3qa). White solid (120 mg, 91%). IR 3267, 2963, 1701, 1569, 1419, 1339, 1163, 1121, 1019, 962, 869, 660
cmꢀ1. 1H NMR (400 MHz, Chloroformꢀd) δ 8.11 (s, 1H), 8.02 (d, J = 8.4 Hz, 2H), 7.41 – 7.38 (m, 1H), 7.36 (d, J = 8.1 Hz, 2H), 6.76 (dd, J
= 1.9, 0.8 Hz, 1H), 2.44 (s, 3H). 13C NMR (101 MHz, Chloroformꢀd) δ 159.9, 147.3, 145.5, 144.5, 135.5, 129.8, 128.6, 120.6, 108.9, 21.8.
HRMS (ESI) m/z: calcd. for C12H16NO3S [M+ Na]+ 288.0306, found: 288.0307.
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Nꢀtosylthiopheneꢀ2ꢀcarboxamide (3ra). White solid (131 mg, 93%). IR 3246, 1680, 1594, 1430, 1323, 1254, 1162, 1070, 1025, 863, 725,
656 cmꢀ1. 1H NMR (400 MHz, Chloroformꢀd) δ 8.03 (d, J = 8.3 Hz, 2H), 7.74 (d, J = 3.8 Hz, 1H), 7.57 (d, J = 4.9 Hz, 1H), 7.33 (d, J = 8.1
Hz, 2H), 7.08 – 6.99 (m, 1H), 2.43 (s, 3H). 13C NMR (101 MHz, Chloroformꢀd) δ 159.3, 145.4, 136.2, 135.6, 133.8, 131.4, 129.8, 128.7,
128.4, 21.8. HRMS (ESI) m/z: calcd. for C12H16NO3S [M+ Na]+ 304.0078, found: 304.0077.
Nꢀ(phenylsulfonyl)benzamide (3ab). White solid (122 mg, 93%). IR 3280, 1697, 1451, 1420, 1335, 1175, 1063, 1027, 897, 834 cmꢀ1. 1H
NMR (300 MHz, DMSOꢀd6) δ 12.58 (s, 1H), 8.03 (d, J = 7.1 Hz, 2H), 7.88 (d, J = 7.3 Hz, 2H), 7.76 – 7.71 (m, 1H), 7.70 – 7.62 (m, 3H),
7.61 (s, 1H), 7.50 (t, J = 7.6 Hz, 2H). 13C NMR (101 MHz, DMSOꢀd6) δ 165.5, 139.5, 133.7, 133.3, 131.5, 129., 128.6, 128.4, 127.7.
HRMS (ESI) m/z: calcd. for C13H12NO3S [M+H]+ 262.0538, found: 262.0536.
Nꢀ((4ꢀmethoxyphenyl)sulfonyl)benzamide (3ac). White solid (130 mg, 89%).IR 3269, 1701, 1686, 1579, 1411, 1335, 1243, 1151, 890, 832,
660 cmꢀ1. 1H NMR (400 MHz, DMSOꢀd6) δ 12.44 (s, 1H), 7.99 (d, J = 8.5 Hz, 2H), 7.89 (d, J = 7.7 Hz, 2H), 7.62 (t, J = 7.4 Hz, 1H), 7.50
(t, J = 7.6 Hz, 2H), 7.17 (d, J = 8.5 Hz, 2H), 3.86 (s, 3H). 13C NMR (101 MHz, DMSOꢀd6) δ 165.3, 163.1, 133.2, 131.6, 130.9, 130.2,
128.6, 128.4 , 114.2, 55.7. HRMS (ESI) m/z: calcd. for C14H14NO4S [M+H]+ 292.0644, found: 292.0647.
