Identification of intermediates in the biosynthesis of PR toxin by Penicillium roqueforti

Angew Chem Int Ed Engl. 2015 Oct 5;54(41):12167-70. doi: 10.1002/anie.201506128. Epub 2015 Aug 12.

Abstract

The sesquiterpenoid 7-epi-neopetasone was synthesized via the Wieland-Miescher ketone. The compound was identical to a previously tentatively identified headspace constituent of Penicillium roqueforti. Feeding experiments with (13) C-labeled mevalonolactone isotopomers demonstrated that oxidation at C12 and an isomerization of the C11C12 to a C7C11 double bond must occur independently and not via a C7-C11-C12 allyl radical in one step. Feeding with (11,12,13-(13) C3 )-7-epi-neopetasone resulted in labelling of the PR toxin, thus establishing this compound as a newly identified pathway intermediate.

Keywords: NMR spectroscopy; biosynthesis; isotopic labeling; terpenoids; total synthesis.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Biosynthetic Pathways
  • Magnetic Resonance Spectroscopy
  • Naphthols / chemistry
  • Naphthols / metabolism*
  • Penicillium / chemistry
  • Penicillium / metabolism*
  • Sesquiterpenes / chemistry
  • Sesquiterpenes / metabolism*

Substances

  • Naphthols
  • Sesquiterpenes
  • PR Toxin