Enantioselective intramolecular cyclopropanation of α-diazo-β- keto sulfones: Asymmetric synthesis of bicyclo[4.1.0]heptanes and tricyclo[4.4.0.0]decenes

Masahiro Honma, Masahisa Nakada

    Research output: Contribution to journalArticle

    54 Citations (Scopus)

    Abstract

    Catalytic asymmetric synthesis of some new chiral building blocks useful for natural product synthesis is described. The intramolecular cyclopropanation (IMCP) reaction of α-diazo-β-keto sulfones affording bicyclo[4.1.0]heptanes such as 9a-d is found to proceed with high enantioselectivity (93-98% ee). The yield is moderate due to the competing intramolecular C-H insertion reaction. As intramolecular C-H insertion reaction is not observed in the reaction of the substrates possessing a quaternary carbon at the allylic position, the reactions of 19a and 19b proceed with high enantioselectivity (95% ee) and yield. It was also found that the substrates possessing an ether group, such as 19a and 19b, could be used in this enantioselective IMCP reaction.

    Original languageEnglish
    Pages (from-to)9007-9011
    Number of pages5
    JournalTetrahedron Letters
    Volume44
    Issue number50
    DOIs
    Publication statusPublished - 2003 Dec 8

    Fingerprint

    Heptanes
    Sulfones
    Enantioselectivity
    Biological Products
    Ether
    Carbon
    Substrates

    Keywords

    • Asymmetric synthesis
    • Cyclopropanation
    • Enantioselection
    • Intramolecular reaction

    ASJC Scopus subject areas

    • Biochemistry
    • Organic Chemistry
    • Drug Discovery

    Cite this

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    title = "Enantioselective intramolecular cyclopropanation of α-diazo-β- keto sulfones: Asymmetric synthesis of bicyclo[4.1.0]heptanes and tricyclo[4.4.0.0]decenes",
    abstract = "Catalytic asymmetric synthesis of some new chiral building blocks useful for natural product synthesis is described. The intramolecular cyclopropanation (IMCP) reaction of α-diazo-β-keto sulfones affording bicyclo[4.1.0]heptanes such as 9a-d is found to proceed with high enantioselectivity (93-98{\%} ee). The yield is moderate due to the competing intramolecular C-H insertion reaction. As intramolecular C-H insertion reaction is not observed in the reaction of the substrates possessing a quaternary carbon at the allylic position, the reactions of 19a and 19b proceed with high enantioselectivity (95{\%} ee) and yield. It was also found that the substrates possessing an ether group, such as 19a and 19b, could be used in this enantioselective IMCP reaction.",
    keywords = "Asymmetric synthesis, Cyclopropanation, Enantioselection, Intramolecular reaction",
    author = "Masahiro Honma and Masahisa Nakada",
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    TY - JOUR

    T1 - Enantioselective intramolecular cyclopropanation of α-diazo-β- keto sulfones

    T2 - Asymmetric synthesis of bicyclo[4.1.0]heptanes and tricyclo[4.4.0.0]decenes

    AU - Honma, Masahiro

    AU - Nakada, Masahisa

    PY - 2003/12/8

    Y1 - 2003/12/8

    N2 - Catalytic asymmetric synthesis of some new chiral building blocks useful for natural product synthesis is described. The intramolecular cyclopropanation (IMCP) reaction of α-diazo-β-keto sulfones affording bicyclo[4.1.0]heptanes such as 9a-d is found to proceed with high enantioselectivity (93-98% ee). The yield is moderate due to the competing intramolecular C-H insertion reaction. As intramolecular C-H insertion reaction is not observed in the reaction of the substrates possessing a quaternary carbon at the allylic position, the reactions of 19a and 19b proceed with high enantioselectivity (95% ee) and yield. It was also found that the substrates possessing an ether group, such as 19a and 19b, could be used in this enantioselective IMCP reaction.

    AB - Catalytic asymmetric synthesis of some new chiral building blocks useful for natural product synthesis is described. The intramolecular cyclopropanation (IMCP) reaction of α-diazo-β-keto sulfones affording bicyclo[4.1.0]heptanes such as 9a-d is found to proceed with high enantioselectivity (93-98% ee). The yield is moderate due to the competing intramolecular C-H insertion reaction. As intramolecular C-H insertion reaction is not observed in the reaction of the substrates possessing a quaternary carbon at the allylic position, the reactions of 19a and 19b proceed with high enantioselectivity (95% ee) and yield. It was also found that the substrates possessing an ether group, such as 19a and 19b, could be used in this enantioselective IMCP reaction.

    KW - Asymmetric synthesis

    KW - Cyclopropanation

    KW - Enantioselection

    KW - Intramolecular reaction

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    U2 - 10.1016/j.tetlet.2003.09.215

    DO - 10.1016/j.tetlet.2003.09.215

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    JO - Tetrahedron Letters

    JF - Tetrahedron Letters

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