title: Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles.
abstract: We report a highly enantioselective CuH-catalyzed Markovnikov hydrosilylation of vinylarenes and vinyl heterocycles. This method has a broad scope and enables both the synthesis of isolable silanes and the conversion of crude products to chiral alcohols. Density functional theory calculations support a mechanism proceeding by hydrocupration followed by σ-bond metathesis with a hydrosilane.
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Michael W
authors.identifier: 0000-0003-2008-3264
authors.initials: MW
authors.lastname: Gribble
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Michael T
authors.initials: MT
authors.lastname: Pirnot
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Jeffrey S
authors.initials: JS
authors.lastname: Bandar
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Richard Y
authors.initials: RY
authors.lastname: Liu
authors.affiliation: Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
authors.forename: Stephen L
authors.initials: SL
authors.lastname: Buchwald
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D006571:Heterocyclic Compounds / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D015394:Molecular Structure; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry; D014753:Vinyl Compounds / Q000737:chemistry*
chemical_list: D000475:Alkenes; D006571:Heterocyclic Compounds; D012821:Silanes; D014753:Vinyl Compounds; D003300:Copper; D006859:Hydrogen