Intermolecular C−H Amidation of (Hetero)arenes to Produce Amides through Rhodium‐Catalyzed Carbonylation of Nitrene Intermediates

Abstract Amide bond formation is one of the most important reactions in organic chemistry because of the widespread presence of amides in pharmaceuticals and biologically active compounds. Existing methods for amides synthesis are reaching their inherent limits. Described herein is a novel rhodium‐catalyzed three‐component reaction to synthesize amides from organic azides, carbon monoxide, and (hetero)arenes via nitrene‐intermediates and direct C−H functionalization. Notably, the reaction proceeds in an intermolecular fashion with N 2 as the only by‐product, and either directing groups nor additives are required. The computational and mechanistic studies show that the amides are formed via a key Rh‐nitrene intermediate.