Direct N−H Activation to Generate Nitrogen Radical for Arylamine Synthesis via Quantum Dots Photocatalysis

Abstract Represented herein is the first example of N ‐radical generation direct from N −H bond activation under mild and redox‐neutral conditions. The in situ generated N ‐radical intercepts a reduced heteroarylnitrile/aryl halide for C−N bond formation under visible‐light irradiation of quantum dots (QDs). A series of aryl and alkylamines with heteroarylnitriles/aryl halides exhibit high efficiency, site‐selectivity and good functional‐group tolerance. Moreover, consecutive C−C and C−N bond formation using benzylamines as substrates is also achieved, producing N ‐aryl‐1,2‐diamines with H 2 evolution. The redox‐neutral conditions, broad substrate scope, and efficiency of N ‐radical formation are advantageous for organic synthesis.