Flexible and enantioselective access to jaspine B and biologically active chain-modified analogues thereof

Org Biomol Chem. 2010 Jul 21;8(14):3227-43. doi: 10.1039/c004218h. Epub 2010 May 24.

Abstract

Whereas the all-cis tetrahydrofuran framework of the cytotoxic anhydrophytosphingosine jaspine B is considered as a relevant pharmacophore, little is known about the influence of the aliphatic chain of this amphiphilic molecule on its activity. We developed a synthetic strategy allowing flexible introduction of various lipophilic fragments in the jaspine's skeleton. The route was validated with two distinct approaches to jaspine B. Five chain-modified analogues were also prepared. Biological evaluation of these derivatives demonstrated a good correlation between their cytotoxicity and their capacity to inhibit conversion of ceramide into sphingomyelin in melanoma cells. A series of potent and selective inhibitors of sphingomyelin production was thus identified. Furthermore, the good overall potency of an omega-aminated analogue allowed us to dissociate of the pharmacological action of jaspine B from its amphiphilic nature.

MeSH terms

  • Acetylene / chemistry
  • Aldehydes / chemistry
  • Animals
  • Antineoplastic Agents / chemical synthesis
  • Antineoplastic Agents / chemistry*
  • Antineoplastic Agents / pharmacology*
  • Cell Line, Tumor
  • Inhibitory Concentration 50
  • Mice
  • Sphingosine / analogs & derivatives*
  • Sphingosine / chemical synthesis
  • Sphingosine / chemistry
  • Sphingosine / pharmacology
  • Stereoisomerism
  • Substrate Specificity
  • Vinyl Compounds / chemistry

Substances

  • Aldehydes
  • Antineoplastic Agents
  • Vinyl Compounds
  • pachastrissamine
  • Sphingosine
  • Acetylene