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Iridium(III)‐Catalyzed Intermolecular C(sp 3 )−H Insertion Reaction of Quinoid Carbene: A Radical Mechanism
Author(s) -
Wang HaiXu,
Richard Yann,
Wan Qingyun,
Zhou CongYing,
Che ChiMing
Publication year - 2020
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.201911138
Subject(s) - chemistry , carbene , regioselectivity , steric effects , insertion reaction , reactivity (psychology) , catalysis , cyclohexene , medicinal chemistry , photochemistry , intermolecular force , yield (engineering) , iridium , migratory insertion , reaction mechanism , stereochemistry , organic chemistry , molecule , medicine , materials science , alternative medicine , pathology , metallurgy
Described herein is an Ir III /porphyrin‐catalyzed intermolecular C(sp 3 )−H insertion reaction of a quinoid carbene (QC). The reaction was designed by harnessing the hydrogen‐atom transfer (HAT) reactivity of a metal‐QC species with aliphatic substrates followed by a radical rebound process to afford C−H arylation products. This methodology is efficient for the arylation of activated hydrocarbons such as 1,4‐cyclohexadienes (down to 40 min reaction time, up to 99 % yield, up to 1.0 g scale). It features unique regioselectivity, which is mainly governed by steric effects, as the insertion into primary C−H bonds is favored over secondary and/or tertiary C−H bonds in the substituted cyclohexene substrates. Mechanistic studies revealed a radical mechanism for the reaction.