Enantioselective cyclopropanation reactions with planar-chiral pyridinium ylides

A substituent effect and a remote steric effect

Nobuhiro Kanomata, Ryo Sakaguchi, Kazuki Sekine, Satomi Yamashita, Hiroko Tanaka

    Research output: Contribution to journalArticle

    24 Citations (Scopus)

    Abstract

    Novel planar-chiral pyridinium ylides were designed, and generated in situ from the corresponding pyridinium salts with triethylamine. Ylides with a common parapyridinophane skeleton reacted efficiently with electron-deficient dicyanoalkenes, or malononitriles, to produce optically active cyclopropane derivatives with high enantioselectivity (up to 99% ee). Remote steric effects were observed on the enantioselectivities, where the R2 groups of the pyridinophane core resulted in higher ee values of the products. Density function theory (DFT) calculations are in good agreement with our experimental results: the energetically favored transition state leads to the major stereoisomer, namely the trans-cyclopropane products.

    Original languageEnglish
    Pages (from-to)2966-2978
    Number of pages13
    JournalAdvanced Synthesis and Catalysis
    Volume352
    Issue number17
    DOIs
    Publication statusPublished - 2010 Nov 22

    Fingerprint

    Enantioselectivity
    Stereoisomerism
    Probability density function
    Salts
    Derivatives
    Electrons
    cyclopropane
    dicyanmethane
    triethylamine

    Keywords

    • cyclophanes
    • cyclopropanes
    • enantioselectivity
    • heterocycles
    • planar chirality
    • ylides

    ASJC Scopus subject areas

    • Catalysis
    • Organic Chemistry

    Cite this

    Enantioselective cyclopropanation reactions with planar-chiral pyridinium ylides : A substituent effect and a remote steric effect. / Kanomata, Nobuhiro; Sakaguchi, Ryo; Sekine, Kazuki; Yamashita, Satomi; Tanaka, Hiroko.

    In: Advanced Synthesis and Catalysis, Vol. 352, No. 17, 22.11.2010, p. 2966-2978.

    Research output: Contribution to journalArticle

    Kanomata, Nobuhiro ; Sakaguchi, Ryo ; Sekine, Kazuki ; Yamashita, Satomi ; Tanaka, Hiroko. / Enantioselective cyclopropanation reactions with planar-chiral pyridinium ylides : A substituent effect and a remote steric effect. In: Advanced Synthesis and Catalysis. 2010 ; Vol. 352, No. 17. pp. 2966-2978.
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