Formation of cyclopentenones from all-(E) hydroperoxides of linoleic acid via allene oxides. New insight into the mechanism of cyclization.
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.
Grechkin
A N
AN
Institute of Biochemistry and Biophysics, Russian Academy of Sciences, P.O. Box 30, Kazan, Russia. grechkin@sci.kcn.ru
Hamberg
M
M
D003517:Cyclopentanes / Q000737:chemistry / Q000378:metabolism*; D019597:Flax / Q000201:enzymology; D008401:Gas Chromatography-Mass Spectrometry; D019746:Intramolecular Oxidoreductases / Q000378:metabolism; D008041:Linoleic Acids / Q000737:chemistry / Q000378:metabolism*; D008956:Models, Chemical; D013237:Stereoisomerism; D003313:Zea mays / Q000201:enzymology
D003517:Cyclopentanes; D008041:Linoleic Acids; D019746:Intramolecular Oxidoreductases; C021377:hydroperoxide isomerase; C013905:cyclopentenone