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First Total Syntheses of Novel Non‐Enzymatic Polyunsaturated Fatty Acid Metabolites and Their Identification in Edible Oils
Author(s) -
Pavlíčková Tereza,
BultelPoncé Valérie,
Guy Alexandre,
Rocher Amandine,
Reversat Guillaume,
Vigor Claire,
Durand Thierry,
Galano JeanMarie,
Jahn Ullrich,
Oger Camille
Publication year - 2020
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202002138
Subject(s) - docosapentaenoic acid , polyunsaturated fatty acid , docosahexaenoic acid , chemistry , eicosapentaenoic acid , lipid peroxidation , enzyme , biochemistry , isoprostanes , fatty acid
Oxidative stress (OS) is an in vivo process leading to free radical overproduction, which triggers polyunsaturated fatty acid (PUFA) peroxidation resulting in the formation of racemic non‐enzymatic oxygenated metabolites. As potential biomarkers of OS, their in vivo quantification is of great interest. However, since a large number of isomeric metabolites is formed in parallel, their quantification remains difficult without primary standards. Three new PUFA‐metabolites, namely 18‐F 3t ‐isoprostane (IsoP) from eicosapentaenoic acid (EPA), 20‐F 4t ‐neuroprostane (NeuroP) from docosahexaenoic acid (DHA) and 20‐F 3t ‐NeuroP from docosapentaenoic acid (DPA n‐3 ) were synthesized by two complementary synthetic strategies. The first one relied on a racemic approach to 18( RS )‐18‐F 3t ‐IsoP using an oxidative radical anion cyclization as a key step, whereas the second used an enzymatic deracemization of a bicyclo[3.3.0]octene intermediate obtained from cyclooctadiene to pursue an asymmetric synthesis. The synthesized metabolites were applied in targeted lipidomics to prove lipid peroxidation in edible oils of commercial nutraceuticals.