ネジキLyonia ovalifolia DRUDE var. elliptica HAND.-MAZZ.の成分研究(第14報) : Diterpenoid, Lyoniol-A (Lyoniatoxin) の構造その3

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Ketolyoniol-A (II) was hydrolyzed to 7-ketolyoniol-B (III) which, on treatment with p-toluenesulfonic acid in acetone, yielded a monoisopropylidene derivative (IV). The carbonyl group in IV was reduced with lithium aluminum hydride to an alcoholic hydroxyl group as shown in formula (V). Therefore, the isopropylidene residue in IV should be attached to C-5 tertiary and C-6 secondary alcoholic oxygens to form a dioxolane ring. This result proves the presence of C-5 OH grouping in lyoniol-A (I). Lyoniol-B (VI) consumes only one mole of sodium periodate. On the basis of nuclear magnetic resonance (NMR) and mass spectral data, the oxidation product was assigned (VII), which is predicted not to consume sodium periodate. The epoxide ring of ketolyoniol-A (II) was opened with dry hydrogen chloride in ether to afford a chlorohydrin derivative (X), which was converted to a diketone (XII) by subsequent chromic acid oxidation. The positions and configuration of Cl and OH group in X have been elucidated as 2α and 3β, respectively, on the basis of infrared and NMR analyses of X, XI, and XII, and optical rotatoly dispersion measurements of IX, X, and XII. Consequently, configuration of the epoxide ring in lyoniol-A was determined as β. Further lyoniol-A furnished 2-acetoxydihydrolyoniol-B tetraacetate (XIII) with acetic anhydride and pyridine at 60-70°. Previously reported dihydrolyoniol-B triacetate (XV) has been revised to tetraacetate (XIV) on the basis of NMR study and three partially hydrolyzed products of XIV were synthesized in this connection.
公益社団法人日本薬学会の論文
1971-11-25

ネジキLyonia ovalifolia DRUDE var. elliptica HAND.-MAZZ.の成分研究(第14報) : Diterpenoid, Lyoniol-A (Lyoniatoxin) の構造その3

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ネジキLyonia ovalifolia DRUDE var. elliptica HAND.-MAZZ.の成分研究(第14報) : Diterpenoid, Lyoniol-A (Lyoniatoxin) の構造 その3

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ネジキLyonia ovalifolia DRUDE var. elliptica HAND.-MAZZ.の成分研究(第14報) : Diterpenoid, Lyoniol-A (Lyoniatoxin) の構造その3