Making epothilones fluoresce: design, synthesis, and biological characterization of a fluorescent N12-aza-epothilone (azathilone)

Chembiochem. 2009 Oct 12;10(15):2513-21. doi: 10.1002/cbic.200900376.

Abstract

A green fluorescent 12-aza-epothilone (azathilone) derivative has been prepared through the attachment of the 4-nitro-2,1,3-benzoxadiazole (NBD) fluorophore to the 12-nitrogen atom of the azamacrolide core structure. While less potent than natural epothilones or different N12-acylated azathilone derivatives, NBD-azathilone (3) promotes tubulin assembly, inhibits cancer cell proliferation in vitro and arrests the cell cycle at the G2/M transition. Most significantly, the binding of 3 to cellular microtubules (MTs) could be directly visualized by confocal fluorescence microscopy. Based on competition binding experiments with laulimalide-stabilized MTs in vitro, the N12-Boc substituted azathilone 1, Epo A, and NBD-azathilone (3) all interact with the same tubulin-binding site. Computational studies provided a structural model of the complexes between beta-tubulin and 1 or 3, respectively, in which the NBD moiety of 3 or the BOC moiety of 1 directly and specifically contribute to MT binding. Collectively, these data demonstrate that the cellular effects of 3 and, by inference, also of other azathilones are the result of their interactions with the cellular MT network.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • 4-Chloro-7-nitrobenzofurazan / analogs & derivatives*
  • 4-Chloro-7-nitrobenzofurazan / chemical synthesis
  • 4-Chloro-7-nitrobenzofurazan / chemistry
  • 4-Chloro-7-nitrobenzofurazan / metabolism
  • 4-Chloro-7-nitrobenzofurazan / pharmacology
  • Binding Sites
  • Cell Cycle / drug effects
  • Cell Line, Tumor
  • Cell Proliferation / drug effects
  • Drug Design*
  • Epothilones / chemical synthesis
  • Epothilones / chemistry*
  • Epothilones / metabolism*
  • Epothilones / pharmacology
  • Fluorescence
  • Fluorescent Dyes / chemical synthesis*
  • Fluorescent Dyes / chemistry
  • Fluorescent Dyes / metabolism*
  • Fluorescent Dyes / pharmacology
  • Humans
  • Microtubules / metabolism
  • Spectrum Analysis
  • Tubulin / metabolism

Substances

  • 10,14-dihydroxy-9,11,13,13-tetramethyl-2-(1-methyl-2-(2-methyl-thiazol-4-yl)-vinyl)-5-(7-nitro-benzo(1,2,5)oxadiazol-4-yl)-1-oxa-5-aza-cyclohexadecane-12,16-dione
  • Epothilones
  • Fluorescent Dyes
  • Tubulin
  • 4-Chloro-7-nitrobenzofurazan