Technical Abstract: The main advantage of heterogeneous catalysis is that the catalyst can be easily separated from the reaction products and reused. There is, therefore, a continuing interest in the preparation of heterogenized catalysts, homogeneous catalysts that have been placed upon an insoluble support. One area of interest is the placement of transition metal complexes onto alumina (aluminum oxide) supports to promote oxidation, particularly epoxide formation. In the subsequent oxidation reactions, it is generally assumed that the alumina acts as an inert support. However, there is reason to be skeptical of this, since prior work has shown that alumina catalyzes nucleophilic addition of alcohols and amines to epoxides. In this study it is shown that the epoxide derivative of oleic acid, methyl 9,10-epoxyoctadecanoate (methyl stearate monoepoxide), is readily hydrolyzed to a diol when exposed to a commercial preparation of neutral alumina. Comparison of proton and carbon 13 NMR spectra of the diol with those of standards showed that the product was the threo isomer. Time course studies showed that the epoxide was converted to diol in 4 h. When methyl 9,10-12,13-diepoxy octadecanoate (methyl stearate diepoxide) was treated with alumina, a mixture of dihydroxytetrahydrofuran regioisomers, methyl 9(12)-oxy-10,13-dihydroxystearate and methyl 10(13)-oxy-9,12-dihydroxystearate, was obtained from the hydrolyzed epoxide. These results show that untreated alumina is an unsuitable support for epoxidation catalysts. However, conversion of fats and oils and their derivatives to polyhydroxy materials may be desirable, as these materials are suitable for several industrial applications. Accordingly, an alumina-based epoxidation may be the most efficient way to achieve the synthesis of these polyhydroxy materials.