Iron-Catalyzed Amination of Strong Aliphatic C(sp3)–H Bonds

A concept for intramolecular denitrogenative C(sp 3 )–H amination of 1,2,3,4-tetrazoles bearing unactivated primary, secondary, and tertiary C–H bonds is discovered. This catalytic amination follows an unprecedented metalloradical activation mechanism. The utility of the method is showcased with the short synthesis of a bioactive molecule. Moreover, an initial effort has been embarked on for the enantioselective C(sp 3 )–H amination through the catalyst design. Collectively, this study underlines the development of C(sp 3 )–H bond functionalization chemistry that should find wide application in the context of drug discovery and natural product synthesis.