Catalyst‐Free Benzylic C(sp 3 )─H Bond Intermolecular Amination

Abstract We present an environmentally benign and efficient strategy for the direct amination of benzylic C(sp 3 )─H bonds. This method operates under metal‐free, photocatalyst‐free, and oxidant‐free conditions. Notably, the protocol demonstrates exceptional functional group tolerance and scalability, enabling gram‐scale synthesis and late‐stage functionalization of complex drug‐like molecules.