A General Photocatalytic Strategy for Nucleophilic Amination of Primary and Secondary Benzylic C–H Bonds

We report a visible-light photoredox-catalyzed method that enables nucleophilic amination of primary and secondary benzylic C­(sp3)–H bonds. A novel amidyl radical precursor and organic photocatalyst operate in tandem to transform primary and secondary benzylic C­(sp3)–H bonds into carbocations via sequential hydrogen atom transfer (HAT) and oxidative radical-polar crossover. The resulting carbocation can be intercepted by a variety of N-centered nucleophiles, including nitriles (Ritter reaction), amides, carbamates, sulfonamides, and azoles, for the construction of pharmaceutically relevant C­(sp3)–N bonds under unified reaction conditions. Mechanistic studies indicate that HAT is amidyl radical-mediated and that the photocatalyst operates via a reductive quenching pathway. These findings establish a mild, metal-free, and modular protocol for the rapid diversification of C­(sp3)–H bonds to a library of aminated products.