title: Complementary catalytic strategies to access alpha-chiral aldehydes.
abstract: The present article summarizes the development of two novel and complementary catalytic methods to access alpha-chiral aldehydes. A C1-symmetric chiral (P,N) ligand with a structure derived from the ubiquitous binepine scaffold has been specifically designed for the Pd-catalyzed alpha-arylation of aldehydes to access indane derivatives with a well-defined quaternary stereocenter in high yields and excellent enantioselectivities. In addition, a dinuclear palladium hydride catalyst has been synthesized for the isomerization of terminal and trisubstituted epoxides into aldehydes and ketones respectively. Combined experimental and theoretical investigations pointed to an unprecedented 'epoxide-opening/hydride-transfer' sequence. The mechanism also features two distinct enantio-determining steps in the kinetic resolution of racemic epoxides.
authors.affiliation: Department of Organic Chemistry, University of Geneva, Geneva. clement.mazet@unige.ch
authors.forename: Clément
authors.initials: C
authors.lastname: Mazet
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D002384:Catalysis; D002625:Chemistry, Organic / Q000379:methods*; D002626:Chemistry, Pharmaceutical / Q000379:methods; D004852:Epoxy Compounds / Q000737:chemistry; D008024:Ligands; D010165:Palladium / Q000737:chemistry; D013237:Stereoisomerism
chemical_list: D000447:Aldehydes; D004852:Epoxy Compounds; D008024:Ligands; D010165:Palladium