Novel d-seco paclitaxel analogues: synthesis, biological evaluation, and model testing

J Org Chem. 2001 May 18;66(10):3321-9. doi: 10.1021/jo0015467.

Abstract

Four new D-secopaclitaxel analogues were synthesized from paclitaxel. The key step of the synthesis involved the opening of the D-ring by Jones oxidation. Two of the compounds had been predicted to be nearly as active as paclitaxel in a minireceptor model of the binding site on tubulin, but all were biologically inactive in an in vitro cytotoxic assay and a tubulin assembly assay. The biological results identify a weakness in our predictive minireceptor model and suggest a corrective remedy in which additional amino acids are needed to accommodate ligand-protein steric effects around the oxetane ring. These changes to the model lead to correct predictions of the bioactivity. Conformational analysis and dynamics simulations of the compounds showed that the 4-acetyl substituent is as important as the oxetane in determining the A ring conformation.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Antineoplastic Agents, Phytogenic / chemical synthesis*
  • Antineoplastic Agents, Phytogenic / chemistry
  • Antineoplastic Agents, Phytogenic / pharmacology
  • Binding Sites
  • Docetaxel
  • Humans
  • Models, Molecular
  • Molecular Conformation
  • Nuclear Magnetic Resonance, Biomolecular
  • Paclitaxel / analogs & derivatives*
  • Paclitaxel / chemistry
  • Paclitaxel / pharmacology*
  • Protein Binding
  • Structure-Activity Relationship
  • Taxoids*
  • Tubulin Modulators
  • Tumor Cells, Cultured / drug effects

Substances

  • Antineoplastic Agents, Phytogenic
  • Taxoids
  • Tubulin Modulators
  • Docetaxel
  • Paclitaxel