Carbamate analogues of fumagillin as potent, targeted inhibitors of methionine aminopeptidase-2

J Med Chem. 2009 Dec 24;52(24):8047-56. doi: 10.1021/jm901260k.

Abstract

Inhibition of methionine aminopeptidase-2 (MetAP2) represents a novel approach to antiangiogenic therapy. We describe the synthesis and activity of fumagillin analogues that address the pharmacokinetic and safety liabilities of earlier candidates in this compound class. Two-step elaboration of fumagillol with amines yielded a diverse series of carbamates at C6 of the cyclohexane spiroepoxide. The most potent of these compounds exhibited subnanomolar inhibition of cell proliferation in HUVEC and BAEC assays. Although a range of functionalities were tolerated at this position, alpha-trisubstituted amines possessed markedly decreased inhibitory activity, and this could be rationalized by modeling based on the known fumagillin-MetAP2 crystal structure. The lead compound resulting from these studies, (3R,4S,5S,6R)-5-methoxy-4-((2R,3R)-2-methyl-3-(3-methylbut-2-enyl)oxiran-2-yl)-1-oxaspiro[2.5]octan-6-yl (R)-1-amino-3-methyl-1-oxobutan-2-ylcarbamate, (PPI-2458), demonstrated an improved pharmacokinetic profile relative to the earlier clinical candidate TNP-470, and has advanced into phase I clinical studies in non-Hodgkin's lymphoma and solid cancers.

MeSH terms

  • Amino Acids / chemistry
  • Aminopeptidases / antagonists & inhibitors*
  • Animals
  • Carbamates / chemistry*
  • Carbamates / pharmacology*
  • Cattle
  • Cell Growth Processes / drug effects
  • Cyclohexanes / chemistry*
  • Cyclohexanes / pharmacology*
  • Endothelial Cells / cytology
  • Endothelial Cells / drug effects
  • Fatty Acids, Unsaturated / chemistry*
  • Fatty Acids, Unsaturated / pharmacology*
  • Humans
  • Metalloendopeptidases / antagonists & inhibitors*
  • Models, Molecular
  • Sesquiterpenes / chemistry
  • Sesquiterpenes / pharmacology
  • Structure-Activity Relationship

Substances

  • Amino Acids
  • Carbamates
  • Cyclohexanes
  • Fatty Acids, Unsaturated
  • Sesquiterpenes
  • fumagillin
  • Aminopeptidases
  • methionine aminopeptidase 2
  • Metalloendopeptidases