Modular Assembly of Allosteric MEK Inhibitor Structural Elements Unravels Potency and Feedback-Modulation Handles

ChemMedChem. 2015 Dec;10(12):2004-13. doi: 10.1002/cmdc.201500442. Epub 2015 Nov 6.

Abstract

Having recently identified a so-far unexplored area adjacent to the known binding site of allosteric mitogen-activated protein kinase kinase (MEK) inhibitors, we now report an extension of these studies by combining our new side chains with different MEK inhibitor cores in a modular manner. Replacement of the amide headgroup with inverse sulfonamides resulted in the identification of new MEK inhibitors with at least 10-fold higher cellular potency against K-Ras-mutated tumor cells. A selected inhibitor from this new series retained the favorable pharmacokinetic profile of its predecessor in rodent and non-rodent species and displayed significant in vivo efficacy at once-daily oral doses of 0.25-1 mg kg(-1) in a K-Ras-mutated xenograft model. The brain penetration potential of this analogue was significantly attenuated relative to PD325901. In a second series, the central fluorophenyl core was replaced by a pyridine moiety which gave rise to a similar boost in cellular potency. Most notably, analogues from this second series do not show MEK feedback phosphorylation in K-Ras-mutated A549 cells. Our results complement recent reports on the structural intricacies of MEK-Raf feedback interactions.

Keywords: MEK; feedback activation; inhibitors; kinases; oncology; structure-based drug design.

MeSH terms

  • Allosteric Regulation
  • Animals
  • Benzamides / chemistry
  • Benzamides / metabolism
  • Benzamides / pharmacology
  • Brain / metabolism
  • Cell Line, Tumor
  • Cell Survival / drug effects
  • Diphenylamine / analogs & derivatives
  • Diphenylamine / chemistry
  • Diphenylamine / metabolism
  • Diphenylamine / pharmacology
  • Female
  • Half-Life
  • Humans
  • MAP Kinase Kinase 1 / antagonists & inhibitors*
  • MAP Kinase Kinase 1 / metabolism
  • Mice
  • Mice, Nude
  • Neoplasms / drug therapy
  • Neoplasms / pathology
  • Phosphorylation / drug effects
  • Protein Kinase Inhibitors / chemistry*
  • Protein Kinase Inhibitors / pharmacokinetics
  • Protein Kinase Inhibitors / pharmacology
  • Rats
  • Signal Transduction / drug effects
  • Structure-Activity Relationship
  • Sulfonamides / chemistry
  • Sulfonamides / pharmacology
  • Sulfonamides / therapeutic use
  • Transplantation, Heterologous

Substances

  • Benzamides
  • Protein Kinase Inhibitors
  • Sulfonamides
  • mirdametinib
  • Diphenylamine
  • MAP Kinase Kinase 1