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Site‐Selective Electrochemical Benzylic C−H Amination
Author(s) -
Hou ZhongWei,
Liu DingJin,
Xiong Peng,
Lai XiaoLi,
Song Jinshuai,
Xu HaiChao
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202013478
Subject(s) - amination , chemistry , carbocation , nucleophile , amine gas treating , combinatorial chemistry , electrochemistry , selectivity , substrate (aquarium) , bond cleavage , catalysis , organic chemistry , electrode , oceanography , geology
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 H 2 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.