Enantioselective syntheses of various chiral multicyclic compounds with quaternary carbon stereocenters by catalytic intramolecular cycloaddition

Takanori Shibata, Yu Ki Tahara, Kohei Tamura, Kohei Endo

    Research output: Contribution to journalArticle

    40 Citations (Scopus)

    Abstract

    The intramolecular cycloaddition of 1,n-diene-ynes (n = 4-6), where alkyne and alkene moieties are connected by a 1,1-disubstituted alkene, was examined using a chiral rhodium catalyst, and various types of cycloadducts with quaternary carbon stereocenter(s) were obtained in high to excellent enantiomeric excess. In the case of 1,4-diene-ynes, tricyclic, bicyclic, and spirocyclic compounds were obtained depending upon the substituents at the 2-position of the 1,4-diene moiety and those at their alkyne termini. On the other hand, 1,5- and 1,6-diene-ynes gave tricyclic and bicyclic compounds, which included medium-sized ring systems. The mechanistic considerations for different reaction pathways and the synthetic transformation of tricyclic products into functionalized spirocyclic compounds are also described. The reaction of enediynes, where two alkyne moieties are connected by a 1,1-disubstituted alkene, was also examined, and sterically strained tricyclic compounds with two carbon stereocenters were obtained.

    Original languageEnglish
    Pages (from-to)3451-3457
    Number of pages7
    JournalJournal of the American Chemical Society
    Volume130
    Issue number11
    DOIs
    Publication statusPublished - 2008 Mar 19

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    Alkynes
    Cycloaddition
    Cycloaddition Reaction
    Alkenes
    Olefins
    Carbon
    Enediynes
    Rhodium
    Catalysts

    ASJC Scopus subject areas

    • Chemistry(all)

    Cite this

    Enantioselective syntheses of various chiral multicyclic compounds with quaternary carbon stereocenters by catalytic intramolecular cycloaddition. / Shibata, Takanori; Tahara, Yu Ki; Tamura, Kohei; Endo, Kohei.

    In: Journal of the American Chemical Society, Vol. 130, No. 11, 19.03.2008, p. 3451-3457.

    Research output: Contribution to journalArticle

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