Palladium-catalyzed decarboxylation-allylation of allylic esters of α-substituted β-keto carboxylic, malonic, cyanoacetic, and nitroacetic acids

Jiro Tsuji, Toshiro Yamada, Ichiro Minami, Masami Yuhara, Mohammad Nisar, Isao Shimizu

    Research output: Contribution to journalArticle

    108 Citations (Scopus)

    Abstract

    Decarboxylation-allylation of allylic β-keto carboxylates using Pd(OAc)2-PPh3 or Pd2(dba)3·CHCl3-dppe as a catalyst proceeds smoothly to give α-allylated ketones. The reaction is highly regioselective. In some cases, diallylated ketones are obtained with allylic esters bearing an active proton(s). Also rhodium, molybdenum, and nickel complexes are active catalysts in this reaction. Similarly allylic esters of α-substituted malonates, cyanoacetates, and nitroacetate undergo the palladium-catalyzed decarboxylation-allylation to afford allylated acetate, acetonitrile, and nitromethane, respectively. The mechanisms of these palladium-catalyzed decarboxylation-allylations are discussed.

    Original languageEnglish
    Pages (from-to)2988-2995
    Number of pages8
    JournalJournal of Organic Chemistry
    Volume52
    Issue number14
    Publication statusPublished - 1987

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    Allylation
    Palladium
    Carboxylic Acids
    Esters
    Ketones
    Malonates
    Bearings (structural)
    Rhodium
    Catalysts
    Molybdenum
    Nickel
    Protons
    Acetates
    malonic acid
    nitroacetic acid
    Decarboxylation
    cyanoacetic acid

    ASJC Scopus subject areas

    • Organic Chemistry

    Cite this

    Palladium-catalyzed decarboxylation-allylation of allylic esters of α-substituted β-keto carboxylic, malonic, cyanoacetic, and nitroacetic acids. / Tsuji, Jiro; Yamada, Toshiro; Minami, Ichiro; Yuhara, Masami; Nisar, Mohammad; Shimizu, Isao.

    In: Journal of Organic Chemistry, Vol. 52, No. 14, 1987, p. 2988-2995.

    Research output: Contribution to journalArticle

    Tsuji, Jiro ; Yamada, Toshiro ; Minami, Ichiro ; Yuhara, Masami ; Nisar, Mohammad ; Shimizu, Isao. / Palladium-catalyzed decarboxylation-allylation of allylic esters of α-substituted β-keto carboxylic, malonic, cyanoacetic, and nitroacetic acids. In: Journal of Organic Chemistry. 1987 ; Vol. 52, No. 14. pp. 2988-2995.
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    abstract = "Decarboxylation-allylation of allylic β-keto carboxylates using Pd(OAc)2-PPh3 or Pd2(dba)3·CHCl3-dppe as a catalyst proceeds smoothly to give α-allylated ketones. The reaction is highly regioselective. In some cases, diallylated ketones are obtained with allylic esters bearing an active proton(s). Also rhodium, molybdenum, and nickel complexes are active catalysts in this reaction. Similarly allylic esters of α-substituted malonates, cyanoacetates, and nitroacetate undergo the palladium-catalyzed decarboxylation-allylation to afford allylated acetate, acetonitrile, and nitromethane, respectively. The mechanisms of these palladium-catalyzed decarboxylation-allylations are discussed.",
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    AU - Tsuji, Jiro

    AU - Yamada, Toshiro

    AU - Minami, Ichiro

    AU - Yuhara, Masami

    AU - Nisar, Mohammad

    AU - Shimizu, Isao

    PY - 1987

    Y1 - 1987

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