Cobalt-Catalyzed Syntheses of Acrylamides and Succindiamides from Alkynes and Amines Promoted by Light.

Catalytic hydrocarbonylations of alkynes hold potential for highly atom-economical and sustainable syntheses of α,β-unsaturated carboxylic acid derivatives. Alkyne hydroaminocarbonylations deliver valuable acrylamides in couplings with amine nucleophiles, but current approaches are limited in scope and rely on precious metal catalysts. Herein, we report a catalytic hydroaminocarbonylation of alkynes using cobalt carbonyl catalysts promoted by visible light. In contrast to the diverse alkene hydrocarbonylations catalyzed by cobalt carbonyl, applications in alkyne hydrocarbonylation are virtually unknown. The reaction couples a broad range of amines with terminal and internal alkynes, and simple reaction modification enables the syntheses of succindiamides in a stereoselective fashion. Alkyne hydroaminocarbonylation is viable even in the absence of a reaction solvent, highlighting the sustainability of this process. Computational and experimental investigations of both the single and double hydroaminocarbonylations support a key role of the cobalt tricarbonyl anion in substrate activation, leading to high reaction regio- and stereoselectivities.