17924-91-3Relevant academic research and scientific papers
Early Oxidative Transformations During the Biosynthesis of Terrein and Related Natural Products
Kahlert, Lukas,Bernardi, Darlon,Hauser, Maurice,Ióca, Laura P.,Berlinck, Roberto G. S.,Skellam, Elizabeth J.,Cox, Russell J.
supporting information, p. 11895 - 11903 (2021/06/27)
The mycotoxin terrein is derived from the C10-precursor 6-hydroxymellein (6-HM) via an oxidative ring contraction. Although the corresponding biosynthetic gene cluster (BGC) has been identified, details of the enzymatic oxidative transformations are lacking. Combining heterologous expression and in vitro studies we show that the flavin-dependent monooxygenase (FMO) TerC catalyzes the initial oxidative decarboxylation of 6-HM. The reactive intermediate is further hydroxylated by the second FMO TerD to yield a highly oxygenated aromatic species, but further reconstitution of the pathway was hampered. A related BGC was identified in the marine-derived Roussoella sp. DLM33 and confirmed by heterologous expression. These studies demonstrate that the biosynthetic pathways of terrein and related (polychlorinated) congeners diverge after oxidative decarboxylation of the lactone precursor that is catalyzed by a conserved FMO and further indicate that early dehydration of the side chain is an essential step.
Zearalenone mimics: Synthesis of (E)-6-(1-Alkenyl)-substituted β-resorcylic acid esters
Mikula, Hannes,Hametner, Christian,Froehlich, Johannes
supporting information, p. 1939 - 1946 (2013/05/22)
Two versatile strategies for the synthesis of mimics of the Fusarium mycotoxin zearalenone (1) have been developed. Optimized preparation of (E)-6-(1-alkenyl) substituted β-resorcylic acid esters was realized via ortho-directed lithiation of variable substrates combined with allylation/isomerization or via formylation/Schlosser-Wittig olefination using different protective group patterns. Spontaneous decarboxylation of (E)-6-(1-alkenyl) substituted β-resorcylic acids indicated the influence of this substituent on the chemical behavior of these compounds. These mimics were already used for the development of optimized standard protocols for the synthesis of phase II metabolites of ZEN (glucosides, glucuronides), and further applications (i.e., sulfate conjugates) are still under investigation. Supplemental materials are available for this article. Go to the publisher's online edition of Synthetic Communications to view the free supplemental file.
Total Synthesis of the Mycotoxin (-)-Zearalenone based on Macrocyclisation using a Cinnamyl Radical Intermediate
Hitchcock, Stephen A.,Pattenden, Gerald
, p. 1323 - 1328 (2007/10/02)
A concise synthesis of optically active (-)-zearalenone, which uses a novel 14-endo-trig macrocyclisation from a cinnamyl radical intermediate onto an α,β-enone electrophore as a key feature, is described.
Synthesis of macrocycles via allylic radical intermediates. A total synthesis of (-)-zearalenone
Hitchcock, Stephen A.,Pattenden, Gerald
, p. 3641 - 3644 (2007/10/02)
A concise synthesis of optically active (-)-zearalenone (1) which uses a novel 14-endo trig macrocyclisation from an allylic radical intermediate (Scheme 1) as a key feature, is described.
