Harnessing Cooperative Energy Transfer and Hydrogen Atom Transfer for Direct Nitrogenations of Non‐Activated Alkanes

While important progress has been achieved recently on direct functionalization of alkanes via photocatalytic methods, direct amination of aliphatic compounds remains a great challenge. Herein we report a conceptually new strategy towards direct conversion of hydrocarbons into amines, based on in situ generation of nitrene radical. Energy transfer between thioxanthone (TXO) photocatalyst and iminoiodinane furnishes the triplet nitrene radical, able to undergo HAT reaction promoting alkane activation and subsequent C─N bond formation step. The user-friendly nature of the metal-free transformation, along with mild reaction conditions further highlight the sustainability of this scalable process delivering a diversity of cycloalkylamines. Combined experimental and computational mechanistic studies support the unusual reaction mechanism.