First Total Synthesis of Phytoprostanes with Prostaglandin‐Like Configuration, Evidence for Their Formation in Edible Vegetable Oils and Orienting Study of Their Biological Activity

Autor:	Emanuela Jahn, Thierry Durand, Radek Pohl, Miroslav Hájek, Camille Oger, Karel Čížek, Jean-Marie Galano, Jakub Smrček, Josef Cvačka, Ullrich Jahn, Ondřej Hodek
Rok vydání:	2021
Předmět:	Autoxidation 010405 organic chemistry Chemistry Organic Chemistry Diastereomer Enantioselective synthesis Prostaglandin Total synthesis Biological activity General Chemistry 010402 general chemistry 01 natural sciences Catalysis 0104 chemical sciences chemistry.chemical_compound Vegetable oil Tandem Mass Spectrometry Vegetables Prostaglandins Plant Oils Organic chemistry Epimer Oxidation-Reduction
Zdroj:	Chemistry – A European Journal. 27:9556-9562
ISSN:	1521-3765 0947-6539
Popis:	Phytoprostanes (PhytoP) are natural products, which form in plants under oxidative stress conditions from α-linolenic acid. However, their epimers with relative prostaglandin configuration termed phytoglandins (PhytoG) have never been detected in Nature, likely because of the lack of synthetic reference material. Here, the first asymmetric total synthesis of such compounds, namely of PhytoGF1α (9-epi-16-F1t -PhytoP) and its diastereomer ent-16-epi-PhytoGF1α (ent-9,16-diepi-16-F1t -PhytoP), has been accomplished. The synthetic strategy is based on radical anion oxidative cyclization, copper(I)-mediated alkyl-alkyl coupling and enantioselective reduction reactions. A UHPLC-MS/MS study using the synthesized compounds as standards indicates PhytoG formation at significant levels during autoxidation of α-linolenic acid in edible vegetable oils. Initial testing of synthetic PhytoGs together with F1 -PhytoP and 15-F2t -IsoP derivatives for potential interactions with the PGF2α (FP) receptor did not reveal significant activity. The notion that PUFA-derived oxidatively formed cyclic metabolites with prostaglandin configuration do not form to a significant extent in biological or food matrices has to be corrected. Strong evidence is provided that oxidatively formed PhytoG metabolites may be ingested with plant-derived food, which necessitates further investigation of their biological profile.
Databáze:	OpenAIRE
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