Novel 3-oxa lipoxin A4 analogues with enhanced chemical and metabolic stability have anti-inflammatory activity in vivo

J Med Chem. 2004 Apr 8;47(8):2157-65. doi: 10.1021/jm030569l.

Abstract

Lipoxin A(4) (LXA(4)) is a structurally and functionally distinct natural product called an eicosanoid, which displays immunomodulatory and anti-inflammatory activity but is rapidly metabolized to inactive catabolites in vivo. A previously described analogue of LXA(4), methyl (5R,6R,7E,9E,11Z,13E,15S)-16-(4-fluorophenoxy)-5,6,15-trihydroxy-7,9,11,13-hexadecatetraenoate (2, ATLa), was shown to have a poor pharmacokinetic profile after both oral and intravenous administration, as well as sensitivity to acid and light. The chemical stability of the corresponding E,E,E-trien-11-yne analogue, 3, was improved over 2 without loss of efficacy in the mouse air pouch model of inflammation. Careful analysis of the plasma samples from the pharmacokinetic assays for both 2 and 3 identified a previously undetected metabolite, which is consistent with metabolism by beta-oxidation. The formation of the oxidative metabolites was eliminated with the corresponding 3-oxatetraene, 4, and the 3-oxatrien-11-yne, 5, analogues of 2. Evaluation of 3-oxa analogues 4 and 5 in calcium ionophore-induced acute skin inflammation model demonstrated similar topical potency and efficacy compared to 2. The 3-oxatrien-11-yne analogue, 5, is equipotent to 2 in an animal model of inflammation but has enhanced metabolic and chemical stability and a greatly improved pharmacokinetic profile.

MeSH terms

  • Acute Disease
  • Animals
  • Anti-Inflammatory Agents, Non-Steroidal / chemical synthesis*
  • Anti-Inflammatory Agents, Non-Steroidal / metabolism
  • Anti-Inflammatory Agents, Non-Steroidal / pharmacology
  • Calcimycin
  • Dermatitis, Contact / drug therapy
  • Dermatitis, Contact / etiology
  • Drug Stability
  • Ionophores
  • Lipoxins / chemical synthesis*
  • Lipoxins / metabolism
  • Lipoxins / pharmacology
  • Male
  • Mice
  • Mice, Inbred BALB C
  • Oxidation-Reduction
  • Phenyl Ethers / chemical synthesis*
  • Phenyl Ethers / metabolism
  • Phenyl Ethers / pharmacology
  • Stereoisomerism
  • Structure-Activity Relationship

Substances

  • 16-(4-fluorophenoxy)-3-oxa-5,6,15-trihydroxy-7,9,11,13-hexadecatetraenoic acid
  • 16-(4-fluorophenoxy)-3-oxa-5,6,15-trihydroxy-7,9,13-hexadecatrien-11-ynoic acid
  • Anti-Inflammatory Agents, Non-Steroidal
  • Ionophores
  • Lipoxins
  • Phenyl Ethers
  • lipoxin A4
  • Calcimycin