Cobalt-Catalyzed Deaminative Amino- and Alkoxycarbonylation of Aryl Trialkylammonium Salts Promoted by Visible Light.

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.