First Total Synthesis of Phytoprostanes with Prostaglandin‐Like Configuration, Evidence for Their Formation in Edible Vegetable Oils and Orienting Study of Their Biological Activity - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Chemistry - A European Journal Année : 2021

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

Résumé

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 PhytoGF 1α (9‐ epi ‐16‐F 1t ‐PhytoP) and its diastereomer ent ‐16‐ epi ‐PhytoGF 1α ( ent ‐9,16‐ diepi ‐16‐F 1t ‐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 F 1 ‐PhytoP and 15‐F 2t ‐IsoP derivatives for potential interactions with the PGF 2α (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.

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Chimie
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Dates et versions

hal-04611944 , version 1 (14-06-2024)

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Jakub Smrček, Miroslav Hájek, Ondřej Hodek, Karel Čížek, Radek Pohl, et al.. First Total Synthesis of Phytoprostanes with Prostaglandin‐Like Configuration, Evidence for Their Formation in Edible Vegetable Oils and Orienting Study of Their Biological Activity. Chemistry - A European Journal, 2021, 27 (37), pp.9556-9562. ⟨10.1002/chem.202100872⟩. ⟨hal-04611944⟩
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