Rhodium(III)‐Catalyzed Amidation of Unactivated C(sp3)H Bonds

Abstract Nitrogenation by direct functionalization of CH bonds represents an important strategy for constructing CN bonds. Rhodium(III)‐catalyzed direct amidation of unactivated C(sp 3 )H bonds is rare, especially under mild reaction conditions. Herein, a broad scope of C(sp 3 )H bonds are amidated under rhodium catalysis in high efficiency using 3‐substituted 1,4,2‐dioxazol‐5‐ones as the amide source. The protocol broadens the scope of rhodium(III)‐catalyzed C(sp 3 )H activation chemistry, and is applicable to the late‐stage functionalization of natural products.