A suite of novel allenes from Australian melolonthine scarab beetles. Structure, synthesis, and stereochemistry

J Org Chem. 2003 May 16;68(10):3739-48. doi: 10.1021/jo026213j.

Abstract

A suite of allenic hydrocarbons, previously unknown as a molecular class from insects, has been characterized from several Australian melolonthine scarab beetles. The allenes are represented by the formula CH(3)(CH(2))(n)()CH=*=CH(CH(2))(7)CH(3) with n being 11-15, 17 and 19, and thus, all have Delta(9,10)-unsaturation. These structures have been confirmed by syntheses and comparisons of spectral and chromatographic properties with those of the natural components. The enantiomers of (+/-)-Delta(9.10)-tricosadiene and Delta(9,10)-pentacosadiene were separable on a modified beta-cyclodextrin column (gas chromatography), and the natural Delta(9,10)-tricosadiene (n = 11) and Delta(9,10)-pentacosadiene (n = 13) were shown to be of >85% ee. Syntheses of nonracemic allenes of known predominating chirality were acquired using both organotin chemistry and sulfonylhydrazine intermediates, and comparisons then demonstrated that the natural allenes were predominantly (R)-configured.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes* / chemical synthesis
  • Alkenes* / chemistry
  • Alkenes* / isolation & purification
  • Animals
  • Australia
  • Chromatography, Gas
  • Coleoptera / chemistry*
  • Indicators and Reagents
  • Molecular Structure
  • Nuclear Magnetic Resonance, Biomolecular
  • Pheromones / chemistry
  • Stereoisomerism

Substances

  • Alkenes
  • Indicators and Reagents
  • Pheromones