A phosgene‐ and metal‐free synthesis of O‐aryl carbamates is realized through a three‐component coupling of carbondioxide, amines and diaryliodoniumsalts. The reaction only requires a base as the promoter, providing access to a diverse array of O‐aryl carbamates in moderate to high yields with excellent chemoselectivity.
An efficient photoredox-catalyzed three-componentcoupling 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