Pyrrolo[3,2-b]quinoxaline derivatives as types I1/2 and II Eph tyrosine kinase inhibitors: structure-based design, synthesis, and in vivo validation

J Med Chem. 2014 Aug 14;57(15):6834-44. doi: 10.1021/jm5009242. Epub 2014 Jul 30.

Abstract

The X-ray crystal structures of the catalytic domain of the EphA3 tyrosine kinase in complex with two type I inhibitors previously discovered in silico (compounds A and B) were used to design type I1/2 and II inhibitors. Chemical synthesis of about 25 derivatives culminated in the discovery of compounds 11d (type I1/2), 7b, and 7g (both of type II), which have low-nanomolar affinity for Eph kinases in vitro and a good selectivity profile on a panel of 453 human kinases (395 nonmutant). Surface plasmon resonance measurements show a very slow unbinding rate (1/115 min) for inhibitor 7m. Slow dissociation is consistent with a type II binding mode in which the hydrophobic moiety (trifluoromethyl-benzene) of the inhibitor is deeply buried in a cavity originating from the displacement of the Phe side chain of the so-called DFG motif as observed in the crystal structure of compound 7m. The inhibitor 11d displayed good in vivo efficacy in a human breast cancer xenograft.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Animals
  • Antineoplastic Agents / chemistry*
  • Antineoplastic Agents / pharmacokinetics
  • Antineoplastic Agents / pharmacology
  • Binding, Competitive
  • Cell Line, Tumor
  • Computer Simulation
  • Crystallography, X-Ray
  • Drug Design
  • Drug Screening Assays, Antitumor
  • Heterografts
  • Humans
  • Male
  • Mice, Inbred ICR
  • Mice, Nude
  • Molecular Docking Simulation
  • Neoplasm Transplantation
  • Pyrroles / chemistry*
  • Pyrroles / pharmacokinetics
  • Pyrroles / pharmacology
  • Quinoxalines / chemistry*
  • Quinoxalines / pharmacokinetics
  • Quinoxalines / pharmacology
  • Receptor, EphA3 / antagonists & inhibitors*
  • Receptor, EphA3 / chemistry
  • Receptor, EphA3 / metabolism
  • Receptor, EphB4 / antagonists & inhibitors
  • Receptor, EphB4 / chemistry
  • Receptor, EphB4 / metabolism
  • Structure-Activity Relationship
  • Thermodynamics

Substances

  • Antineoplastic Agents
  • Pyrroles
  • Quinoxalines
  • Receptor, EphA3
  • Receptor, EphB4

Associated data

  • PDB/4P4C
  • PDB/4P5Q
  • PDB/4P5Z