10.1002/adsc.201900047
Advanced Synthesis & Catalysis
References
[1] For selected reviews, see: a) B. M. Trost, Chem. Rev.
1978, 78, 363-382; b) E. Block, Angew. Chem., Int. Ed.
1992, 31, 1135-1178; c) I. Fernández, N. Khiar, Chem.
Rev. 2003, 103, 3651-3705; d) G.-Q. Lin, M.-H. Xu,
Y.-W. Zhong, X.-W. Sun, Acc. Chem. Res. 2008, 41,
831-840; e) T. G. Back, K. N. Clary, D. Gao, Chem.
Rev. 2010, 110, 4498-4553; f) L. Omann, C. D. F.
Kꢀnigs, H. F. T. Klare, M. Oestreich, Acc. Chem. Res.
2017, 50, 1258-1269.
[2] a) L. D. Small, J. H. Bailey, C. J. Cavallito, J. Am.
Chem. Soc. 1949, 71, 3565-3566; b) J. P. Weidner, S. S.
Block, J. Med. Chem. 1964, 7, 671-673;. c) A. Sotirova,
T. Avramova, S. Stoitsova, I. Lazarkevich, V. Lubenets,
E. Karpenko, D. Galabova, Curr. Microbiol. 2012, 65,
534-541.
[3] F. J. Baerlocher, M. O. Baerlocher, C. L. Chaulk, R. F.
Langler, S. L. MacQuarrie, Aust. J. Chem. 2000, 53,
399-402.
[4] M. Smith, R. Hunter, N. Stellenboom, D. A. Kusza, M.
I. Parker, A. N. H. Hammouda, G. Jackson, C. H.
Kaschula, Biochim. Biophys. Acta 2016, 1860, 1439-
1449.
[5] a) J. A. Javitch, X. Li, J. Kaback, A. Karlin, Proc. Natl.
Acad. Sci. U. S. A. 1994, 91, 10355-10359; b) J. A.
Javitch, D. Fu, J. Chen, A. Karlin, Neuron, 1995, 14,
825-831; c) A. Gallardo-Godoy, M. I. Torres-Altoro, K.
J. White, E. L. Barker, D. E. Nichols, Bioorg. Med.
Chem. 2007, 15, 305-311.
Scheme 7. Proposed mechanism.
In summary, we have developed an efficient
electrosynthesis of unsymmetrical thiosulfonates and
selenosulfonates. Various aryl or heterocyclic
thiophenols and arylsulfinic acids were found to be
compatible in this electrochemical oxidative cross-
dehydrogenative coupling reaction. Additionally,
disulfides and diselenides were also practicable under
similar conditions. The reaction could be scaled to
gram-scale with maintenance of good reaction
efficiency. The reactions were operationally simple
under oxidant- and catalyst-free conditions. Further
transformation through electrochemical oxidative
cross-coupling reactions is ongoing in our laboratory.
[6] a) K. Sugata, L. Song, M. Nakamura, S. Ueki, P. G.
Fajer, T. Arata, J. Mol. Biol. 2009, 386, 626-636; b) P.
J. Roth, D. Kessler, R. Zentel, P. Theato, J. Polym. Sci.,
Part A: Polym. Chem. 2009, 47, 3118-3130.
[7] a) P. K. Shyam, S. Son, H.-Y. Jang, Eur. J. Org. Chem.
2017, 5025-5031; b) P. K. Shyam, H.-Y. Jang, J. Org.
Chem. 2017, 82, 1761-1767; c) S. J. Hwang, P. K.
Shyam, H.-Y. Jang, Bull. Korean Chem. Soc. 2018, 39,
535-539; d) R. J. Reddy, A. Shankar, M. Waheed, J. B.
Nanubolu, Tetrahedron Lett. 2018, 59, 2014-2017.
[8] a) S. Ozaki, E. Matsui, T. Saiki, H. Yoshinaga, H.
Ohmori, Tetrahedron Lett. 1998, 39, 8121-8124; b) S.
Kim, S. Kim, N. Otsuka, I. Ryu, Angew. Chem., Int. Ed.
2005, 44, 6183-6186; c) V. Girijavallabhan, C. Alvarez,
F. G. Njoroge, J. Org. Chem. 2011, 76, 6442-6446; d)
P. Mampuys, Y. Zhu, T. Vlaar, E. Ruijter, R. V. A.
Orru, B. U. W. Maes, Angew. Chem., Int. Ed. 2014, 53,
12849-12854; e) S. Yoshida, Y. Sugimura, Y. Hazama,
Y. Nishiyama, T. Yano, S. Shimizu, T. Hosoya, Chem.
Commun. 2015, 51, 16613-16616; f) P. Mampuys, Y.
Zhu, S. Sergeyev, E. Ruijter, R. V. A. Orru, S. Van
Doorslaer, B. U. W. Maes, Org. Lett. 2016, 18, 2808-
2811; g) K. Kanemoto, Y. Sugimura, S. Shimizu, S.
Yoshida, T. Hosoya, Chem. Commun. 2017, 53, 10640-
10643; h) K. Kanemoto, S. Yoshida, T. Hosoya, Chem.
Lett. 2018, 47, 85-88.
Experimental Section
In an undivided three-necked flask (25 mL), 4-
methylbenzenesulfinic acid (1a, 0.6 mmol, 94 mg), 4-
methoxybenzenethiol (2a, 0.4 mmol, 56 mg), LiClO4 (3
mmol, 319 mg) and CH3CN (10 mL) were continuously
added. The flask was equipped with platinum plate
electrodes (1.0×1.0 cm2) as the cathode and anode. The
reaction mixture was stirred and electrolyzed at a constant
current of 5 mA under air at room temperature for 5 h.
After the reaction was completed, the mixture was diluted
with water (30 mL) and then extracted by DCM (10 mL×3).
The combined organic phases were dried over anhydrous
Na2SO4, filtered, concentrated in vacuo and the crude
product was obtained. The pure product 3aa was obtained
by silica gel chromatography using petroleum ether/ ethyl
acetate (30:1) as eluent.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Project 21672104, 21502097), the Natural
Science Foundation of the Education Department of Jiangsu
province (15KJB150015), and the Priority Academic Program
Development of Jiangsu Higher Education Institutions. The
authors also thank Mr. Hailong Liu for the determination of
HRMS.
[9] a) L. Field, T. F. Parsons, J. Org. Chem. 1965, 30, 657-
659; b) S. Oae, Y. H. Kim, T. Takata, D. Fukushima,
Tetrahedron Lett. 1977, 18, 1195-1198; c) Y. H. Kirn,
T. Takata, S. Oae, Tetrahedron Lett. 1978, 19, 2305-
2308; d) S. Oae, T. Takata, Tetrahedron Lett. 1980, 21,
3213-3216; e) N. O. Brace, J. Fluorine Chem. 2000,
5
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