Divergent Aminocarbonylations of Alkynes Enabled by Photoredox/Nickel Dual Catalysis

A metallaphotoredox‐catalyzed strategy for the selective and divergent aminocarbonylation of alkynes with amines and 1 atm of CO is reported. This synergistic protocol not only enables the Markovnikov‐selective hydroaminocarbonylation of alkynes to afford α,β‐unsaturated amides, but also facilitates a sequential four‐component hydroaminocarbonylation/radical alkylation in the presence of tertiary and secondary alkyl boronate esters, which allows for straightforward conversion of alkynes into corresponding amides. Preliminary mechanistic studies disclose that a photoinduced oxidative insertion of aniline and CO into nickel followed by a migratory insertion of (carbamoyl)nickel species could be involved. A metallaphotoredox‐catalyzed strategy for the Markovnikov‐selective hydroaminocarbonylation of alkynes with amines and 1 atm of CO is reported, offering a novel and complementary platform for accessing α,β‐unsaturated amides. This synergistic protocol facilitates an unprecedented sequential hydroaminocarbonylation/radical alkylation process with tertiary and secondary alkyl boronate esters.