Controllable Double Difluoromethylene Insertions into S-Cu Bonds: (Arylthio)tetrafluoroethylation of Aryl Iodides with TMSCF2Br

Shitao Pan; Qiqiang Xie; Xiu Wang; Rumin Huang; Yuhao Lu; Chuanfa Ni; Jinbo Hu

doi:10.1002/anie.202400839

Controllable Double Difluoromethylene Insertions into S-Cu Bonds: (Arylthio)tetrafluoroethylation of Aryl Iodides with TMSCF₂Br

Angew Chem Int Ed Engl. 2024 Apr 2;63(14):e202400839. doi: 10.1002/anie.202400839. Epub 2024 Mar 4.

Authors

Shitao Pan¹, Qiqiang Xie¹, Xiu Wang¹, Rumin Huang¹, Yuhao Lu¹, Chuanfa Ni¹, Jinbo Hu¹

Affiliation

¹ Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, China.

PMID: 38358953
DOI: 10.1002/anie.202400839

Abstract

A new method of constructing "ArSCF₂CF₂Cu" from ArSCu and TMSCF₂Br (TMS=trimethylsilyl) has been developed. The cross-coupling reactions of the obtained "ArSCF₂CF₂Cu" with diverse aryl iodides (Ar'I) provide an efficient access to Ar'CF₂CF₂SAr. Mechanistic studies demonstrate that the "ArSCF₂CF₂Cu" species were generated through controllable double difluoromethylene insertions into ArS-Cu bonds rather than the 1,2-addition of ArSCu to tetrafluoroethylene.

Keywords: (arylthio)tetrafluoroethylation; C−S bond; Difluorocarbene; copper carbene; fluoroalkylcopper; homologation.

Abstract

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