Lewis Acids: From Conventional Homogeneous to Green Homogeneous and Heterogeneous Catalysis

https://zenodo.org/record/1258617/files/article.pdf

Oxygen radical chemistry of polyunsaturated fatty acids

The biogeneration of green odour by green leaves

Recent investigations into the lipoxygenase pathway of plants

Chemistry of free radical and singlet oxidation of lipids

Treatment of isomeric methyl linoleate hydroperoxides with a Lewis acid, BF3, in anhydrous ether led to a carbon-to-oxygen rearrangement that caused cleavage into shorter-chain aldehydes. Methyl (9Z,11E)-13-hydroperoxy-9,11-octadecadienoate afforded mainly hexanal and methyl (E)-12-oxo-10-dodecenoate, whereas methyl (10E,12Z)-9-hydroperoxy-10,12-octadecadienoate cleaved into 2-nonenal and methyl 9-oxononanoate. The 2 aldehydes obtained from each hydroperoxide isomer were uncharacteristic of the complex volatile profile usually obtained by β-scission of oxy radicals derived from homolysis of the hydroperoxide group. Rather, the reaction resembled the one catalyzed by the plant enzyme, hydroperoxide lyase.

R. D. Plattner

Papers

Linoleate hydroperoxides are cleaved heterolytically into aldehydes by a Lewis acid in aprotic solvent.