Nꢀ((4ꢀcyanophenyl)sulfonyl)benzamide (3ad). White solid (102 mg, 71%). IR 3263, 2231, 1697, 1416, 1351, 1165, 1058, 1028, 890, 704,
628 cmꢀ1. 1H NMR (400 MHz, DMSOꢀd6) δ 8.16 (q, J = 8.2 Hz, 4H), 7.88 (d, J = 7.8 Hz, 2H), 7.63 (t, J = 7.4 Hz, 1H), 7.59 – 7.43 (m, 2H).
13C NMR (101 MHz, DMSOꢀd6) δ 165.8, 143.5, 133.5, 133.3, 131.3, 128.6, 128.6, 128.4, 117.6, 116.0. HRMS (ESI) m/z: calcd. for
C14H11N2O3S [M+H]+ 287.0490, found: 287.0487.
Nꢀ((4ꢀbromophenyl)sulfonyl)benzamide (3ae). White solid (136 mg, 80%). IR 3286, 1692, 1571, 1412, 1340, 1156, 1058, 833, 737, 700cm
ꢀ1. 1H NMR (400 MHz, DMSOꢀd6) δ 12.63 (s, 1H), 8.11 (dd, J = 8.6, 5.1 Hz, 2H), 7.89 (d, J = 7.7 Hz, 2H), 7.64 (t, J = 7.4 Hz, 1H), 7.51 (t,
J = 8.0 Hz, 4H). 13C NMR (75 MHz, DMSOꢀd6) δ 165.6, 138.7, 133.4, 132.3, 131.3, 129.7, 128.6, 128.5, 127.7. HRMS (ESI) m/z: calcd. f
or C13H10BrNNaO3S [M+Na]+ 361.9462, found: 361.9458.
Nꢀ((4ꢀiodophenyl)sulfonyl)benzamide (3af). White solid (182 mg, 94%). IR 3291, 1693, 1566, 1451, 1346, 1163, 1062, 884, 685 cmꢀ1. 1H
NMR (400 MHz, Chloroformꢀd) δ 9.60 (s, 1H), 7.84 (dt, J = 15.2, 7.9 Hz, 6H), 7.54 (t, J = 7.5 Hz, 1H), 7.40 (t, J = 7.6 Hz, 2H). 13C NMR
(101 MHz, Chloroformꢀd) δ 164.7, 138.4, 138.1, 133.8, 130.9, 130.0, 129.0, 128.1, 102.3. HRMS (ESI) m/z: calcd. for C13H11INO3S
[M+H]+ 387.9504, found: 387.9511.
Nꢀ(naphthalenꢀ2ꢀylsulfonyl)benzamide (3ag). White solid (145 mg, 93%). IR 3246, 2959, 2922, 2852, 1689, 1451, 1411, 1344, 1254, 1156,
892, 793, 747, 652 cmꢀ1. 1H NMR (400 MHz, DMSOꢀd6) δ 12.66 (s, 1H), 8.71 (s, 1H), 8.26 (d, J = 7.9 Hz, 1H), 8.17 (d, J = 8.8 Hz, 1H), 8.
07 (d, J = 8.0 Hz, 1H), 7.99 (dd, J = 8.7, 1.8 Hz, 1H), 7.92 – 7.84 (m, 2H), 7.79 – 7.67 (m, 2H), 7.62 (t, J = 7.4 Hz, 1H), 7.48 (t, J = 7.7 Hz,
2H). 13C NMR (101 MHz, DMSOꢀd6) δ 165.7, 136.7, 134.6, 133.2, 131.8, 131.5, 129.5, 129.3, 129.3, 129.2, 128.6, 128.4, 127.9, 127.7, 1
22.6. HRMS (ESI) m/z: calcd. for C17H14NO3S [M+H]+ 312.0694, found: 312.0701.
Nꢀ(ethylsulfonyl)benzamide (3ah). White solid (89 mg, 83%). IR 3226, 3072, 2980, 2939, 1682, 1431, 1342, 1153, 894, 720 cmꢀ1. 1H NMR
(400 MHz, DMSOꢀd6) δ 12.04 (s, 1H), 7.94 (d, J = 7.3 Hz, 2H), 7.66 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.7 Hz, 2H), 3.52 (q, J = 7.4 Hz, 2H),
1.26 (t, J = 7.4 Hz, 3H). 13C NMR (75 MHz, DMSOꢀd6) δ 166.5, 133.3, 131.6, 128.6, 128.5, 47.0, 7.8. HRMS (ESI) m/z: calcd. for
C9H11NO3NaS [M+Na]+ 236.0357, found: 236.0370.
