Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition

Takanori Shibata, Mayu Miyoshi, Toshifumi Uchiyama, Kohei Endo, Nobuaki Miura, Kenji Monde

    Research output: Contribution to journalArticle

    20 Citations (Scopus)

    Abstract

    An enantioselective intramolecular [2+2+2] cycloaddition of 2-aminophenol-tethered triynes and diyne-nitriles proceeded using the chiral Rh catalysts, and tripodal cyclophanes and pyridinophanes with a long ansa chain (up to [16]pyridinophane) were obtained in acceptable yield with high to almost perfect ee. In the reaction of triynes, we elucidated that the oxygen atom at the alkyne terminus is essential for the excellent enantioselectivity. For the construction of cage-type molecule, the choice of rigid tether, which connects 1,6-diyne moiety with a side carbon chain having alkyne or cyano group on its terminus, was important, and 8-amino-2-naphthol moiety was also a preferable tether.

    Original languageEnglish
    Pages (from-to)2679-2686
    Number of pages8
    JournalTetrahedron
    Volume68
    Issue number12
    DOIs
    Publication statusPublished - 2012 Mar 25

    Fingerprint

    Alkynes
    Cycloaddition
    Cycloaddition Reaction
    Nitriles
    Enantioselectivity
    Carbon
    Oxygen
    Atoms
    Catalysts
    Molecules
    2-naphthol
    2-aminophenol

    Keywords

    • Cycloaddition
    • Cyclophane
    • Enantioselective
    • Planar chirality

    ASJC Scopus subject areas

    • Biochemistry
    • Organic Chemistry
    • Drug Discovery

    Cite this

    Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition. / Shibata, Takanori; Miyoshi, Mayu; Uchiyama, Toshifumi; Endo, Kohei; Miura, Nobuaki; Monde, Kenji.

    In: Tetrahedron, Vol. 68, No. 12, 25.03.2012, p. 2679-2686.

    Research output: Contribution to journalArticle

    Shibata, Takanori ; Miyoshi, Mayu ; Uchiyama, Toshifumi ; Endo, Kohei ; Miura, Nobuaki ; Monde, Kenji. / Enantioselective synthesis of tripodal cyclophanes and pyridinophanes by intramolecular [2+2+2] cycloaddition. In: Tetrahedron. 2012 ; Vol. 68, No. 12. pp. 2679-2686.
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    AU - Miyoshi, Mayu

    AU - Uchiyama, Toshifumi

    AU - Endo, Kohei

    AU - Miura, Nobuaki

    AU - Monde, Kenji

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