New synthetic methods for α,β -unsaturated ketones, aldehydes, esters and lactones by the palladium-catalyzed reactions of silyl enol ethers, ketene silyl acetals, and enol acetates with allyl carbonates

Ichiro Minami, Kazuhiko Takahashi, Isao Shimizu, Tsuneo Kimura, Jiro Tsuji

    Research output: Contribution to journalArticle

    96 Citations (Scopus)

    Abstract

    Silyl enol ethers and ketene silyl acetals derived from ketones, aldehydes, esters and lactones are converted into α,β-unsaturated ketones, aldehydes, esters and lactones by treatment with allyl carbonates in high yields using the palladium-bis(diphenylphosphino)ethane (dppe) complex as catalyst. Phosphine-free palladium catalyst instead of the palladium-phosphine complex gives a higher selectivity for the preparation of cyclopentenone, cyclooctenone, dienones, α,β-unsaturated esters and lactones. As a solvent, the use of nitriles such as acetonitrile is essential. In other solvents, allylation takes place. Enol acetates derived from ketones are converted into α,β-unsaturated ketones by reaction with allyl carbonate in acetonitrile using the palladium complex and tributyltin methoxide as bimetallic catalysts.

    Original languageEnglish
    Pages (from-to)2971-2977
    Number of pages7
    JournalTetrahedron
    Volume42
    Issue number11
    DOIs
    Publication statusPublished - 1986

    ASJC Scopus subject areas

    • Biochemistry
    • Organic Chemistry
    • Drug Discovery

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