Direct <i>N</i>−H Activation to Generate Nitrogen Radical for Arylamine Synthesis via Quantum Dots Photocatalysis
Qi‐Chao Gan, Jia Qiao, Chao Zhou, Rui‐Nan Ci, Jia‐Dong Guo, Bin Chen, Chen‐Ho Tung, Li‐Zhu Wu
Abstract
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.