Nꢀ(propylsulfonyl)benzamide (3ai). White solid (78 mg, 69%). IR 3158, 2969, 2879, 1657, 1454, 1347, 1263, 1150, 982, 797, 715, 688,
631 cmꢀ1. 1H NMR (400 MHz, DMSOꢀd6) δ 12.07 (s, 1H), 7.99 – 7.89 (m, 2H), 7.65 (t, J = 7.4 Hz, 1H), 7.53 (t, J = 7.7 Hz, 2H), 3.55 –
3.46 (m, 2H), 1.74 (h, J = 7.5 Hz, 2H), 1.00 (t, J = 7.4 Hz, 3H). 13C NMR (75 MHz, DMSOꢀd6) δ 166.5, 133.2, 131.7, 128.6, 128.5, 54.0,
16.8, 12.5. HRMS (ESI) m/z: calcd. for C10H13NO3NaS [M+Na]+ 250.0514, found: 250.0530.
Nꢀ(butylsulfonyl)benzamide (3aj). White solid (87 mg, 72%). IR 3054, 2966, 2872, 1503, 1385, 1213, 1088, 909, 853, 715, 684 cmꢀ1. 1H
NMR (400 MHz, DMSOꢀd6) δ 8.01 – 7.93 (m, 2H), 7.46 – 7.30 (m, 3H), 3.12 – 3.04 (m, 2H), 1.68 – 1.53 (m, 2H), 1.35 (q, J = 7.4 Hz,
2H), 0.85 (t, J = 7.3 Hz, 3H). 13C NMR (101 MHz, DMSOꢀd6) δ 170.4, 138.7, 130.3, 128.4, 127.5, 51.6, 25.8, 21.3, 13.8. HRMS (ESI)
m/z: calcd. for C11H16NO3S [M+H]+ 242.0851, found: 242.0854.
Nꢀ((5ꢀbromothiophenꢀ2ꢀyl)sulfonyl)ꢀ2,4ꢀdichlorobenzamide (3sk). White solid (158 mg, 76%). IR 3311, 3097, 1687, 1395, 1165, 1085,
971, 812, 755, 671 cmꢀ1. 1H NMR (400 MHz, DMSOꢀd6) δ 7.73 (dd, J = 9.3, 2.9 Hz, 2H), 7.58 (d, J = 8.3 Hz, 1H), 7.52 (dd, J = 8.3, 1.9
Hz, 1H), 7.43 (d, J = 4.1 Hz, 1H). 13C NMR (75 MHz, DMSOꢀd6) δ 164.4, 139.9, 136.3, 135.1, 132.3, 131.4, 131.3, 130.7, 129.6, 127.6,
121.2. HRMS (ESI) m/z: calcd. for C11H7BrCl2NO3S2 [M+H]+ 413.8428, found: 413.8449.
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ACKNOWLEDGMENT
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We gratefully acknowledge the National Natural Science Foundation of China (21672157, 21772137,
and 21542015), the Major Basic Research Project of the Natural Science Foundation of the Jiangsu
Higher Education Institutions (No. 16KJA150002), PAPD, the project of scientific and technologic
infrastructure of Suzhou (SZS201708), and Soochow University for financial support, and State and
Local Joint Engineering Laboratory for Novel Functional Polymeric Materials.
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Supporting Information Available.
The copies of 1H and 13C NMR spectra of the products. This material is available free of charge via the
Internet at http://pubs.acs.org.
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−7919.
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