Transition-Metal-Free Synthesis of Thiosulfonates through Radical Coupling Reaction

Guodong Zhou; Xu-Dong Xu; Gan-Ping Chen; Wen-Ting Wei; Zhiyong Guo

doi:10.1055/s-0037-1610649

Synlett, Table of Contents

Synlett 2018; 29(15): 2076-2080
DOI: 10.1055/s-0037-1610649

letter

Transition-Metal-Free Synthesis of Thiosulfonates through Radical Coupling Reaction

◊

Guodong Zhou

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn Email: guozhiyong@nbu.edu.cn

,

Xu-Dong Xu

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn Email: guozhiyong@nbu.edu.cn

,

Gan-Ping Chen

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn Email: guozhiyong@nbu.edu.cn

,

Wen-Ting Wei*

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn Email: guozhiyong@nbu.edu.cn

^bState Key Laboratory of Chemo/Biosensing and Chemometrics, Hunan University, Changsha 410082, P. R. of China

,

Zhiyong Guo*

^aSchool of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, P. R. of China Email: weiwenting@nbu.edu.cn Email: guozhiyong@nbu.edu.cn

› Author Affiliations

Abstract

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^◊ These authors contributed equally to this work

Abstract

An efficient and practical transition-metal-free radical coupling reaction of sulfonyl hydrazides mediated by NIS/K₂S₂O₈ has been developed to afford a variety of biological activity thiosulfonates in moderate to excellent yields. Compared to a known approach for the synthesis of thiosulfonates from sulfonyl hydrazides, this strategy features high yields, mild reaction conditions, and broad substrate scope. The mechanistic studies revealed that the procedure undergoes via a radical cross-coupling process for the construction of S–S bonds.

Keywords

transition-metal-free - radical coupling reaction - S–S bonds - thiosulfonates

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References

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11 General Procedure To a Schlenk tube were added sulfonyl hydrazides (0.3 mmol), NIS (0.06 mmol), K₂S₂O₈ (0.36 mmol), and THF (2 mL). Then the tube was stirred open in air at 70 °C for the indicated time until complete consumption of starting material as monitored by TLC analysis. After the reaction was finished, the solution was concentrated under reduced pressure, and the mixture was purified by ﬂash column chromatography over silica gel (hexane/ethyl acetate) to afford the desired product 2 and was analyzed by ¹H NMR and ¹³C NMR spectroscopy (see Supporting Information). Typical Data for Representative Compound: S-(p-Tolyl)4-methylbenzenesulfonothioate (2a) Yellow oil (36.3 mg, 87% yield). ¹H NMR (400 MHz, DMSO-d ₆): δ = 7.45 (d, J = 7.6 Hz, 2 H), 7.38 (d, J = 7.6 Hz, 2 H), 7.26–7.20 (m, 4 H), 2.40 (s, 3 H), 2.34 (s, 3 H). ¹³C NMR (100 MHz, DMSO-d ₆): δ = 145.6, 142.6, 140.1, 136.5, 130.9, 130.3, 127.6, 124.2, 21.6, 21.4.
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Supplementary Material

Supporting Information