Stereoselective synthesis of medium-sized cyclic ethers: Application of C -glycosylation chemistry to seven- to nine-membered lactone-derived thioacetals and their sulfone counterparts

Yuto Suga, Haruhiko Fuwa, Makoto Sasaki

    Research output: Contribution to journalArticlepeer-review

    7 Citations (Scopus)

    Abstract

    Stereoselective synthesis of α,α′-substituted medium-sized cyclic ethers has been achieved by means of nucleophilic substitution of the corresponding lactone-derived thioacetals and their sulfone counterparts. Nucleophilic substitution of medium-sized lactone-derived thioacetals could be achieved efficiently either by (i) activation with NIS/TMSOTf in the presence of allyltrimethylsilane or TMSCN or by (ii) oxidation to the corresponding sulfones followed by treatment with an appropriate organometallic species such as divinylzinc or dimethyl(2-phenylethynyl)aluminum. Interestingly, the stereochemical consequence was found to be largely dependent on the local structure of substrates. In some cases, the gauche steric interaction developed in the transition state was considered to be responsible for the observed diastereoselectivity. The present method enables an efficient synthesis of a variety of α,α′-substituted seven- to nine-membered cyclic ethers from readily accessible lactone precursors.

    Original languageEnglish
    Pages (from-to)1656-1682
    Number of pages27
    JournalJournal of Organic Chemistry
    Volume79
    Issue number4
    DOIs
    Publication statusPublished - 2014 Feb 21

    ASJC Scopus subject areas

    • Organic Chemistry

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