Gan Qi-Chao, Qiao Jia, Zhou Chao, Ci Rui-Nan, Guo Jia-Dong, Chen Bin, Tung Chen-Ho, Wu Li-Zhu
Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry Chinese Academy of Sciences, Beijing, 100190, China.
School of Future Technology, University of Chinese Academy of Sciences, Beijing, 100049, China.
Angew Chem Int Ed Engl. 2023 Apr 17;62(17):e202218391. doi: 10.1002/anie.202218391. Epub 2023 Mar 10.
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 evolution. The redox-neutral conditions, broad substrate scope, and efficiency of N-radical formation are advantageous for organic synthesis.
本文展示了在温和且氧化还原中性条件下直接由N-H键活化生成N-自由基的首个实例。原位生成的N-自由基在量子点（QD）可见光照射下与还原的杂芳基腈/芳基卤化物发生反应以形成C-N键。一系列芳基和烷基胺与杂芳基腈/芳基卤化物反应表现出高效率、位点选择性和良好的官能团耐受性。此外，还实现了以苄胺为底物的连续C-C和C-N键形成，生成伴有氢气释放的N-芳基-1,2-二胺。氧化还原中性条件、广泛的底物范围以及N-自由基形成的效率对有机合成具有优势。
