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ChemComm
Kunz, R. Bartels, G. Lehwark-Yvetot, W. Hansel, K. J. Schaper, J.
K. Seydel, J. Med. Chem., 2004, 47, 240 and references cited therein.
of benzamide was involved in the rate-determining step of the
sulfonylation (see SI for details).
7
W. Su, Tetrahedron Lett., 1994, 35, 4955.
DOI: 10.1039/C5CC00202H
KHCO3
+KOAc
O
O
65 8 Selected references: (a) B. M. Graybill, J. Org. Chem., 1967, 32,
2931; (b) S. J. Nara, J. R. Harjani, M. M. Salunkhe, J. Org. Chem.,
2001, 66, 8616; (c) R. Singh, R. Kamble, K. Chandra, P. Saravanan,
V. Singh, Tetrahedron 2001, 57, 241 and references cited therein.
Cu(OAc)2
K2CO3
Cu(OAc)2
Cu+
N
CuII
N
CuII
1a
N
N
O
H
AcO
A
5
KHCO3
+KOAc
K2CO3
O
B
O
9
Selected references: (a) S. Cacchi, G. Fabrizi, A. Goggiamani, L. M.
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-
PhSO2
N
CuIII
N
N
70
H
N
CuIII
N
N
Cu+
SO2Ph
AcO
PhO2S
C
D
3a
Scheme 1 Plausible mechanism.
10
10 (a) F. Huang, R. A. Batey, Tetrahedron 2007, 63, 7667; (b) A. Kar, I.
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Though the mechanism of this reaction is still unclear at this
moment, based on the above investigations and literature
precedents,18a,22,23 a tentative reaction mechanism is proposed in
Scheme 1. Firstly, Coordination of 1a to Cu(OAc)2 followed by
15 ligand exchange provides intermediate A which undergoes C-H
activation to form the aryl/CuII species B. Next copper(III)
complex C is formed via Cu(OAc)2-promoted oxidation of
B.18a,22 C will next react with sodium sulfinate to afford copper
complex D.19,23 Subsequent reductive elimination of D provides
20 the desired sulfonylated product 3a.
75
85
5094; (d) T. W. Lyons, M. S. Sanford, Chem. Rev., 2010, 110, 1147;
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O
8AQ
HN
8AQ
N
1.NaH, THF
oC, 1 h
O
O
OH
O
O
S
NaOH
O
S
0
14 A. E. Wendlandt, A. M. Suess, S. S. Stahl, Angew. Chem., Int. Ed.,
2011, 50, 11062.
90 15 V. G. Zaitsev, D. Shabashov, O. Daugulis, J. Am. Chem. Soc., 2005,
127, 13154.
S
O
EtOH, 130 oC
2.MeI, 0 oC
8AQ = 8-aminoquinolyl
O
O
65% in 2 steps
25
Scheme 2 Removal of 8-Aminoquinoline directing group.
16 For a recent review, see: G. Rouquet, N. Chatani, Angew. Chem., Int.
Ed., 2013, 52, 11726.
17 (a) L. D. Tran, I. Popov, O. Daugulis, J. Am. Chem. Soc., 2012, 134,
To demonstrate the synthetic utility of our procedure, we
attempted to remove the 8-aminoquinoline directing group. As
shown in Scheme 2, N-methylation of the secondary amide
followed by base hydrolysis gave 2-tosylbenzoic acid in a good
95
100
105
110
115
120
125
18237; (b) T. Truong, K. Klimovica, O. Daugulis, J. Am. Chem.
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30 overall yield of 65%.
In conclusion, we have developed a novel copper-mediated
auxiliary-assisted ortho C-H bond sulfonylation of benzoic acid
derivative with a variety of sodium sulfinates. Notable features of
this newly developed protocol include high monosulfonylation
35 selectivity, excellent ortho-sulfonylation selectivity and broad
functional group compatibility. Exploration on extending this
strategy for the synthesis of complex sulfones is currently
underway in our lab and the results will be reported in due course.
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Notes and references
40 a State Key Laboratory of Chemo/Biosensing and Chemometrics, College
of Chemistry and Chemical Engineering, Hunan University, Changsha
† Electronic Supplementary Information (ESI) available: [Detail
experimental procedures, analytical data]. See DOI: 10.1039/b000000x/
45 We gratefully acknowledge the National Natural Science Foundation of
China (21072051) for their financial support.
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