Relative stereochemical determination and synthesis of the C17-C25 δ-lactone fragment of hemicalide

J Org Chem. 2013 Feb 1;78(3):855-64. doi: 10.1021/jo302440a. Epub 2013 Jan 23.

Abstract

Hemicalide is a novel marine metabolite polyketide distinguished by a unique mechanism of action. Because of insufficient quantities of purified material, this natural product has evaded complete stereochemical assignments. Recently, we have determined the relative stereochemistry of the C8-C13 hexad by synthesizing the C1-C13 fragment. Presently, we report the assignment of the C17-C25 δ-lactone fragment. NMR analysis of authentic hemicalide along with a computational conformation study allowed us to reduce the number of putative relative isomers from 16 to 4. Concise syntheses of the four candidate diastereomers were achieved using a common strategy based on a Dias aldehyde allylation reaction, an intramolecular Horner-Wadsworth-Emmons olefination, and a dihydroxylation reaction. Finally, thorough NMR comparisons enabled us to deduce the relative stereochemistry of the C1-C17 fragment with high certainty.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Lactones / chemical synthesis*
  • Lactones / chemistry
  • Macrolides / chemical synthesis*
  • Macrolides / chemistry
  • Magnetic Resonance Spectroscopy
  • Molecular Conformation
  • Polyketides / chemical synthesis*
  • Polyketides / chemistry
  • Stereoisomerism

Substances

  • Lactones
  • Macrolides
  • Polyketides