Reactivity of the Vinylogous Epoxyketone Moiety
The lipid peroxidation process produces lipid hydroperoxides which decompose to a variety of secondary lipid peroxidation products such as epoxides, aldehydes, and ketones. A vinylogous epoxyketone, 5,6-epoxy-3-nonen-2-one was chosen as a model of one lipid oxidation product. The synthesis and characterization of the model are presented. The reactivity of the model was predicted from molecular orbital calculations and the hard and soft acid base (HSAB) theory. These results are compared to experimental results obtained from adding various nucleophiles. A hard nucleophile, phenyl lithium, was shown to add according to predications based on the HSAB theory. The reactivity of a soft nucleophile, the enolate of diethyl malonate, was not explained by the HSAB theory but by other factors such as ring strain and steric hindrance of the epoxide ring.
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