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 H2 evolution. The redox-neutral conditions, broad substrate scope, and efficiency of N-radical formation are advantageous for organic synthesis.