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Donor–Acceptor Complex Enables Alkoxyl Radical Generation for Metal‐Free C(sp 3 )–C(sp 3 ) Cleavage and Allylation/Alkenylation
Author(s) -
Zhang Jing,
Li Yang,
Xu Ruoyu,
Chen Yiyun
Publication year - 2017
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201707171
Subject(s) - alkoxy group , chemistry , radical , cleavage (geology) , acceptor , metal , bond cleavage , stereochemistry , photochemistry , medicinal chemistry , organic chemistry , catalysis , alkyl , materials science , physics , fracture (geology) , condensed matter physics , composite material
The alkoxyl radical is an essential and prevalent reactive intermediate for chemical and biological studies. Here we report the first donor–acceptor complex‐enabled alkoxyl radical generation under metal‐free reaction conditions induced by visible light. Hantzsch ester forms the key donor–acceptor complex with N ‐alkoxyl derivatives, which is elucidated by a series of spectrometry and mechanistic experiments. Selective C(sp 3 )‐C(sp 3 ) bond cleavage and allylation/alkenylation is demonstrated for the first time using this photocatalyst‐free approach with linear primary, secondary, and tertiary alkoxyl radicals.