Mechanism of lipoxidase reaction. I. Specificity of hydroperoxidation of linoleic acid

Linoleate hydroperoxides from autoxidation of methyl linoleate and from lipoxidase oxidation of linoleic acid are compared. Data indicate an equal amount of methyl 9- and 13-hydroperoxyoctadecadienoate produced by autoxidation of methyl linoleate, and the exclusive formation of 13-hydroperoxyoctadeca-9,11-dienoic acid from the incubation of lipoxidase with linoleic acid. As a result of these findings, a specific mechanism for the reaction of lipoxidase with linoleic acid is postulated.