Deoxygenation of ClSO2CF2COOMe with Triphenylphosphine for the Metal-Free Direct Electrophilic Difluoroalkylthiolation of Various Heterocycles

Liping Zheng; Xin Qiu; Zhiwei Xiao; Xiaoyu Ma; Tianzeng Gao; Xiumiao Zhou; Yufei Wang; Yong Guo; Qing-Yun Chen; Chao Liu

doi:10.1021/acs.joc.3c00342

Deoxygenation of ClSO₂CF₂COOMe with Triphenylphosphine for the Metal-Free Direct Electrophilic Difluoroalkylthiolation of Various Heterocycles

J Org Chem. 2023 Jun 2;88(11):7518-7524. doi: 10.1021/acs.joc.3c00342. Epub 2023 May 3.

Authors

Liping Zheng¹, Xin Qiu², Zhiwei Xiao³, Xiaoyu Ma^{3

2}, Tianzeng Gao⁴, Xiumiao Zhou¹, Yufei Wang¹, Yong Guo³, Qing-Yun Chen³, Chao Liu^{3

2}

Affiliations

¹ School of Chemical Engineering and Food Science, Zhengzhou University of Technology, 18 Yingcai Street, Zhengzhou 450044, China.
² School of Chemical and Environmental Engineering, Shanghai Institute of Technology, 100 Haiquan Road, Shanghai 201418, China.
³ Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai 200032, China.
⁴ Henan Ground Biological Science & Technology Co., Ltd., 3 Tanxiang Road, Zhengzhou 450001, China.

PMID: 37134234
DOI: 10.1021/acs.joc.3c00342

Abstract

A direct electrophilic difluoroalkylthiolation reaction of indole derivatives and other electron-rich heterocycles using methyl 2,2-difluoro-2-(chlorsulfonyl)acetate (ClSO₂CF₂COOMe) derived from Chen's reagent (FSO₂CF₂COOMe) is described. The ester group in the product can be further utilized in subsequent versatile transformations. The reactions provide good yields of the corresponding difluoroalkylthiolation products and exhibit high functional group compatibility. It is expected to serve as an alternative and practical protocol for difluoroalkylthiolation of various heterocycles.