Experimental and Theoretical Studies on Corvol Ether Biosynthesis

Chembiochem. 2016 Jan;17(2):146-9. doi: 10.1002/cbic.201500543. Epub 2015 Dec 4.

Abstract

The biosynthesis of corvol ethers A and B, two sesquiterpenes from Kitasatospora setae, proceeds with involvement of either one 1,3- or two sequential 1,2-hydride shifts. Quantum chemical calculations revealed that the sequence of two 1,2-hydride shifts is energetically favoured. Labelling experiments were in agreement with this finding. In addition, the stereochemical course of a reprotonation step was investigated by incubation of (13)C-labelled isotopomers of farnesyl diphosphate in water and in deuterium oxide.

Keywords: NMR spectroscopy; isotopic labeling; quantum chemical calculations; reaction mechanisms; terpene biosynthesis.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Cyclohexanols / chemistry
  • Ethers / chemical synthesis*
  • Ethers / chemistry
  • Eucalyptol
  • Magnetic Resonance Spectroscopy
  • Models, Theoretical*
  • Molecular Structure
  • Monoterpenes / chemistry
  • Salvia
  • Sesquiterpenes / chemical synthesis*
  • Sesquiterpenes / chemistry

Substances

  • Cyclohexanols
  • Ethers
  • Monoterpenes
  • Sesquiterpenes
  • Eucalyptol