Development of Novel Peptide-Based Michael Acceptors Targeting Rhodesain and Falcipain-2 for the Treatment of Neglected Tropical Diseases (NTDs)

J Med Chem. 2017 Aug 24;60(16):6911-6923. doi: 10.1021/acs.jmedchem.7b00405. Epub 2017 Aug 11.

Abstract

This paper describes the development of a class of peptide-based inhibitors as novel antitrypanosomal and antimalarial agents. The inhibitors are based on a characteristic peptide sequence for the inhibition of the cysteine proteases rhodesain of Trypanosoma brucei rhodesiense and falcipain-2 of Plasmodium falciparum. We exploited the reactivity of novel unsaturated electrophilic functions such as vinyl-sulfones, -ketones, -esters, and -nitriles. The Michael acceptors inhibited both rhodesain and falcipain-2, at nanomolar and micromolar levels, respectively. In particular, the vinyl ketone 3b has emerged as a potent rhodesain inhibitor (k2nd = 67 × 106 M-1 min-1), endowed with a picomolar binding affinity (Ki = 38 pM), coupled with a single-digit micromolar activity against Trypanosoma brucei brucei (EC50 = 2.97 μM), thus being considered as a novel lead compound for the discovery of novel effective antitrypanosomal agents.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Antimalarials / chemical synthesis
  • Antimalarials / pharmacology*
  • Antimalarials / toxicity
  • Carbamates / chemical synthesis
  • Carbamates / pharmacology*
  • Carbamates / toxicity
  • Cathepsin L / metabolism
  • Cysteine Endopeptidases / metabolism*
  • Cysteine Proteinase Inhibitors / chemical synthesis
  • Cysteine Proteinase Inhibitors / pharmacology*
  • Cysteine Proteinase Inhibitors / toxicity
  • Dipeptides / chemical synthesis
  • Dipeptides / pharmacology*
  • Dipeptides / toxicity
  • HeLa Cells
  • Humans
  • Hydrogen Bonding
  • Malaria / drug therapy
  • Molecular Docking Simulation
  • Molecular Dynamics Simulation
  • Neglected Diseases / drug therapy
  • Phenylalanine / analogs & derivatives*
  • Phenylalanine / chemical synthesis
  • Phenylalanine / pharmacology
  • Phenylalanine / toxicity
  • Plasmodium falciparum / drug effects
  • Stereoisomerism
  • Structure-Activity Relationship
  • Trypanocidal Agents / chemical synthesis
  • Trypanocidal Agents / pharmacology*
  • Trypanocidal Agents / toxicity
  • Trypanosoma brucei brucei / drug effects
  • Trypanosomiasis, African / drug therapy

Substances

  • Antimalarials
  • Carbamates
  • Cysteine Proteinase Inhibitors
  • Dipeptides
  • Trypanocidal Agents
  • benzyl (1-oxo-1-((6-oxo-1-phenylhept-4-en-3-yl)amino)-3-phenylpropan-2-yl)carbamate
  • Phenylalanine
  • Cysteine Endopeptidases
  • falcipain 2
  • rhodesain
  • Cathepsin L