Specificity of extended O-aryloxycarbonyl hydroxamates as inhibitors of a class C β-lactamase

Bioorg Med Chem. 2019 Apr 1;27(7):1430-1436. doi: 10.1016/j.bmc.2019.02.023. Epub 2019 Feb 12.

Abstract

Class C β-lactamases have previously been shown to be efficiently inactivated by O-aryloxycarbonyl hydroxamates. O-Phenoxycarbonyl-N-benzyloxycarbonylhydroxylamine (1) and O-phenoxycarbonyl-N-(R)-[(4-amino-4-carboxy-1-butyl)oxycarbonyl]hydroxylamine (2), for example, were found to be effective inactivators. The present paper describes a structure-activity study of these molecules to better define the important structural elements for high inhibitory activity. The results show that a well-positioned hydrophobic element (which may interact with the Tyr221 residue of the enzyme) and a negatively charged element, e.g. a carboxylate group (which may interact with Arg204), are required for high reactivity with the enzyme. The new compounds were found to inactivate by forming a carbonyl cross-linked enzyme (probably Ser64OCONHLys 315) as for 1 rather than the inert hydroxamoyl derivative observed with 2.

Keywords: Covalent inhibitor; Inhibition kinetics; Irreversible inhibitor; O-Aryloxycarbonyl hydroxamate; β-Lactamase inhibitor.

MeSH terms

  • Dose-Response Relationship, Drug
  • Enterobacter cloacae / enzymology
  • Hydroxamic Acids / chemical synthesis
  • Hydroxamic Acids / chemistry
  • Hydroxamic Acids / pharmacology*
  • Hydroxylamines / chemical synthesis
  • Hydroxylamines / chemistry
  • Hydroxylamines / pharmacology
  • Kinetics
  • Molecular Structure
  • Structure-Activity Relationship
  • beta-Lactamase Inhibitors / chemical synthesis
  • beta-Lactamase Inhibitors / chemistry
  • beta-Lactamase Inhibitors / pharmacology*
  • beta-Lactamases / metabolism*

Substances

  • Hydroxamic Acids
  • Hydroxylamines
  • beta-Lactamase Inhibitors
  • beta-Lactamases