Design and Synthesis of Highly Selective Brain Penetrant p38α Mitogen-Activated Protein Kinase Inhibitors

J Med Chem. 2022 Jan 27;65(2):1225-1242. doi: 10.1021/acs.jmedchem.0c01773. Epub 2021 May 11.

Abstract

Stress-induced p38α mitogen-activated protein (MAP) kinase activation modulates cytokine overproduction and is associated with neuroinflammation and neurodegeneration. As a potential therapeutic approach, novel Skepinone-based p38α MAP kinase inhibitors were optimized to cross the blood-brain barrier via either amino acid transporters or hydrophobic diffusion. To enhance absorption from the oral route, we used methyl ester prodrugs of the active carboxy analogs. Of these, 3-(8-((2,4-difluorophenyl)amino)-5-oxo-10,11-dihydro-5H-dibenzo[a,d][7]annulene-3-carboxamido)propanoic acid (43; p38α, IC50 = 5.5 nM) and 4-(8-((2,4-difluorophenyl)amino)-5-oxo-10,11-dihydro-5H-dibenzo[a,d][7]annulene-3-carboxamido)butanoic acid (44; p38α, IC50 = 12 nM) had brain-to-plasma ratios of 1.4 and 4.4, respectively. Compound 70, 3-(8-((2-aminophenyl)amino)-5-oxo-10,11-dihydro-5H-dibenzo[a,d][7]annulene-3-carboxamido)propanoic acid (p38α, IC50 = 1.0 nM), the Skepinone-N counterpart of 43, was most present in the mouse brain (brain-to-plasma ratio of 4.7; 0.4 mg/kg p.o., 2 h, 580 nmol/kg). Compounds 43, 44, and 70 were p38α-MAP-kinase-selective, metabolically stable, hERG nonbinding, and able to modulate IL-6 and TNF-α production in cell-based assays.

Trial registration: ClinicalTrials.gov NCT02423200 NCT02423122 NCT03402659 NCT03435861 NCT03980938.

MeSH terms

  • Animals
  • Brain / drug effects
  • Brain / metabolism*
  • Drug Design*
  • Female
  • Interleukin-6 / metabolism
  • Male
  • Mice
  • Mice, Inbred BALB C
  • Mice, Inbred C57BL
  • Molecular Docking Simulation*
  • Molecular Structure
  • Oncogene Proteins / metabolism
  • Protein Kinase Inhibitors / chemical synthesis*
  • Protein Kinase Inhibitors / pharmacology*
  • Pyrimidines / chemistry*
  • Transcriptional Regulator ERG / metabolism
  • Tumor Necrosis Factor-alpha / metabolism
  • p38 Mitogen-Activated Protein Kinases / antagonists & inhibitors*

Substances

  • ERG protein, mouse
  • Interleukin-6
  • Oncogene Proteins
  • Protein Kinase Inhibitors
  • Pyrimidines
  • Transcriptional Regulator ERG
  • Tumor Necrosis Factor-alpha
  • p38 Mitogen-Activated Protein Kinases

Associated data

  • ClinicalTrials.gov/NCT02423200
  • ClinicalTrials.gov/NCT02423122
  • ClinicalTrials.gov/NCT03402659
  • ClinicalTrials.gov/NCT03435861
  • ClinicalTrials.gov/NCT03980938