Erik J. Alexanian

Catalytic carbonylations of aryl electrophiles via C(sp 2 )−N cleavage remains a significant challenge. Herein, we demonstrate an aminocarbonylation of aniline‐derived trialkylammonium salts promoted by visible light with a simple cobalt catalyst. The reaction proceeds under mild conditions suitable for late‐stage functionalization and is amenable to telescoped carbonylations directly from anilines. A range of alkylamines are successful partners, and alkoxycarbonylation is also demonstrated. Mechanistic studies and DFT calculations support a novel mechanism for catalytic carbonylations of aryl electrophiles involving a key visible light‐induced carbonyl photodissociation.