Alena M Vasquez1, John A Gurak1, Candice L Joe2, Emily C Cherney3, Keary M Engle1. 1. Department of Chemistry, The Scripps Research Institute, 10550 North Torrey Pines Road, La Jolla, California 92037, United States. 2. Chemical Process Development, Bristol Myers Squibb, 1 Squibb Drive, New Brunswick, New Jersey 08903, United States. 3. Discovery Chemistry, Bristol Myers Squibb, US Rt. 206 and Province Line Road, Princeton, New Jersey 08540, United States.
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.
The palladium-catalyzed, α-selective hydropan class="Chemical">arylation 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.
Authors: Yining Ji; R Erik Plata; Christopher S Regens; Michael Hay; Michael Schmidt; Thomas Razler; Yuping Qiu; Peng Geng; Yi Hsiao; Thorsten Rosner; Martin D Eastgate; Donna G Blackmond Journal: J Am Chem Soc Date: 2015-10-13 Impact factor: 15.419
Authors: John J Molloy; Ciaran P Seath; Matthew J West; Calum McLaughlin; Neal J Fazakerley; Alan R Kennedy; David J Nelson; Allan J B Watson Journal: J Am Chem Soc Date: 2017-12-22 Impact factor: 15.419