Usnic Acid Conjugates with Monoterpenoids as Potent Tyrosyl-DNA Phosphodiesterase 1 Inhibitors

J Nat Prod. 2020 Aug 28;83(8):2320-2329. doi: 10.1021/acs.jnatprod.9b01089. Epub 2020 Jul 28.

Abstract

Hybrid molecules created from different pharmacophores of natural and synthetic equivalents are successfully used in pharmaceutical practice. One promising target for anticancer therapy is tyrosyl-DNA phosphodiesterase 1 (Tdp1) because it can repair DNA lesions caused by DNA-topoisomerase 1 (Top1) inhibitors, resulting in drug resistance. In this study, new hybrid compounds were synthesized by combining the pharmacophoric moiety of a set of natural compounds with inhibitory properties against Tdp1, particularly, phenolic usnic acid and a set of different monoterpenoid fragments. These fragments were connected through a hydrazinothiazole linker. The inhibitory properties of the new compounds mainly depended on the structure of the terpenoid moieties. The two most potent compounds, 9a and 9b, were synthesized from citral and citronellal, which contain acyclic fragments with IC50 values in the range of 10-16 nM. Some synthesized derivatives showed low cytotoxicity against HeLa cells and increased the effect of the Top1 inhibitor topotecan in vitro by three to seven times. These derivatives may be considered as potential agents for the development of anticancer therapies when combined with Top1 inhibitors.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Benzofurans / chemistry*
  • Benzofurans / pharmacology
  • Crystallography, X-Ray
  • HeLa Cells
  • Humans
  • Hydrogen Bonding
  • Models, Molecular
  • Molecular Structure
  • Monoterpenes / chemistry*
  • Monoterpenes / pharmacology
  • Phosphodiesterase Inhibitors / pharmacology*
  • Phosphoric Diester Hydrolases / drug effects*
  • Spectrum Analysis / methods
  • Structure-Activity Relationship

Substances

  • Benzofurans
  • Monoterpenes
  • Phosphodiesterase Inhibitors
  • usnic acid
  • Phosphoric Diester Hydrolases
  • tyrosyl-DNA phosphodiesterase