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Catalytic α-Hydroarylation of Acrylates and Acrylamides via an Interrupted Hydrodehalogenation Reaction.

ABSTRACT: The palladium-catalyzed, α-selective hydroarylation of acrylates and acrylamides is reported. Under optimized conditions, this method is highly tolerant of a wide range of substrates including those with base sensitive functional groups and/or multiple enolizable carbonyl groups. A detailed mechanistic study was undertaken, and the high selectivity of this transformation was shown to be enabled by the formation of a [Pd^II(Ar)(H)] intermediate, which performs selective hydride insertion into the β-position of α,β-unsaturated carbonyl compounds.

SUBMITTER: Vasquez AM

PROVIDER: S-EPMC7293711 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Catalytic α-Hydroarylation of Acrylates and Acrylamides via an Interrupted Hydrodehalogenation Reaction.

Vasquez Alena M AM Gurak John A JA Joe Candice L CL Cherney Emily C EC Engle Keary M KM

Journal of the American Chemical Society 20200528 23

The palladium-catalyzed, α-selective hydroarylation of acrylates and acrylamides is reported. Under optimized conditions, this method is highly tolerant of a wide range of substrates including those with base sensitive functional groups and/or multiple enolizable carbonyl groups. A detailed mechanistic study was undertaken, and the high selectivity of this transformation was shown to be enabled by the formation of a [Pd<sup>II</sup>(Ar)(H)] intermediate, which performs selective hydride insertio ...[more]

PMID: 32379433

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