title: Palladium-Catalyzed Cross-Coupling of α-Bromocarbonyls and Allylic Alcohols for the Synthesis of α-Aryl Dicarbonyl Compounds.
abstract: The palladium-catalyzed coupling of olefins and organohalides is a versatile approach for synthesizing complex molecules from simple starting materials. We have developed a palladium-catalyzed coupling of α-bromocarbonyl compounds with allylic alcohols for the generation of acyclic aryl-substituted dicarbonyl compounds. The reaction proceeds via a tandem olefin insertion of an α-acyl radical followed by a 1,2-aryl migration. In addition to providing preliminary evidence for a free radical mediated mechanism, we demonstrate unprecedented levels of 1,3-stereoinduction for the 1,2-migration step.
authors.affiliation: The University of Texas Southwestern Medical Center at Dallas, Department of Biochemistry, 5323 Harry Hines Boulevard, Dallas, Texas 75390-9038, USA.
authors.forename: Yang
authors.initials: Y
authors.lastname: Yu
authors.affiliation: The University of Texas Southwestern Medical Center at Dallas, Department of Biochemistry, 5323 Harry Hines Boulevard, Dallas, Texas 75390-9038, USA.
authors.forename: Uttam K
authors.initials: UK
authors.lastname: Tambar