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Interplay of Cascade Oxidative Cyclization and Hydride Shifts in the Synthesis of the ABC Spiroketal Ring System of Pectenotoxin-4

Authors

  • Prof. Timothy J. Donohoe,

    Corresponding author
    1. Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA (UK)
    • Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA (UK)
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  • Radosław M. Lipiński

    1. Department of Chemistry, University of Oxford, Chemistry Research Laboratory, Mansfield Road, Oxford, OX1 3TA (UK)
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  • We thank the Dulverton Trust for supporting this project and P. G. Turner, A. E. Gatland, and X. Yang for carrying out some preliminary experiments.

Abstract

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Concepts: The formation of stereochemically defined bis-THF units through a double cyclization and a hydride-shift-initiated route to spiroketals is described (see scheme; Xc=chiral auxiliary). The resulting sequence has been used in a synthesis of the C1–16 fragment of the naturally occurring antitumor agent pectenotoxin-4.

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