Potent noncovalent thrombin inhibitors that utilize the unique amino acid D-dicyclohexylalanine in the P3 position. Implications on oral bioavailability and antithrombotic efficacy

J Med Chem. 1997 May 23;40(11):1565-9. doi: 10.1021/jm970140s.

Abstract

In an effort to prepare orally bioavailable analogs of our previously reported thrombin inhibitor 1, we have synthesized a series of compounds that utilize the unique amino acid D-dicyclohexylalanine as a P3 ligand. The resulting compounds are extremely potent and selective thrombin inhibitors, and the N-terminal Boc derivative 8 exhibited excellent oral bioavailability and pharmacokinetics in both rats and dogs. The des-Boc analog 6 was not orally bioavailable in rats. The high level of oral bioavailability observed with 8 appears to be a direct function of its increased lipophilicity versus other close analogs. Although increased lipophilicity may serve to increase the oral absorption of tripeptide thrombin inhibitors, it also appears to have detrimental effects on the antithrombotic properties observed with the compounds. Compound 6 performed extremely well in our in vivo antithrombotic assay, while the much more lipophilic but essentially equipotent analog 8 performed poorly. We have found that in general with this series of thrombin inhibitors as well as with other unreported series, increased lipophilicity and the associated increases in plasma protein binding have detrimental effects on 2X APTT values and subsequent performance in in vivo antithrombotic models.

MeSH terms

  • Animals
  • Biological Availability
  • Dipeptides / chemical synthesis*
  • Dipeptides / pharmacokinetics
  • Dipeptides / therapeutic use
  • Dogs
  • Fibrinolytic Agents / chemical synthesis*
  • Fibrinolytic Agents / pharmacokinetics
  • Fibrinolytic Agents / therapeutic use
  • Lipid Metabolism
  • Male
  • Molecular Structure
  • Partial Thromboplastin Time
  • Phenylalanine / analogs & derivatives*
  • Phenylalanine / chemistry
  • Rats
  • Rats, Sprague-Dawley
  • Structure-Activity Relationship
  • Thrombin / antagonists & inhibitors*
  • Thrombosis / drug therapy

Substances

  • 3,3-dicyclohexylalanyl-L-proline-N-((4-aminocyclohexyl)methyl)amide
  • Dipeptides
  • Fibrinolytic Agents
  • N-((1,1-dimethylethoxy)carbonyl)-3,3-dicyclohexylalanyl-L-proline-N-((4-aminocyclohexyl)methyl)amide
  • cyclohexylalanine
  • Phenylalanine
  • Thrombin