title: Pd-catalyzed asymmetric β-hydride elimination en route to chiral allenes.
abstract: We wish to report our preliminary results on the discovery and development of a catalytic, asymmetric β-hydride elimination from vinyl Pd(II)-complexes derived from enol triflates to access chiral allenes. To achieve this, we developed a class of chiral phosphite ligands that demonstrate high enantioselectivity, allow access of either allene enantiomer, and are readily synthesized. The methodology is demonstrated on over 20 substrates, and application to the formal asymmetric total synthesis of the natural product, (+)-epibatidine, is also provided.
authors.affiliation: Department of Chemistry, The University of Texas at San Antonio , San Antonio, Texas 78249, United States.
authors.forename: Ian T
authors.initials: IT
authors.lastname: Crouch
authors.forename: Robynne K
authors.initials: RK
authors.lastname: Neff
authors.forename: Doug E
authors.initials: DE
authors.lastname: Frantz
mesh_terms: D000483:Alleles; D019086:Bridged Bicyclo Compounds, Heterocyclic / Q000138:chemical synthesis / Q000737:chemistry; D002384:Catalysis; D002851:Chromatography, High Pressure Liquid; D056831:Coordination Complexes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*; D011725:Pyridines / Q000138:chemical synthesis / Q000737:chemistry; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D019086:Bridged Bicyclo Compounds, Heterocyclic; D056831:Coordination Complexes; D011725:Pyridines; D014753:Vinyl Compounds; D010165:Palladium; D006859:Hydrogen; C082748:epibatidine