Formation of cyclopentenones from all‐(E) hydroperoxides of linoleic acid via allene oxides. New insight into the mechanism of cyclization

FEBS Letters

Grechkin, Alexander N.²  Hamberg, Mats¹ 

[1] Division of Physiological Chemistry II, Department of Medical Biochemistry and Biophysics, Karolinska Institutet, Stockholm, Sweden;Institute of Biochemistry and Biophysics, Russian Academy of Sciences, P.O. Box 30, Kazan 420503, Russia

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;   

DOI  :  10.1016/S0014-5793(99)01759-7

学科分类：生物化学/生物物理

来源: John Wiley & Sons Ltd.

【 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.

【 授权许可】

Unknown