Structure Activity of β-Amidomethyl Vinyl Sulfones as Covalent Inhibitors of Chikungunya nsP2 Cysteine Protease with Antialphavirus Activity

J Med Chem. 2024 Sep 26;67(18):16505-16532. doi: 10.1021/acs.jmedchem.4c01346. Epub 2024 Sep 5.

Abstract

Despite their widespread impact on human health, there are no approved drugs for combating alphavirus infections. The heterocyclic β-aminomethyl vinyl sulfone RA-0002034 (1a) is a potent irreversible covalent inhibitor of the alphavirus nsP2 cysteine protease with broad-spectrum antiviral activity. Analogs of 1a that varied each of the three regions of the molecule were synthesized to establish structure-activity relationships for the inhibition of Chikungunya (CHIKV) nsP2 protease and viral replication. The vinyl sulfone covalent warhead was highly sensitive to modifications. However, alterations to the core five-membered heterocycle and aryl substituent were well tolerated. The 5-(2,5-dimethoxyphenyl)pyrazole (1o) and 4-cyanopyrazole (8d) analogs exhibited kinact/Ki ratios >9000 M-1 s-1. 3-Arylisoxazole (10) was identified as an isosteric replacement for the five-membered heterocycle, which circumvented the intramolecular cyclization of pyrazole-based inhibitors like 1a. A ligand-based model of the enzyme active site was developed to aid the design of nsP2 protease inhibitors as potential therapeutics against alphaviruses.

MeSH terms

  • Animals
  • Antiviral Agents* / chemical synthesis
  • Antiviral Agents* / chemistry
  • Antiviral Agents* / pharmacology
  • Chikungunya virus* / drug effects
  • Chikungunya virus* / enzymology
  • Cysteine Endopeptidases* / metabolism
  • Cysteine Proteinase Inhibitors / chemical synthesis
  • Cysteine Proteinase Inhibitors / chemistry
  • Cysteine Proteinase Inhibitors / pharmacology
  • Humans
  • Structure-Activity Relationship
  • Sulfones* / chemical synthesis
  • Sulfones* / chemistry
  • Sulfones* / pharmacology
  • Virus Replication / drug effects

Substances

  • Antiviral Agents
  • Sulfones
  • Cysteine Endopeptidases
  • Cysteine Proteinase Inhibitors
  • nsP2 proteinase
  • divinyl sulfone