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Minimization of Back‐Electron Transfer Enables the Elusive sp 3 C−H Functionalization of Secondary Anilines
Author(s) -
Zhao Huaibo,
Leonori Daniele
Publication year - 2021
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202100051
Subject(s) - deprotonation , surface modification , aniline , electron transfer , radical , chemistry , catalysis , photoredox catalysis , combinatorial chemistry , photochemistry , organic chemistry , photocatalysis , ion
Anilines are some of the most used class of substrates for application in photoinduced electron transfer. N,N‐Dialkyl‐derivatives enable radical generation α to the N‐atom by oxidation followed by deprotonation. This approach is however elusive to monosubstituted anilines owing to fast back‐electron transfer (BET). Here we demonstrate that BET can be minimised by using photoredox catalysis in the presence of an exogenous alkylamine. This approach synergistically aids aniline SET oxidation and then accelerates the following deprotonation. In this way, the generation of α‐anilinoalkyl radicals is now possible and these species can be used in a general sense to achieve divergent sp 3 C−H functionalization.