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 alpha,beta-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.

Automated summary

A metallaphotoredox-catalyzed strategy for the aminocarbonylation of alkynes with amines and CO has been developed. This method allows for selective synthesis of alpha,beta-unsaturated amides and a sequential four-component hydroaminocarbonylation/radical alkylation, demonstrating great potential in the selective and divergent functionalization of alkynes. Preliminary mechanistic studies suggest a photoinduced oxidative insertion of aniline and CO into nickel followed by a migratory insertion of (carbamoyl)nickel species may be involved.