Development of novel selective peptidomimetics containing a boronic acid moiety, targeting the 20S proteasome as anticancer agents

ChemMedChem. 2014 Aug;9(8):1801-16. doi: 10.1002/cmdc.201402075. Epub 2014 May 28.

Abstract

This paper describes the design, synthesis, and biological evaluation of peptidomimetic boronates as inhibitors of the 20S proteasome, a validated target in the treatment of multiple myeloma. The synthesized compounds showed a good inhibitory profile against the ChT-L activity of 20S proteasome. Compounds bearing a β-alanine residue at the P2 position were the most active, that is, 3-ethylphenylamino and 4-methoxyphenylamino (R)-1-{3-[4-(substituted)-2-oxopyridin-1(2H)-yl]propanamido}-3-methylbutylboronic acids (3 c and 3 d, respectively), and these derivatives showed inhibition constants (Ki ) of 17 and 20 nM, respectively. In addition, they co-inhibited post glutamyl peptide hydrolase activity (3 c, Ki=2.57 μM; 3 d, Ki=3.81 μM). No inhibition was recorded against the bovine pancreatic α-chymotrypsin, which thus confirms the selectivity towards the target enzyme. Docking studies of 3 c and related inhibitors into the yeast proteasome revealed the structural basis for specificity. The evaluation of growth inhibitory effects against 60 human tumor cell lines was performed at the US National Cancer Institute. Among the selected compounds, 3 c showed 50% growth inhibition (GI50) values at the sub-micromolar level on all cell lines.

Keywords: anticancer agents; boronates; bortezomib; docking studies; inhibitors; peptidomimetics; proteasomes.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Antineoplastic Agents / chemical synthesis
  • Antineoplastic Agents / chemistry*
  • Antineoplastic Agents / pharmacology
  • Binding Sites
  • Boronic Acids / chemical synthesis
  • Boronic Acids / chemistry*
  • Boronic Acids / pharmacology*
  • Cell Line, Tumor
  • Cell Survival / drug effects
  • Drug Screening Assays, Antitumor
  • Humans
  • Molecular Docking Simulation
  • Peptidomimetics*
  • Proteasome Endopeptidase Complex / chemistry*
  • Proteasome Endopeptidase Complex / metabolism
  • Proteasome Inhibitors / chemical synthesis
  • Proteasome Inhibitors / chemistry*
  • Proteasome Inhibitors / pharmacology
  • Protein Structure, Tertiary
  • Saccharomyces cerevisiae / enzymology
  • Substrate Specificity

Substances

  • Antineoplastic Agents
  • Boronic Acids
  • Peptidomimetics
  • Proteasome Inhibitors
  • Proteasome Endopeptidase Complex