Abstract

AbstractA Markovnikov‐selective hydrodifluoromethylation of alkynes with BrCF2H via nickel catalysis is described. This protocol proceeds via a migratory insertion of nickel hydride to alkyne followed by a CF2H‐coupling, enabling straightforward access to diverse branched CF2H‐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.

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