Nickel-Catalyzed Markovnikov-Selective Hydrodifluoromethylation of Alkynes Using BrCF2 H

Angew Chem Int Ed Engl. 2023 Aug 1;62(31):e202305426. doi: 10.1002/anie.202305426. Epub 2023 Jun 26.

Abstract

A Markovnikov-selective hydrodifluoromethylation of alkynes with BrCF2 H via nickel catalysis is described. This protocol proceeds via a migratory insertion of nickel hydride to alkyne followed by a CF2 H-coupling, enabling straightforward access to diverse branched CF2 H-alkenes with high efficiency and exclusive regioselectivity. The mild condition applies to a wide array of aliphatic and aryl alkynes with good functional group compatibility. Mechanistic studies are presented to support the proposed pathway.

Keywords: Alkyne; Difluoromethylation; Fluoromethyl Alkenes; Nickel Catalysis; Regioselectivity.