Optimization of the efflux ratio and permeability of covalent irreversible BTK inhibitors

Bioorg Med Chem Lett. 2018 Nov 1;28(20):3307-3311. doi: 10.1016/j.bmcl.2018.09.018. Epub 2018 Sep 15.

Abstract

Bruton's tyrosine kinase (Btk) is a member of the Tec kinase family that is expressed in cells of hematopoietic lineage (e.g. B cells, macrophages, monocytes, and mast cells). Small molecule covalent irreversible Btk inhibitors targeting Cys481 within the ATP-binding pocket have been applied in the treatment of B-cell malignancies. Starting from a fragment, we discovered a novel series of potent covalent irreversible Btk inhibitors that bear N-linked groups occupying the solvent accessible pocket (SAP) of the active site of the Btk kinase domain. The hit molecules, however, displayed high P-gp mediated efflux ratio (ER) and poor A-B permeability in Caco-2 assay. By decreasing tPSA, installing steric hindrance and adjusting clogP, one top molecule 9 was discovered, which showed a 99% decrease in efflux ratio and a 90-fold increase in A-B permeability compared to hit molecule 1.

Keywords: Btk inhibitor; Efflux ratio; Steric hindrance; cLogP; tPSA.

MeSH terms

  • Adenine / analogs & derivatives
  • Agammaglobulinaemia Tyrosine Kinase / antagonists & inhibitors*
  • Agammaglobulinaemia Tyrosine Kinase / chemistry
  • Animals
  • Caco-2 Cells
  • Catalytic Domain
  • Humans
  • Mice
  • Molecular Structure
  • Niacinamide / analogs & derivatives
  • Niacinamide / chemical synthesis
  • Niacinamide / pharmacokinetics
  • Niacinamide / pharmacology*
  • Permeability
  • Piperidines
  • Protein Kinase Inhibitors / chemical synthesis
  • Protein Kinase Inhibitors / pharmacokinetics
  • Protein Kinase Inhibitors / pharmacology*
  • Pyrazoles / pharmacology
  • Pyrimidines / pharmacology

Substances

  • Piperidines
  • Protein Kinase Inhibitors
  • Pyrazoles
  • Pyrimidines
  • ibrutinib
  • Niacinamide
  • Agammaglobulinaemia Tyrosine Kinase
  • BTK protein, human
  • Adenine