gem-Difluoroolefination of Diazo Compounds with TMSCF₃ or TMSCF₂Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors

Mingyou Hu, Chuanfa Ni, Lingchun Li, Yongxin Han and Jinbo Hu*

*Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Ling-Ling Road, Shanghai, 200032, China, Email: jinbohusioc.ac.cn

M. Hu, C. Ni, L. Li, Y. Han, J. Hu, J. Am. Chem. Soc., 2015, 137, 14496-14501.

DOI: 10.1021/jacs.5b09888

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Abstract

A transition-metal-free cross-coupling of two carbene fragments proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene derived from Ruppert-Prakash reagent (TMSCF₃) or TMSCF₂Br followed by elimination of N₂. This transition-metal-free protocol efficiently affords various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins.

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Copper-Catalyzed gem-Difluoroolefination of Diazo Compounds with TMSCF₃ via C-F Bond Cleavage

M. Hu, Z. He, B. Gao, L. Li, C. Ni, J. Hu, J. Am. Chem. Soc., 2013, 135, 17302-17305.

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Key Words

alkenyl halides, vinyl fluorides

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ID: J48-Y2015