Identification of intermediates in the biosynthesis of PR toxin by Penicillium roqueforti.
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.
Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn (Germany).
Ramona
R
Riclea
Kekulé-Institut für Organische Chemie und Biochemie, Rheinische Friedrich-Wilhelms-Universität Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn (Germany). dickschat@uni-bonn.de.
Jeroen S
JS
Dickschat
D053898:Biosynthetic Pathways; D009682:Magnetic Resonance Spectroscopy; D009284:Naphthols / Q000737:chemistry / Q000378:metabolism*; D010407:Penicillium / Q000737:chemistry / Q000378:metabolism*; D012717:Sesquiterpenes / Q000737:chemistry / Q000378:metabolism*
D009284:Naphthols; D012717:Sesquiterpenes; C015483:PR Toxin
NMR spectroscopy; biosynthesis; isotopic labeling; terpenoids; total synthesis