Optimization of Cyclic Plasmin Inhibitors: From Benzamidines to Benzylamines

J Med Chem. 2016 Jul 14;59(13):6370-86. doi: 10.1021/acs.jmedchem.6b00606. Epub 2016 Jun 17.

Abstract

New macrocyclic plasmin inhibitors based on our previously optimized P2-P3 core segment have been developed. In the first series, the P4 residue was modified, whereas the 4-amidinobenzylamide in P1 position was maintained. The originally used P4 benzylsulfonyl residue could be replaced by various sulfonyl- or urethane-like protecting groups. In the second series, the P1 benzamidine was modified and a strong potency and excellent selectivity was retained by incorporation of p-xylenediamine. Several analogues inhibit plasmin in the subnanomolar range, and their potency against related trypsin-like serine proteases including trypsin itself could be further reduced. Selected derivatives have been tested in a plasma fibrinolysis assay and are more effective than the reference inhibitor aprotinin. The crystal structure of one inhibitor was determined in complex with trypsin. The binding mode reveals a sterical clash of the inhibitor's linker segment with the 99-hairpin loop of trypsin, which is absent in plasmin.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Antifibrinolytic Agents / chemical synthesis
  • Antifibrinolytic Agents / chemistry
  • Antifibrinolytic Agents / pharmacology*
  • Benzamidines / chemical synthesis
  • Benzamidines / chemistry
  • Benzamidines / pharmacology*
  • Benzylamines / chemical synthesis
  • Benzylamines / chemistry
  • Benzylamines / pharmacology*
  • Dose-Response Relationship, Drug
  • Fibrinolysin / antagonists & inhibitors*
  • Fibrinolysin / metabolism
  • Humans
  • Models, Molecular
  • Molecular Structure
  • Structure-Activity Relationship

Substances

  • Antifibrinolytic Agents
  • Benzamidines
  • Benzylamines
  • Fibrinolysin