Total Synthesis of Discodermolide: Optimization of the Effective Synthetic Route

書誌事項

公開日
2008-12
権利情報
  • http://onlinelibrary.wiley.com/termsAndConditions#vor
DOI
  • 10.1002/chem.200801478
公開者
Wiley

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説明

<jats:title>Abstract</jats:title><jats:p>An efficient and modulable total synthesis of discodermolide (DDM), a unique marine anticancer polyketide is described including related alternative synthetic approaches. Particularly notable is the repeated application of a crotyltitanation reaction to yield homoallylic (<jats:italic>Z</jats:italic>)‐<jats:italic>O</jats:italic>‐ene‐carbamate alcohols with excellent selectivity. Advantage was taken of this reaction not only for the stereocontrolled building of the <jats:italic>syn</jats:italic>–<jats:italic>anti</jats:italic> methyl–hydroxy–methyl triads of DDM, but also for the direct construction of the terminal (<jats:italic>Z</jats:italic>)‐diene. Of particular interest is also the installation of the C13C14 (<jats:italic>Z</jats:italic>)‐double bond through a highly selective dyotropic rearrangement. The preparation of the middle C8–C14 fragment in two sequential stages and its coupling to the C1–C7 moiety was a real challenge and required careful optimization. Several synthetic routes were explored to allow high and reliable yields. Due to the flexibility and robust character of this approach, it might enable a systematic structural variation of DDM and, therefore, the elaboration and exploration of novel discodermolide structural analogues.</jats:p>

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