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

    94 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

    Fingerprint

    Acetals
    phosphine
    Ethers
    Carbonates
    Palladium
    Lactones
    Ketones
    Aldehydes
    Esters
    Acetates
    Catalysts
    Allylation
    Nitriles
    ketene
    allyl acetate
    acetonitrile

    ASJC Scopus subject areas

    • Biochemistry
    • Organic Chemistry
    • Drug Discovery

    Cite this

    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. / Minami, Ichiro; Takahashi, Kazuhiko; Shimizu, Isao; Kimura, Tsuneo; Tsuji, Jiro.

    In: Tetrahedron, Vol. 42, No. 11, 1986, p. 2971-2977.

    Research output: Contribution to journalArticle

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    AU - Takahashi, Kazuhiko

    AU - Shimizu, Isao

    AU - Kimura, Tsuneo

    AU - Tsuji, Jiro

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