title: Stereoselective Luche reduction of deoxynivalenol and three of its acetylated derivatives at C8.
abstract: The trichothecene mycotoxin deoxynivalenol (DON) is a well known and common contaminant in food and feed. Acetylated derivatives and other biosynthetic precursors can occur together with the main toxin. A key biosynthetic step towards DON involves an oxidation of the 8-OH group of 7,8-dihydroxycalonectrin. Since analytical standards for the intermediates are not available and these intermediates are therefore rarely studied, we aimed for a synthetic method to invert this reaction, making a series of calonectrin-derived precursors accessible. We did this by developing an efficient protocol for stereoselective Luche reduction at C8. This method was used to access 3,7,8,15-tetrahydroxyscirpene, 3-deacetyl-7,8-dihydroxycalonectrin, 15-deacetyl-7,8-dihydroxycalonectrin and 7,8-dihydroxycalonectrin, which were characterized using several NMR techniques. Beside the development of a method which could basically be used for all type B trichothecenes, we opened a synthetic route towards different acetylated calonectrins.
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, Vienna 1060, Austria. philipp.fruhmann@tuwien.ac.at.
authors.forename: Philipp
authors.initials: P
authors.lastname: Fruhmann
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, Vienna 1060, Austria. christian.hametner@tuwien.ac.at.
authors.forename: Christian
authors.initials: C
authors.lastname: Hametner
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, Vienna 1060, Austria. hannes.mikula@tuwien.ac.at.
authors.forename: Hannes
authors.initials: H
authors.lastname: Mikula
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, Vienna 1060, Austria. gerhard.adam@boku.ac.at.
authors.forename: Gerhard
authors.initials: G
authors.lastname: Adam
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, Vienna 1060, Austria. rudolf.krska@boku.ac.at.
authors.forename: Rudolf
authors.initials: R
authors.lastname: Krska
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9, Vienna 1060, Austria. johannes.froehlich@tuwien.ac.at.
authors.forename: Johannes
authors.initials: J
authors.lastname: Fröhlich
mesh_terms: D000107:Acetylation; D002855:Chromatography, Thin Layer; D009682:Magnetic Resonance Spectroscopy; D013329:Structure-Activity Relationship; D014255:Trichothecenes / Q000138:chemical synthesis* / Q000737:chemistry*
chemical_list: D014255:Trichothecenes; C007262:deoxynivalenol