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Iridium(III)-Catalyzed Intermolecular C(sp3 )-H Insertion Reaction of Quinoid Carbene: A Radical Mechanism.

Hai-Xu WangYann RichardQingyun WanCong-Ying ZhouChi-Ming Che
Published in: Angewandte Chemie (International ed. in English) (2019)
Described herein is an IrIII /porphyrin-catalyzed intermolecular C(sp3 )-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.
Keyphrases
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