13C-NMR study of the ruthenium(II)-catalyzed degradation of labeled G-factor endoperoxides: proposal of a likely biogenetic pathway and evidence for CO2 release

Chem Biodivers. 2006 Mar;3(3):349-58. doi: 10.1002/cbdv.200690038.

Abstract

G-factor endoperoxides are natural products acting as phytohormones and contribute to root inhibition and frost resistance in Eucalyptus grandis and other Myrtaceae. Several (Z)- and (E)-configured cyclopentane-1,3-dione metabolites of G-factors have been found in some Eucalyptus extracts. Interestingly, these probable metabolites are identical to the products obtained by Ru(II)-catalyzed reduction of G-factors. In the present work, we, thus, studied the mechanism involved in the formation of these compounds by means of in-depth NMR distribution analysis of two differently 13C-labeled G3-factors. The observed CO2 release is underlined, and a comparison with the corresponding Fe(II)-induced degradation of G-factor endoperoxides is made. Also, the type of electron transfer proposed in the two processes is discussed and, tentatively, connected to the role of endoperoxides in plants.

MeSH terms

  • Carbon Dioxide / analysis*
  • Carbon Dioxide / pharmacokinetics
  • Carbon Isotopes
  • Catalysis
  • Magnetic Resonance Spectroscopy / methods*
  • Peroxides / analysis*
  • Peroxides / pharmacokinetics
  • Plant Growth Regulators / analysis*
  • Plant Growth Regulators / pharmacokinetics
  • Ruthenium / analysis*
  • Ruthenium / pharmacokinetics

Substances

  • Carbon Isotopes
  • Peroxides
  • Plant Growth Regulators
  • Carbon Dioxide
  • Ruthenium