Study On Steroidal Saponins From Ophiopogon Japonicus

The tuber of Ophiopogon japonicus is a common used herb in traditional Chinese medicine. The tuber of O. japonicus (Liliaceae) was recorded on the Chinese Pharmacopoeia (2005 Version). Chinese traditional medicine theory consides that the drug has the effects to nourish yin and promote the production of body fluid, to moisten the lung and ease the mind. Modern clinic and pharmacologic researches found that O. japonicus could have effects on enduring hypoxia, anti-arrhythmia, improving mycoardial contractive, anti-cancer, declining the blood-sugar and so on. It has been reported that steroidal saponins and homoisoflavones are the chief active ingredients. For the purpose of studying comprehensive and chemical constituents of this plant, we selected the fresh tubers of O. japonicus which were planted in Sichuan province, and carried out systematic investigation of the steroidal saponins,. The aim was to obtain variety of steroidal saponins, which were closely related to the aglycons or sugar units, so as to study the pharmacological action and structure-activity relationships.26 constituents were separated through SP825 macroporous resin, chromatography of silica gel, RP C18 silica gel, Sephadex LH-20, PTLC and PHPLC, and 24 of their structures were elucidated with physical and chemical constant, MS, 1D和2D NMR (1H-1H COSY,HSQC,HMBC,HSQC-TOCSY). There were 11 new compounds.The structures of 24 compounds were as follows:(25R)-26-O-[β-D-glucopyranosyl-(1→2)-β-D-glucopyranosyl]-3β, 22α, 26- trihydroxy-furost-5-ene-3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside(Ophiopogonin F, 1), (25R)-26-O-[β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl]-3β, 22α, 26-trihydroxy-furost-5-ene-3-O-α-L-rhamnopyrano- syl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside(Ophiopogonin G, 2), (25R)-26-O-[β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl]-3β, 14α, 17α, 22α, 26- pentahydroxy-furost-5-ene-3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside(Ophiopogonin H, 3), (25R)-26-O-β-D-glucopyranosyl-3β, 14α, 22α, 26-tetrahydroxy-furost-5-ene-3-O-α-L–rhamnopyranosyl-(1→2)-[β-D- xylopyranosyl-(1→4)]-β- D-glucopyranoside(Ophiopogonin I, 4), (25R)-26-O-[β-D -glucopyranosyl-(1→2)-β-D-glucopyranosyl]-3β, 14α, 22α, 26-tetrahydroxy-furost-5 -ene-3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyran- oside(Ophiopogonin J, 5), (25R)-26-O-[β-D-glucopyranosyl-(1→6)-β-D-glucopy- ranosyl]-3β, 14α, 17α, 22α, 26-pentahydroxy-furost-5-ene-3-O-α-L-rhamnopyranosyl -(1→2)-β-D-glucopyranoside(Ophiopogonin K , 6), (25R)-26-O-β-D-glucopyranosyl -3β, 12β, 14α, 22α, 26-pentahydroxy-furost-5-ene-3-O-α-L-rhamnopyranosyl-(1→2) -[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside(Ophiopogonin L, 7), (25R)-26-O-β-D-glucopyranosyl-3β, 12β, 14α, 17α, 22α, 26-hexahydroxy-furost-5-ene-3-O-α-L- rhamnopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside (Ophiop- ogonin M, 8), (25R)-26-O-[β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl]-3β, 14α, 22α,26-tetrahydroxy-furost-5-ene-3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-xylopyran- osyl-(1→4)]-β-D-glucopyranoside(Ophiopogonin N, 9), 24-O-β-D-glucopyranosyl -3β, 12β, 14α, 24β-tetrahydroxy-25R-spirost-5-ene-3-O-α-L-rhamnopyranosyl-(1→2) -[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside (Ophiopogonin O, 10), 25R -spirost-5-ene-3β, 14α-dihydroxy-3-O-[4′-O-acetyl-α-L-rhamnopyranosyl-(1→2)]–β-D-glucopyranoside(Ophiopogonin P, 11), 25R-spirost-5-ene-3β, 14α-dihydroxy-3- O-α-L-rhamnopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β-D-glucopyranoside(12),25R-spirost-5-ene-3-O-α-L-rhamnopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→4)]-β- D-glucopyranoside(Ophiopogonin D′, 13), 25R-spirost-5-ene-1β, 3β-dihydroxy-3-O -α-L-rhamnopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-fucopyranoside(Ophiopogonin D, 14), 25R-spirost-5-ene-3β, 14α, 17α-trihydroxy-3-O-α-L-rhamnopy ranosyl-(1→2)-β-D-glucopyranoside(15), 25R-spirost-5-ene-3β, 14α-dihydroxy-3-O -α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside(25R-Dracaenoside F, 16), 25R- spirost-5-ene-3β, 14α, 17α-trihydroxy-3-O-α-L-rhamnopyranosyl-(1→2)-[β-D- xylopyranosyl-(1→4)]-β-D-glucopyranoside(17), 25R-spirost-5-ene-3-O-β-D-xylopy ranosyl-(1→3)-[2-O-acetyl-α-L-rhamnopyranosyl-(1→2)]-β-D-glucopyranoside (18), (3β, 6α, 12β)-20-(β-D-glucopyranosyloxy)-3, 12-dihydroxydammar-24-ene-6-O-α-L- rhamnopyranosyl-(1→2)-β-D-glucopyranoside(19), (3β, 6α, 12β)-20-(β-D-glucopy ranosyloxy)-3, 12-dihydroxydammar-24-ene-6-O-β-D-glucopyranoside(20), 5, 7 -dihydroxy-6, 8-dimethyl-3-(3′, 4′-methylenedioxybenzyl)chroman-4-one (methyl- ophiopogonanone A, 21a), 5, 7-dihydroxy-6, 8-dimethyl-3-(4′-methoxybenzyl) chroman-4-one(methylophiopogonanone B, 21b), 5, 7 -dihydroxy-6, 8-dimethyl-3-(3′, 4′-methylenedioxybenzyl)chromone(methylophiopogonone A, 22), L-borneol O-β-D -apiofuranosyl(1→6)-O-β-D-glucopyranoside(23), 4-allyl-1,2-benzenediol 1-O-α- L-rhamnopyranosyl(1→6)-O-β-D-glucopyranoside(24).Compounds 1, 2, 3, 4, 5, 6, 7, 8, 9, 10 and 11 were new compounds, which their structures were steroidal saponins. The structures of 6 new compounds are the first isolation of rare furostanol saponins with two glucosyl residues at C-26 position from natural source. The structures of 13 known compounds included 7 steroidal saponins, 2 homoisoflavanones, 2 triterpenoid saponins, 1 monoterpene glycoside, 1 phenol glycoside. Compound 16 was isolated from the genus Ophiopogon for the first time. Compounds 19 and 20 were isolated from O. japonicus for the first time.