title: Cu(II)-catalyzed asymmetric hydrosilylation of diaryl- and aryl heteroaryl ketones: application in the enantioselective synthesis of orphenadrine and neobenodine.
abstract: With certain amounts of sodium tert-butoxide and tert-butanol as additives, catalytic amounts of an inexpensive and easy-to-handle copper source Cu(OAc)(2)⋅H(2)O, a commercially available and air-stable non-racemic dipyridylphosphine ligand, as well as the stoichiometric desirable hydride donor polymethylhydrosiloxane (PMHS), formed a versatile in situ catalyst system for the enantioselective reduction of a broad spectrum of prochiral diaryl and aryl heteroarylketones in air, in high yields and with good to excellent enantioselectivities (up to 96 %). In particular, the practical viability of this process was evinced by its successful applications in the asymmetric synthesis of optically enriched potent antihistaminic drugs orphenadrine and neobenodine.
authors.affiliation: 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, PR China.
authors.forename: Yao-Zong
authors.initials: YZ
authors.lastname: Sui
authors.forename: Xi-Chang
authors.initials: XC
authors.lastname: Zhang
authors.forename: Jun-Wen
authors.initials: JW
authors.lastname: Wu
authors.forename: Shijun
authors.initials: S
authors.lastname: Li
authors.forename: Ji-Ning
authors.initials: JN
authors.lastname: Zhou
authors.forename: Min
authors.initials: M
authors.lastname: Li
authors.forename: Wenjun
authors.initials: W
authors.lastname: Fang
authors.forename: Albert S C
authors.initials: AS
authors.lastname: Chan
authors.forename: Jing
authors.initials: J
authors.lastname: Wu
mesh_terms: D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006633:Histamine Antagonists / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D007659:Ketones / Q000737:chemistry*; D008024:Ligands; D015394:Molecular Structure; D009966:Orphenadrine / Q000031:analogs & derivatives* / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D013237:Stereoisomerism; D020002:tert-Butyl Alcohol / Q000737:chemistry
chemical_list: D006633:Histamine Antagonists; D007659:Ketones; D008024:Ligands; D003300:Copper; C574921:neobenodine; D009966:Orphenadrine; D020002:tert-Butyl Alcohol