Zhong-Wei Hou1, Ding-Jin Liu2, Peng Xiong2, Xiao-Li Lai2, Jinshuai Song3, Hai-Chao Xu2. 1. Advanced Research Institute and Department of Chemistry, Taizhou University, Taizhou, 318000, P. R. China. 2. Laboratory of Chemical Biology of Fujian Province, State Key Laboratory of Physical Chemistry of Solid Surfaces, iChEM, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, P. R. China. 3. College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou, 450001, P. R. China.
Abstract
C-H/N-H cross-coupling is an ideal strategy to synthesize various amines but remains challenging owing to the requirement for sacrificial chemical oxidants and the difficulty in controlling the regio- and chemo-selectivity. Herein we report a site-selective electrochemical amination reaction that can convert benzylic C-H bonds into C-N linkages via H2 evolution without need for external oxidants or metal catalysts. The synthetic strategy involves anodic cleavage of benzylic C-H to form a carbocation intermediate, which is then trapped with an amine nucleophile leading to C-N bond formation. Key to the success is to include HFIP as a co-solvent to modulate the oxidation potentials of the alkylbenzene substrate and the aminated product to avoid overoxidation of the latter.
C-H/N-H cross-coupling is an ideal strategy to synthesize various n class="Chemical">amines but remains challenging owing to the requirement for sacrificial chemical oxidants and the difficulty in controlling the regio- and chemo-selectivity. Herein we report a site-selective electrochemical amination reaction that can convert benzylic C-H bonds into C-N linkages via H2 evolution without need for external oxidants or metal catalysts. The synthetic strategy involves anodic cleavage of benzylic C-H to form a carbocation intermediate, which is then trapped with an amine nucleophile leading to C-N bond formation. Key to the success is to include HFIP as a co-solvent to modulate the oxidation potentials of the alkylbenzene substrate and the aminated product to avoid overoxidation of the latter.
Authors: Alexander P Atkins; Albert C Rowett; David M Heard; Joseph A Tate; Alastair J J Lennox Journal: Org Lett Date: 2022-07-13 Impact factor: 6.072