Nickel‐Catalyzed Markovnikov‐Selective Hydrodifluoromethylation of Alkynes Using BrCF2H

Abstract A Markovnikov‐selective hydrodifluoromethylation of alkynes with BrCF 2 H via nickel catalysis is described. This protocol proceeds via a migratory insertion of nickel hydride to alkyne followed by a CF 2 H‐coupling, enabling straightforward access to diverse branched CF 2 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.