Formation of cyclopentenones from all‐(E) hydroperoxides of linoleic acid via allene oxides. New insight into the mechanism of cyclization
[摘要] Conversions of (Z,E)- and (E,E)-isomers of linoleic acid 13- and 9-hydroperoxides with flax and maize allene oxide synthase were studied. All-(E) but not (Z,E) hydroperoxides readily undergo cyclization via allene oxides into trans-cyclopentenones. These results suggest that double bond geometry dramatically affects the formation of pericyclic pentadienyl cation intermediate and thus the capability of 18:2-allene oxides to undergo electrocyclization into cyclopentenones.
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[效力级别] [学科分类] 生物化学/生物物理
[关键词] Linoleic acid hydroperoxide;Allene oxide synthase;Cyclization mechanism;Cyclopentenone formation;Oxylipin;LOX;lipoxygenase;AOS;allene oxide synthase;12-oxo-PDA;(15Z)-12-oxo-10;15-phytodienoic acid;13-H(P)OD;13-hydro(per)oxy-9;11-octadecadienoic acid;9-H(P)OD;9-hydro(per)oxy-10;12-octadecadienoic acid;13(S)-HPOT;(9Z;11E;13S;15Z)-13-hydroperoxy-9;11;15-octadecatrienoic acid;9(S)-HPOT(γ);(6Z;9S;10E;12Z)-9-hydroperoxy-6;10;12-octadecatrienoic acid;GC-MS;gas chromatography-mass spectrometry;SIM;selected ion monitoring;TMS;trimethylsilyl [时效性]
