Mechanistic studies on the intramolecular cyclization of O-tosyl phytosphingosines to jaspines

Nat Prod Commun. 2014 Aug;9(8):1087-90.

Abstract

A theoretical study to elucidate the mechanistic aspects involved in the tosylation-cyclization reaction of diastereomeric phytosphingosines 1a-1d to jaspines 4a-4d is presented. The stereochemistry of the starting stereoisomers is crucial for the development of weak interactions, both in the reactants and in the transition states. The analysis of the energy barriers of each elementary reaction is consistent with the observed reluctance of tosylate 2d to undergo cyclization. In addition, the initial tosylation can be identified as the limiting step in cyclizations from la and 1b.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Bridged Bicyclo Compounds, Heterocyclic / chemical synthesis*
  • Bridged Bicyclo Compounds, Heterocyclic / chemistry
  • Cyclization
  • Marine Toxins / chemical synthesis*
  • Marine Toxins / chemistry
  • Models, Molecular
  • Molecular Structure
  • Sphingosine / analogs & derivatives*
  • Sphingosine / chemistry

Substances

  • Bridged Bicyclo Compounds, Heterocyclic
  • Marine Toxins
  • phytosphingosine
  • Sphingosine