Synthetic reactions with rare taccalonolides reveal the value of C-22,23 epoxidation for microtubule stabilizing potency

J Med Chem. 2014 Jul 24;57(14):6141-9. doi: 10.1021/jm500619j. Epub 2014 Jul 2.

Abstract

The taccalonolides are microtubule stabilizers isolated from plants of the genus Tacca. Taccalonolide AF is 231 times more potent than the major metabolite taccalonolide A and differs only by the oxidation of the C-22,23 double bond in A to an epoxy group in AF. In the current study, 10 other rare natural taccalonolides were epoxidized and in each case epoxidation improved potency. The epoxidation products of taccalonolide T and AI were the most potent, with IC50 values of 0.43 and 0.88 nM, respectively. These potent taccalonolides retained microtubule stabilizing effects, and T-epoxide demonstrated antitumor effects in a xenograft model of breast cancer. Additional reactions demonstrated that reduction of the C-6 ketone resulted in an inactive taccalonolide and that C-22,23 epoxidation restored its activity. These studies confirm the value of C-22,23 epoxidation as an effective strategy for increasing the potency of a wide range of structurally diverse taccalonolide microtubule stabilizers.

Publication types

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

MeSH terms

  • Animals
  • Antineoplastic Agents, Phytogenic / chemical synthesis
  • Antineoplastic Agents, Phytogenic / chemistry
  • Antineoplastic Agents, Phytogenic / pharmacology*
  • Cell Proliferation / drug effects
  • Dioscoreaceae / chemistry
  • Dose-Response Relationship, Drug
  • Drug Screening Assays, Antitumor
  • Epoxy Compounds / chemistry
  • Epoxy Compounds / pharmacology*
  • Female
  • HeLa Cells
  • Humans
  • Mice
  • Mice, Nude
  • Microtubules / drug effects*
  • Microtubules / metabolism
  • Molecular Conformation
  • Neoplasms, Experimental / drug therapy*
  • Neoplasms, Experimental / pathology
  • Steroids / chemical synthesis*
  • Steroids / chemistry
  • Steroids / pharmacology*
  • Structure-Activity Relationship

Substances

  • Antineoplastic Agents, Phytogenic
  • Epoxy Compounds
  • Steroids
  • taccalonolide A
  • taccalonolide AF
  • taccalonolide AI
  • taccalonolide T