title: Transformation of zirconocene-olefin complexes into zirconocene allyl hydride and their use as dual nucleophilic reagents: reactions with acid chloride and 1,4-diketone.
abstract: Zirconocene-olefin complexes Cp(2)Zr(H(2)C=CHR), prepared in benzene-THF at 0 degrees C, react with acid chlorides to provide homoallylic alcohols. The key is an equilibrium between the zirconocene-olefin complexes and the corresponding zirconocene allyl hydride complexes via allylic C-H bond cleavage of the coordinating alkenes. Furthermore, the zirconocene-olefin complexes are also available for the reaction with 1,4-diketone to afford anti-1,4-diols with excellent diastereoselectivity. Thus, Cp(2)Zr(H(2)C=CHR) serves as a donor of both hydride and an allylic group. These reactions also proceed efficiently by using zirconocene-olefin complexes, derived from Cp(2)ZrCl(2), Mg metal, and 1-alkenes.
authors.affiliation: Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-daigaku Katsura, Nishikyo-ku, Kyoto 615-8510, Japan.
authors.forename: Kazuya
authors.initials: K
authors.lastname: Fujita
authors.forename: Hideki
authors.initials: H
authors.lastname: Yorimitsu
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Shinokubo
authors.forename: Koichiro
authors.initials: K
authors.lastname: Oshima