Vanadium-catalyzed transformation of 13(S)-hydroperoxy-9(Z), 11(E)-octadecadienoic acid: Structural studies on epoxy alcohols and trihydroxy acids
✍ Scribed by Mats Hamberg
- Publisher
- Elsevier Science
- Year
- 1987
- Tongue
- English
- Weight
- 643 KB
- Volume
- 43
- Category
- Article
- ISSN
- 0009-3084
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✦ Synopsis
Treatment of methyl 13(S)-hydroperoxy-9(Z),ll(E)-octadecadienoate with vanadium oxyacetylacetonate led to the formation of two diastereomeric ~,#-epoxy alcohols, i.e. methyl ll(R),12(R).epoxy-13(S)-hydroxy-9(Z)-octadecenoate and methyl ll(S),12(S)-epoxy-13(S)hydroxy-9(Z)-octadecenoate. The epoxy alcohols underwent spontaneous hydrolysis into isomeric trihydroxyesters. The first mentioned epoxy alcohol afforded methyl 9(R),12(S),13(S)and methyl 9(S),12(S),13(S)-trihydroxy-10(E)-octadecenoates as major hydrolysis products whereas the latter epoxy alcohol afforded methyl 9(R),12(R),I3(S)and methyl 9(S),12(R),-13(S)-trihydroxy-10(E)-oetadecenoates as major compounds. Smaller amounts of diastereomeric methyl ll,12,13-trihydroxy-9-octadecenoates were also formed from both epoxy alcohols. The vanadium-catalyzed conversion of 13(S)-hydroperoxy-9(Z),l l(E)-octadecadienoic acid (13(S)HPOD) (methyl ester) into a,#-epoxy alcohols and their further conversion into trihydroxy derivatives offers a model system for similar transformations of certain polyunsaturated fatty acids reeentiy described in the fungus, Saprolcgnia parasitica.