title: Copper(II)-catalyzed hydrosilylation of ketones using chiral dipyridylphosphane ligands: highly enantioselective synthesis of valuable alcohols.
abstract: In the presence of PhSiH(3) as the reductant, the combination of enantiomeric dipyridylphosphane ligands and Cu(OAc)(2)·H(2)O, which is an easy-to-handle and inexpensive copper salt, led to a remarkably practical and versatile chiral catalyst system. The stereoselective formation of a selection of synthetically interesting β-, γ- or δ-halo alcohols bearing high degrees of enantiopurity (up to 99.9% enantiomeric excess (ee)) was realized with a substrate-to-ligand molar ratio (S/L) of up to 10,000. The present protocol also allowed the hydrosilylation of a diverse spectrum of alkyl aryl ketones with excellent enantioselectivities (up to 98% ee) and exceedingly high turn-over rates (up to 50,000 S/L molar ratio in 50 min reaction time) in air, under very mild conditions, which offers great opportunities for the preparation of various physiologically active targets. The synthetic utility of the chiral products obtained was highlighted by the efficient conversion of optically enriched β-halo alcohols into the corresponding styrene oxide, β-amino alcohol, and β-azido alcohol, respectively.
authors: College of Material, Chemistry and Chemical Engineering and Key Laboratory of Organosilicon Chemistry and Material Technology of Ministry of Education, Hangzhou Normal University, Hangzhou 310036, P. R. China.
authors: Feng
authors: F
authors: Yu
authors: Ji-Ning
authors: JN
authors: Zhou
authors: Xi-Chang
authors: XC
authors: Zhang
authors: Yao-Zong
authors: YZ
authors: Sui
authors: Fei-Fei
authors: FF
authors: Wu
authors: Lin-Jie
authors: LJ
authors: Xie
authors: Albert S C
authors: AS
authors: Chan
authors: Jing
authors: J
authors: Wu
mesh_terms: D000438:Alcohols / Q000138:chemical synthesis*; D000605:Amino Alcohols / Q000138:chemical synthesis* / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D004852:Epoxy Compounds / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D017646:Organosilicon Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism
chemical_list: D000438:Alcohols; D000605:Amino Alcohols; D004852:Epoxy Compounds; D007659:Ketones; D008024:Ligands; D017646:Organosilicon Compounds; D003300:Copper; C013690:styrene oxide