title: Synthesis of zearalenone-16-β,D-glucoside and zearalenone-16-sulfate: A tale of protecting resorcylic acid lactones for regiocontrolled conjugation.
abstract: The development of a reliable procedure for the synthesis of the 16-glucoside and 16-sulfate of the resorcylic acid lactone (RAL) type compound zearalenone is presented. Different protective group strategies were considered and applied to enable the preparation of glucosides and sulfates that are difficult to access up to now. Acetyl and p-methoxybenzyl protection led to undesired results and were shown to be inappropriate. Finally, triisopropylsilyl-protected zearalenone was successfully used as intermediate for the first synthesis of the corresponding mycotoxin glucoside and sulfate that are highly valuable as reference materials for further studies in the emerging field of masked mycotoxins. Furthermore, high stability was observed for aryl sulfates prepared as tetrabutylammonium salts. Overall, these findings should be applicable for the synthesis of similar RAL type and natural product conjugates.
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology (VUT), Getreidemarkt 9/163, A-1060 Vienna, Austria.
authors.forename: Hannes
authors.initials: H
authors.lastname: Mikula
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology (VUT), Getreidemarkt 9/163, A-1060 Vienna, Austria.
authors.forename: Julia
authors.initials: J
authors.lastname: Weber
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology (VUT), Getreidemarkt 9/163, A-1060 Vienna, Austria.
authors.forename: Dennis
authors.initials: D
authors.lastname: Svatunek
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology (VUT), Getreidemarkt 9/163, A-1060 Vienna, Austria.
authors.forename: Philipp
authors.initials: P
authors.lastname: Skrinjar
authors.affiliation: Department of Applied Genetics and Cell Biology, University of Natural Resources and Life Sciences, Vienna (BOKU), Konrad Lorenz Str. 24, 3430 Tulln, Austria.
authors.forename: Gerhard
authors.initials: G
authors.lastname: Adam
authors.affiliation: Center for Analytical Chemistry, Department for Agrobiotechnology (IFA-Tulln), University of Natural Resources and Life Sciences, Vienna (BOKU), Konrad Lorenz Str. 20, 3430 Tulln, Austria.
authors.forename: Rudolf
authors.initials: R
authors.lastname: Krska
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology (VUT), Getreidemarkt 9/163, A-1060 Vienna, Austria.
authors.forename: Christian
authors.initials: C
authors.lastname: Hametner
authors.affiliation: Institute of Applied Synthetic Chemistry, Vienna University of Technology (VUT), Getreidemarkt 9/163, A-1060 Vienna, Austria.
authors.forename: Johannes
authors.initials: J
authors.lastname: Fröhlich
keywords: glycosylation; masked mycotoxins; resorcylic acid esters; sulfation; zearalenone