BrCF2CN for photocatalytic cyanodifluoromethylation

Xin-Jun Yang; Jin-Hong Lin; Ji-Chang Xiao

doi:10.1038/s41467-024-55797-4

BrCF₂CN for photocatalytic cyanodifluoromethylation

Nat Commun. 2025 Jan 7;16(1):445. doi: 10.1038/s41467-024-55797-4.

Authors

Xin-Jun Yang¹, Jin-Hong Lin^{2

3}, Ji-Chang Xiao⁴

Affiliations

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, 200032, Shanghai, China.
² 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, 200032, Shanghai, China. [email protected].
³ Department of Chemistry, Innovative Drug Research Center, Shanghai University, 200444, Shanghai, China. [email protected].
⁴ 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, 200032, Shanghai, China. [email protected].

Abstract

Considering the unique electronic properties of the CF₂ and the CN groups, the CF₂CN group has significant potential in drug and agrochemical development, as well as material sciences. However, incorporating a CF₂CN group remains a considerable challenge. In this work, we disclose a use of bromodifluoroacetonitrile (BrCF₂CN), a cost-effective and readily available reagent, as a radical source for cyanodifluoromethylation of alkyl alkenes, aryl alkenes, alkynes, and (hetero)arenes under photocatalytic conditions. This protocol demonstrates an exceptionally broad substrate scope and remarkable tolerance to various functional groups. Notably, the cyanodifluoromethylation of alkynes predominantly provides sterically hindered alkenes, a thermodynamically unfavorable outcome, and (hetero)arene C-H bonds are directly amenable to cyanodifluoromethylation without pre-functionalization.