Michael acceptor in gambogic acid--Its role and application for potent antitumor agents

Bioorg Med Chem Lett. 2015 Jul 15;25(14):2844-8. doi: 10.1016/j.bmcl.2015.04.100. Epub 2015 May 11.

Abstract

Gambogic acid (GA), a natural product with unique structure, was reported to have broad antiproliferation activities against cancer cell lines. As a reactive Michael acceptor, the 10-position of GA is susceptible to nucleophiles, thus limiting its clinical application as an anticancer agent. Moreover, the 6-OH forms an intramolecular hydrogen bond with 8-CO, which can make the 9, 10 double bond more reactive to nucleophiles. In this essay, two strategies (A and B) were applied to solve the above-mentioned problems. Strategy A was to increase the steric hindrance of C-10 to reduce the activity of GA towards nucleophiles. Strategy B was to replace the hydroxyl of C-6 with other substituents based on the assumption that the intra-molecular hydrogen bond could increase the electrophilicity of C-10. Results showed the electrophilicity of C-10 disappeared as well as the antiproliferation activity against cancer cell lines by introducing a methyl group at C-10. Strategy B showed that the electrophilicity of C-10 was reduced dramatically while maintained the activity by replacement of the hydroxyl of C-6 with neutral or basic groups.

Keywords: Gambogic acid; Intramolecular hydrogen bond; Michael acceptor.

MeSH terms

  • Animals
  • Antineoplastic Agents / chemistry
  • Antineoplastic Agents / pharmacokinetics
  • Antineoplastic Agents / pharmacology
  • Cell Line, Tumor
  • Cell Proliferation / drug effects
  • Half-Life
  • Humans
  • Mice
  • Morpholines / chemistry
  • Structure-Activity Relationship
  • Xanthones / chemical synthesis
  • Xanthones / chemistry*
  • Xanthones / pharmacology*

Substances

  • Antineoplastic Agents
  • Morpholines
  • Xanthones
  • morpholine
  • gambogic acid