title: Innovative reactions mediated by zirconocene.
abstract: Radical reactions mediated by Schwartz reagent and zirconocene(alkene) complex are firstly described. Schwartz reagent is a promising alternative to tributyltin hydride and the first transition metal hydrido complex used as a radical mediator in organic synthesis. A zirconocene(alkene) complex effects single electron transfer to alkyl halide to generate the corresponding alkyl radical. Secondly, serendipitous allylic C-H bond activation of the coordinating alkene of zirconocene(alkene) complex and its application to organic synthesis are summarized. By utilizing equilibrium between zirconocene(alkene) and zirconocene 2-alkenyl hydride, reaction of acid chloride with zirconocene(alkene) provides the corresponding homoallylic alcohol by sequential attacks of the hydride and 2-alkenyl moieties. A set of hydride and 2-alkenyl attacks on 1,4-diketone yields 6-heptene-1,4-diol derivative in high yield with high stereoselectivity. Selective capture of the hydride with diisopropyl ketone gives zirconocene 2-alkenyl alkoxide, which is a useful reagent for stereoselective allylation of aldehyde and imine. alpha-Halo carbonyl compounds undergo radical allylation with the zirconocene 2-alkenyl alkoxide which serves as a substitute for allyltin.
authors.affiliation: Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-Daigaku Katsura, Nishikyo, Kyoto, 615-8510, Japan.
authors.forename: Kazuya
authors.initials: K
authors.lastname: Fujita
authors.forename: Hideki
authors.initials: H
authors.lastname: Yorimitsu
authors.forename: Koichiro
authors.initials: K
authors.lastname: Oshima