Biosynthesis of 3-acetyldeoxynivalenol and sambucinol. Identification of the two oxygenation steps after trichodiene.
The first two oxygenation steps post-trichodiene in the biosyntheses of the trichothecenes 3-acetyldeoxynivalenol and sambucinol were investigated. The plausible intermediates 2-hydroxytrichodiene (2alpha- and 2beta-) and 12,13-epoxytrichodiene and the dioxygenated compounds 12,13-epoxy-9,10-trichoene-2-ol (2alpha- and 2beta-) were prepared specifically labeled with stable isotopes. They were then fed separately and/or together to Fusarium culmorum cultures, and the derived trichothecenes were isolated, purified, and analyzed. The stable isotopes enable easy localization of the labels in the products by 2H NMR, 13C NMR, and mass spectrometry. We found that 2alpha-hydroxytrichodiene is the first oxygenated step in the biosynthesis of both 3-acetyldeoxynivalenol and sambucinol. The stereoisomer 2beta-hydroxytrichodiene and 12,13-epoxytrichodiene are not biosynthetic intermediates and have not been isolated as metabolites. We also demonstrated that the dioxygenated 12, 13-epoxy-9,10-trichoene-2alpha-ol is a biosynthetic precursor to trichothecenes as had been suggested in a preliminary work. Its stereoisomer was not found in the pathway. A further confirmation of our results was the isolation of both oxygenated trichodiene derivatives 2alpha-hydroxytrichodiene and 12,13-epoxy-9, 10-trichoene-2alpha-ol as natural metabolites in F. culmorum cultures.
Zamir
L O
LO
Department of Chemistry, McGill University, Montreal, Québec H3Z 2K6, Canada. Lolita_Zamir@iaf.uquebec.ca
Nikolakakis
A
A
Huang
L
L
St-Pierre
P
P
Sauriol
F
F
Sparace
S
S
Mamer
O
O
D053138:Cyclohexenes; D005670:Fusarium / Q000378:metabolism; D009682:Magnetic Resonance Spectroscopy; D013058:Mass Spectrometry; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D012717:Sesquiterpenes / Q000737:chemistry*; D014255:Trichothecenes / Q000096:biosynthesis* / Q000737:chemistry
D053138:Cyclohexenes; D012717:Sesquiterpenes; D014255:Trichothecenes; C043247:3-acetyldeoxynivalenol; C012075:trichodiene; C054183:sambucinol; D010100:Oxygen