Chinese Journal of Catalysis ›› 2024, Vol. 67: 54-60.DOI: 10.1016/S1872-2067(24)60139-7

• Communication • Previous Articles     Next Articles

Site-selective benzylic C-H oxidation through mediated electrolysis

Yi-Fan Xia, Rui-Xing Gaoa, Ping Fanga, Ya-Ping Hanb(), Cong Maa, Tian-Sheng Meia()   

  1. aState Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai 200032, China
    bSchool of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
  • Received:2024-09-02 Accepted:2024-09-10 Online:2024-11-30 Published:2024-11-30
  • Contact: Ya-Ping Han, Tian-Sheng Mei
  • Supported by:
    National Key R&D Program of China(2021YFA1500100);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0610000);National Natural Science Foundation of China(21821002);National Natural Science Foundation of China(22361142834);National Natural Science Foundation of China(22425111);National Natural Science Foundation of China(22101294);S&TCSM of Shanghai(21ZR1476500);Natural Science Foundation of Ningbo(2023J035)

Abstract:

A novel strategy for site-selective benzylic C-H oxidation has been developed through mediated electrolysis. A bulky maleimide N-oxyl radical (MINO) generated by proton-coupled electrochemical oxidation of N-hydroxymaleimide (NHMI), serves as a hydrogen atom-transfer mediator. Good-to-excellent site selectivity was observed among different substrates, providing a practical approach for site-selective benzylic C-H oxidation. Additionally, the hydrogen-atom transfer mechanism for C-H electrochemical oxidation allows the oxidation to proceed at much lower anode potentials relative to direct electrolysis and with minimal reliance on the substrate's electronic properties.

Key words: Organic electrochemistry, Hydrogen atom transfer, Site-selective oxidation, N-Hydroxymaleimide, Radical oxidation