Selective Fluoromethyl Couplings of Alkynes via Nickel Catalysis

We describe here a Ni‐catalyzed intermolecular carbo‐fluoromethylation of alkynes with aliphatic halides and fluoromethyl halides (BrCF 2 H and ICH 2 F) in the presence of zinc, enabling the facile and selective access to a diverse range of biologically valuable CF 2 H/CH 2 F‐incorporated alkenes with excellent regio‐ and stereoselectivity. Notably, merging intramolecular radical cyclization with fluoromethyl coupling enables the expedient constructions of CF 2 H/CH 2 F‐incorporated lactones and lactams with high efficiency and selectivity. Mechanistic studies disclose that this catalytic protocol proceeds via a radical addition to an alkyne followed by selective coupling with the fluoromethyl unit.