Dramatic enhancement of reactivity of organosilicon compounds induced by complexation of bis(allyl)silanes with fluoride ion

Atsushi Shibato, Yoshifumi Itagaki, Eiji Tayama, Yasutoshi Hokke, Naoki Asao, Keiji Maruoka

    Research output: Contribution to journalArticlepeer-review

    19 Citations (Scopus)

    Abstract

    New type of fluoride ion catalyzed allylation agent (1a, 1b), allenylation agent (9, 10), and alkynylation agent (17) can be successfully utilized for various carbonyl substrates. The rate acceleration is ascribable to the shift of equilibrium to the chelate complexes with Bu4NF by the favorable chelation of bis(silyl) compounds toward the fluoride ion. The 19F NMR spectrum (ethyl trifluoroacetate as external standard) of a mixture of la and BU4NF in CDCl3 showed two peaks at δ -81.75 and -77.67 (integration ratio ~ 9:1). The large signal corresponds to the original peak of Bu4NF and the small one might be ascribed to the chelate complex [B] between 1a and Bu4NF. The fluoride ion mediated reaction of bis(crotyldimethylsilyl)methane (7) with benzaldehyde was examined and the only γ-adduct 8 was obtained regioselectively. (C) 2000 Elsevier Science Ltd.

    Original languageEnglish
    Pages (from-to)5373-5382
    Number of pages10
    JournalTetrahedron
    Volume56
    Issue number30
    DOIs
    Publication statusPublished - 2000 Jul 21

    Keywords

    • Bis(allyl)sitanes
    • Fluoride ion
    • Organosilicon compounds

    ASJC Scopus subject areas

    • Biochemistry
    • Drug Discovery
    • Organic Chemistry

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