Direct gem-difluoromethylenation of sp(3)-hybridized carbon center through copper-mediated radical/radical cross-coupling for the construction of a CH2-CF2 linkage

Haizhen Jiang; Minjun Xu; Wenjun Lu; Wenfeng Tian; Wen Wan; Yunrong Chen; Hongmei Deng; Shaoxiong Wu; Jian Hao

doi:10.1039/c5cc05677b

Direct gem-difluoromethylenation of sp(3)-hybridized carbon center through copper-mediated radical/radical cross-coupling for the construction of a CH2-CF2 linkage

Chem Commun (Camb). 2015 Nov 11;51(87):15756-9. doi: 10.1039/c5cc05677b.

Authors

Haizhen Jiang¹, Minjun Xu², Wenjun Lu², Wenfeng Tian², Wen Wan², Yunrong Chen², Hongmei Deng³, Shaoxiong Wu⁴, Jian Hao¹

Affiliations

¹ Department of Chemistry, Shanghai University, Shanghai, 200444, P. R. China. hzjiang@shu.edu.cn jhao@shu.edu.cn and Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, 200032, P. R. China.
² Department of Chemistry, Shanghai University, Shanghai, 200444, P. R. China. hzjiang@shu.edu.cn jhao@shu.edu.cn.
³ Laboratory for Microstructures, Shanghai University, Shanghai, 200444, P. R. China.
⁴ Emory NMR Research Center, Emory University, 201 Dowman Drive, Atlanta, Georgia 30322, USA.

PMID: 26313464
DOI: 10.1039/c5cc05677b

Abstract

Efficient direct gem-difluoromethylenation of an sp(3)-hybridized carbon center in benzyl bromides using benzo-1,3-azolic (oxa-, thia- or aza-) difluoromethyl bromides for construction of a CH2-CF2 linkage has been developed through radical/radical C-C cross-coupling via two separate single electron transfer processes (SET) under the promotion of different copper sources.

Publication types

Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

Alkylation
Benzimidazoles / chemical synthesis
Benzothiazoles / chemical synthesis
Benzoxazoles / chemical synthesis
Benzyl Compounds / chemistry*
Bromides / chemistry
Catalysis
Copper / chemistry
Cyclic N-Oxides / chemistry
Free Radicals / chemistry*
Hydrocarbons, Fluorinated / chemical synthesis*
Oxidation-Reduction

Substances

Benzimidazoles
Benzothiazoles
Benzoxazoles
Benzyl Compounds
Bromides
Cyclic N-Oxides
Free Radicals
Hydrocarbons, Fluorinated
cupric bromide
Copper
TEMPO