Catalytic α-Hydroarylation of Acrylates and Acrylamides via an Interrupted Hydrodehalogenation Reaction
Alena M. Vasquez, John A. Gurak, Candice L. Joe, Emily C. Cherney, Keary M. Engle
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 [PdII(Ar)(H)] intermediate, which performs selective hydride insertion into the β-position of α,β-unsaturated carbonyl compounds.
Topics & Concepts
ChemistryPalladiumCatalysisSelectivityHydrideCombinatorial chemistryOrganic chemistryHydrogenCatalytic C–H Functionalization MethodsCatalytic Cross-Coupling ReactionsAsymmetric Hydrogenation and Catalysis