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Iridium-catalyzed hydroacylation reactions of C1-substituted oxabenzonorbornadienes with salicylaldehyde: an experimental and computational study.

ABSTRACT: An experimental and theoretical investigation on the iridium-catalyzed hydroacylation of C₁-substituted oxabenzonorbornadienes with salicylaldehyde is reported. Utilizing commercially available [Ir(COD)Cl]₂ in the presence of 5 M KOH in dioxane at 65 °C, provided a variety of hydroacylated bicyclic adducts in up to a 95% yield with complete stereo- and regioselectivity. The mechanism and origins of selectivity in the iridium-catalyzed hydroacylation reaction has been examined at the M06/Def2TZVP level of theory. The catalytic cycle consists of three key steps including oxidative addition into the aldehyde C-H bond, insertion of the olefin into the iridium hydride, and C-C bond-forming reductive elimination. Computational results indicate the origin of regioselectivity is involved in the reductive elimination step.

SUBMITTER: Ho A

PROVIDER: S-EPMC8919423 | biostudies-literature | 2022

REPOSITORIES: biostudies-literature

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Iridium-catalyzed hydroacylation reactions of C1-substituted oxabenzonorbornadienes with salicylaldehyde: an experimental and computational study.

Ho Angel A Pounder Austin A Valluru Krish K Chen Leanne D LD Tam William W

Beilstein journal of organic chemistry 20220302

An experimental and theoretical investigation on the iridium-catalyzed hydroacylation of C<sub>1</sub>-substituted oxabenzonorbornadienes with salicylaldehyde is reported. Utilizing commercially available [Ir(COD)Cl]<sub>2</sub> in the presence of 5 M KOH in dioxane at 65 °C, provided a variety of hydroacylated bicyclic adducts in up to a 95% yield with complete stereo- and regioselectivity. The mechanism and origins of selectivity in the iridium-catalyzed hydroacylation reaction has been examin ...[more]

PMID: 35330776

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