title: Highly modular C(1) -symmetric chiral (P,N) ligands with a stereolabile P center: experimental and theoretical studies.
abstract: An improved synthesis of a novel class of bidentate (P,N) ligands is presented, the structures of which are characterized by three distinct elements of chirality. The stereoselective installation of the elements of central chirality (at the benzylic carbon and the phosphorus atom) depends on the size of the phosphorus substituent. Thermal inversion of the phosphorus center has been studied experimentally and further correlated by DFT calculations. The potential of these ligands and the role of the phosphorus atom in the asymmetric α-arylation of aldehydes (Pd) and hydrogenation of allylic alcohols (Ir) have also been investigated.
authors: Department of Organic Chemistry, University of Geneva, Quai Ernest Ansermet 30, 1211 Geneva 4 (Switzerland), Fax: (+41) 22-379-3215.
authors: Nicolas
authors: N
authors: Humbert
authors: Evgeny
authors: E
authors: Larionov
authors: Luca
authors: L
authors: Mantilli
authors: Pradeep
authors: P
authors: Nareddy
authors: Céline
authors: C
authors: Besnard
authors: Laure
authors: L
authors: Guénée
authors: Clément
authors: C
authors: Mazet
mesh_terms: D000447:Aldehydes / Q000737:chemistry; D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D008024:Ligands; D008962:Models, Theoretical; D008968:Molecular Conformation; D009584:Nitrogen / Q000737:chemistry*; D010758:Phosphorus / Q000737:chemistry*; D020005:Propanols / Q000737:chemistry; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D000447:Aldehydes; D008024:Ligands; D020005:Propanols; D010758:Phosphorus; C006463:allyl alcohol; D002244:Carbon; D009584:Nitrogen
keywords: N,P ligands; arylation; asymmetric catalysis; chirality; stereoinversion