A Key Intermediate in Copper-Mediated Arene Trifluoromethylation, [nBu4 N][Cu(Ar)(CF3 )3 ]: Synthesis, Characterization, and C(sp2 )-CF3 Reductive Elimination

Zehai Lu; He Liu; Shihan Liu; Xuebing Leng; Yu Lan; Qilong Shen

doi:10.1002/anie.201904041

A Key Intermediate in Copper-Mediated Arene Trifluoromethylation, [nBu₄ N][Cu(Ar)(CF₃ )₃ ]: Synthesis, Characterization, and C(sp² )-CF₃ Reductive Elimination

Angew Chem Int Ed Engl. 2019 Jun 17;58(25):8510-8514. doi: 10.1002/anie.201904041. Epub 2019 May 13.

Authors

Zehai Lu¹, He Liu¹, Shihan Liu², Xuebing Leng¹, Yu Lan², Qilong Shen¹

Affiliations

¹ Key Laboratory of Organofluorine Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, P. R. China.
² School of Chemistry and Chemical Engineering, Chongqing University, Chongqing, 400030, P. R. China.

PMID: 31004379
DOI: 10.1002/anie.201904041

Abstract

The synthesis, characterization, and C(sp² )-CF₃ reductive elimination of stable aryl[tris(trifluoromethyl)]cuprate(III) complexes [nBu₄ N][Cu(Ar)(CF₃ )₃ ] are described. Mechanistic investigations, including kinetic studies, studies of the effect of temperature, solvent, and the para substituent of the aryl group, as well as DFT calculations, suggest that the C(sp² )-CF₃ reductive elimination proceeds through a concerted carbon-carbon bond-forming pathway.

Keywords: copper; fluorine; reductive elimination; transition metals; trifluoromethyl groups.

Abstract

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