title: Enantioselective construction of all-carbon quaternary centers by branch-selective Pd-catalyzed allyl-allyl cross-coupling.
abstract: The Pd-catalyzed cross-coupling of racemic tertiary allylic carbonates and allylboronates is described. This reaction generates all-carbon quaternary centers in a highly regioselective and enantioselective fashion. The outcome of these reactions is consistent with a process that proceeds by way of 3,3'-reductive elimination of bis(η(1)-allyl)palladium intermediates. Strategies for distinguishing the product alkenes and application to the synthesis of (+)-α-cuparenone are also described.
authors.affiliation: Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, USA.
authors.forename: Ping
authors.initials: P
authors.lastname: Zhang
authors.forename: Hai
authors.initials: H
authors.lastname: Le
authors.forename: Robert E
authors.initials: RE
authors.lastname: Kyne
authors.forename: James P
authors.initials: JP
authors.lastname: Morken
mesh_terms: D000498:Allyl Compounds / Q000737:chemistry*; D002384:Catalysis; D019281:Dimerization; D010165:Palladium; D012717:Sesquiterpenes / Q000138:chemical synthesis
chemical_list: D000498:Allyl Compounds; D012717:Sesquiterpenes; C518145:alpha-cuparenone; D010165:Palladium