Manganese(I)-Catalyzed C-H Aminocarbonylation of Heteroarenes

A versatile manganese(I) catalyst was employed in CH aminocarbonylation reactions of heteroarenes with aryl as well as with alkyl isocyanates using a removable directing group approach. Detailed experimental mechanistic studies were suggestive of an organometallic CH manganesation step, followed by a rate‐determining migratory insertion. Heteroaromatic amides were obtained by a step‐economical, manganese(I)‐catalyzed CH aminocarbonylation reaction between heteroarenes and aryl and alkyl isocyanates. The catalytic cycle was initiated by a facile organometallic CH manganesation step, followed by a rate‐determining migratory insertion. DG = directing group.