Light-Driven Deaminative Formal Nucleophilic Substitution Via C(sp3)-N Bond Cleavage: Nucleophilic Transamination of Alkyl Amines.

Herein, we report a photoredox-enabled catalytic transamination strategy that enables direct amine-to-amine interconversion without prefunctionalization. The reaction proceeds via a polarity inversion pathway, in which one amine is converted into an electrophilic iminium intermediate that couples with a second amine nucleophile. The method exhibits broad scope across benzylic, unactivated, and tertiary amines. Mechanistic studies support the intermediacy of iminium species and reveal that selectivity is governed by two key principles: reaction directionality is controlled by relative nucleophilicity, while site selectivity in C(sp3)-N bond cleavage is dictated by electronic activation or steric accessibility. This work establishes a direct catalytic transamination strategy for native amines, with potential applications in the late-stage modification of complex and bioactive molecules.