Stereocontrolled synthesis and investigation of the biosynthetic transformations of 16(S),17(S)-epoxy-PDn-3 DPA

Org Biomol Chem. 2017 Oct 18;15(40):8606-8613. doi: 10.1039/c7ob02113e.

Abstract

PD1n-3 DPA is a specialized pro-resolving lipid mediator that displays potent anti-inflammatory properties and pro-resolving bioactivities. Such naturally occurring compounds are of current interest in biomolecular chemistry and drug discovery. To investigate the involvement of an epoxide intermediate in the biosynthesis of PD1n-3 DPA from n-3 docosapentaenoic acid, the epoxy acid 16(S),17(S)-epoxy-PDn-3 DPA, herein named ePDn-3 DPA, was prepared by stereoselective total synthesis. The synthetic material of ePDn-3 DPA allowed investigations of its role in the biosynthesis of PD1n-3 DPA. The obtained results establish that the biosynthesis of PD1n-3 DPA in neutrophils occurs with ePDn-3 DPA as the intermediate, and that 15-LOX produces ePDn-3 DPA from n-3 docosapentaenoic acid. Furthermore, support for the involvement of a hydrolytic enzyme in the biosynthetic conversion of ePDn-3 DPA to PD1n-3 DPA was found. In addition, ePDn-3 DPA was found to regulate the formation of the potent neutrophil chemoattractant LTB4 with equal potencies to that obtained with PD1n-3 DPA.

MeSH terms

  • Anti-Inflammatory Agents / chemistry
  • Anti-Inflammatory Agents / metabolism*
  • Anti-Inflammatory Agents / pharmacology*
  • Arachidonate 15-Lipoxygenase / metabolism
  • Epoxy Compounds / chemistry
  • Epoxy Compounds / metabolism*
  • Epoxy Compounds / pharmacology
  • Fatty Acids, Unsaturated / biosynthesis*
  • Fatty Acids, Unsaturated / chemistry
  • Fatty Acids, Unsaturated / pharmacology
  • Humans
  • Leukotriene B4 / antagonists & inhibitors
  • Leukotriene B4 / biosynthesis
  • Leukotriene B4 / chemistry
  • Molecular Structure
  • Neutrophils / chemistry
  • Neutrophils / drug effects
  • Neutrophils / metabolism
  • Stereoisomerism

Substances

  • Anti-Inflammatory Agents
  • Epoxy Compounds
  • Fatty Acids, Unsaturated
  • Leukotriene B4
  • Arachidonate 15-Lipoxygenase
  • docosapentaenoic acid