Photoredox-catalyzed coupling of aryl sulfonium salts with CO 2 and amines to access O -aryl carbamates.

An efficient photoredox-catalyzed three-component coupling reaction of aryl sulfonium salts, carbon dioxide and amines has been developed for the first time. This reaction provides a new strategy for the synthesis of a range of valuable O -aryl carbamates from readily available arenes via a site-selective thianthrenation/carbamoyloxylation two-step process. Mild conditions, broad substrate scope and good functional group tolerance are the features of the transformation. The synthetic utility of the method was demonstrated by the late-stage modification of bioactive molecules and pharmaceuticals.