Synthesis of vinylic iodides for incorporation into the C17-C27 fragment of bryostatins

Thomas Gregson, Eric J. Thomas*

*Corresponding author for this work

    Research output: Contribution to journalArticlepeer-review

    Abstract

    Vinylic iodides were identified as useful intermediates for the synthesis of the C17-C27 fragment of the bryostatins with control of the geometry of the exocyclic methoxycarbonylmethylene group. Following literature precedent, the Piers (E)-stereoselective addition of tributyltin hydride to an alkynoate followed by ester reduction and tin-iodine exchange gave vinylic iodides that could be used to form the C20-C21 bond of the bryostatins. Chelation controlled addition of lithiated 3-silyloxypropynes to 2-alkoxyaldehydes followed by reductive iodination was used to prepare vinylic iodides that could be used in the complementary assembly of the C21-C22 bond of the bryostatins. Initial studies of the synthesis of intermediates for metathesis studies using metal catalysed reactions of a vinylic iodide for C21-C22 bond formation were complicated by cyclisation reactions.

    Original languageEnglish
    Pages (from-to)3316-3328
    Number of pages13
    JournalTetrahedron
    Volume73
    Issue number24
    Early online date22 Apr 2017
    DOIs
    Publication statusPublished - 15 Jun 2017

    Keywords

    • Chelation control
    • Conjugate addition
    • Stereoselective synthesis
    • Tin-iodine exchange
    • Vinylic iodides

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