Iridium(III)-Catalyzed Intermolecular C(sp3 )-H Insertion Reaction of Quinoid Carbene: A Radical Mechanism.
Angew Chem Int Ed Engl
; 59(5): 1845-1850, 2020 Jan 27.
Article
em En
| MEDLINE
| ID: mdl-31755156
ABSTRACT
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 40â
min reaction time, up to 99 % yield, up to 1.0â
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.
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MEDLINE
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En
Ano de publicação:
2020
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Article