Studies on the Sapogenins of Dioscorea tokoro Mdkino. II The Structure of Tokorogenin

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(1) The correlation of tokorogenin (I) with the known steroid, 25D-5β-spirostan (IX), was established: Tokorogenin formed an acetonide (IIa), which could be tosylated and then hydrolyzed to give tokorogenin monotosylate (IVb). On treatment with alkali, IVb was led to anhydrotokorogenin (Va), which on oxidation with Py.—CrO3 and subsequent reduction with CrCl2 gave rise to an α,β-unsaturated ketone (VII). Catalytic hydrogenation of VII followed by the Huang-Minion reaction furnished 25D-5β-spirostan (IX).<BR>(2) In order to determine the configuration of the hydroxyl group at C3, IIa was oxidized with Py.—CrO3 and the product was reduced with LiAlH4 to give a mixture of IIa and XIII. Careful chromatography of the mixture revealed that the substance eluted first was XIII, while the second which eluted from the column was IIa, thus leaving only the structural possibility of 25D-5β-spirostan-1β,2β,3α-triol (I) to tokorogenin.

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