A new triterpenoid saponin from Ardisia crenata.

A new triterpenoid saponin, ardicrenin (1), isolated from the roots of Ardisia crenata Sims was established as cyclamiretin A-3-O-[alpha-L-rhamnopyranosyl-(1----4)-beta-D-glucopyranosyl-(1----4)][ beta-D-glucopyranosyl-(1----2)]-alpha-L-arabinopyranoside. A partially hydrolyzed saponin (3) was characterized as cyclamiretin A-3-O-beta-D-glucopyranosyl-(1----2)-alpha-L-arabinopyranoside .     

Two new triterpenoid saponins from Ardisia crenata

Two new triterpenoid saponins, ardisicrenoside K (1) and ardisicrenoside L (2), have been isolated from the roots of Ardisia crenata Sims. Their structures have been determined as 3beta-O-[alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-glucopyranosyl-(1 --> 2)]-alpha-L-arabinopyranosyl]-13beta,28-epoxy-16-oxo-30,30-dimethoxyoleanane and 3beta-O-[beta-D-xylopyranosyl-(1 --> 2)-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-glucopyranosyl-(1 --> 2)]-alpha-L-arabinopyranosyl]-13beta,28-epoxy-16alpha,20-dihydroxyoleanane by means of chemical evidences and spectral analysis. Their weak anti-fungal activity against the plant pathogenic fungus Pyricularia oryzae was evaluated in vitro.     

A triterpene saponin from Lysimachia thyrsiflora L

A triterpene saponoside (LTS-4) isolated from the underground parts of Lysimachia thyrsiflora L. was defined as 3-O-{beta-D-xylopyranosyl-(1 --> 2)-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-glucopyranosyl-(1 --> 2)]-alpha-L-arabinopyranosyl}-cyclamiretin A. Structure assignment was performed on the basis of spectroscopic data including homo- and heteronuclear 1D and 2D NMR (COSY, TOCSY, NOESY, HETCOR, HMBC and DEPT) and FAB-MS studies. The compound was tested in vitro for antimicrobial and cytotoxic activity.     

PTP1B inhibitors from Ardisia japonica

In bioassay-directed isolation from the whole plant of Ardisia japonica, sixteen known compounds: chrysophanol (1), physcion (2), oleanolic acid (3), euscaphic acid (4), tormentic acid (5), quercetin (6), quercitrin (7), myricitrin (8), kaempferol 3-O-alpha-L-rhamnopyranoside (9), cyclamiretin A 3-O-alpha--rhamnopyranosyl(1-->4)-beta-D-glucopyranosyl(1-->2)-[beta-D-glucopyranosyl(1-->4)]-alpha-L-arabinopyranoside (10), (7E)-9-hydroxymegastigma-4, 7-dien-3-on-9-O-beta-D-glucopyranoside (11), bergenin (12), norbergenin (13), rutin (14), kaempferol 3,7-O-alpha-L-dirhamnopyranoside (15), (-)-epigallacatechin 3-O-gallate (16) were obtained. Compounds 1-5, 9, 11 and 14-16 have not been reported previously from this plant. Among these isolates, 2, 3, 6 and 12 showed moderate bioactivity against PTP1B in vitro with IC50 values of 121.50, 23.90, 28.12 and 157 microM, respectively.     

Chemical constituents of the rhizomes of Coeloglossum viride var. bracteatum

Seven new compounds, named coelovirins A-G (1-7), along with fourteen known constituents were isolated from the rhizomes of Coeloglossom viride var. bracteatum (Orchidaceae). On the basis of chemical and spectroscopic methods, including 2D-NMR techniques, the structures of new compounds were elucidated as 1-(4-beta-D-glucopyranosyloxybenzyl)-(2R,3S)-2-isobutyltartrate (1), 4-(4-beta-glucopyranosyloxybenzyl)-(2R,3S)-2-isobutyltartrate (2), 1-(4-beta-D-glucopyranosyloxybenzyl)-(2R,3S)-2-beta-D-glucopyranosyl-2-isobutyltartrate (3), 4-(4-beta-D-glucopyranosyloxybenzyl)-(2R,3S)-2-beta-D-glucopyranosyl-2-isobutyltartrate (4), (2R,3S)-2-beta-D-glucopyranosyl-2-isobutyltartaric acid (5), bis(4-beta-D-glucopyranosyloxybenzyl)-(2R,3S)-2-[beta-D-glucopyranosyl-(1 --> 4)-beta-D-glucopyranosyl]-2-isobutyltartrate (6) and bis(4-beta-D-glucopyranosyloxybenzyl)-(2R)-2-[beta-D-glucopyranosyl-(1 --> 4)-beta-D-glucopyranosyl]-2-isobutylmalate (7). The known compounds are 4-hydroxybenzaldehyde, 4-hydroxybenzyl alcohol, 4,4'-dihydroxydibenzyl ether, 4,4'-dihydroxydiphenylmethane, 4-(4-hydroxybenzyloxy)benzyl alcohol, gastrodin, quercetin-3,7-diglucoside, thymidine, loroglossin, militarine, dactylorhin A, dactylorhin B, beta-sitosterol and daucosterol.     

Isolation and structure elucidation of further new saponins from Solidago canadensis]

Four new main saponins (canadensis-saponins 5-8) (compounds 5-8) were isolated from Solidago canadensis L. (Asteraceae). Using GC/MS, FAB-MS, and mainly 2D-NMR techniques their structures were identified as 3-O-[beta-D-glucopyranosyl(1----3)-beta-D- glucopyranosyl]-28-O-[beta-D-galactopyranosyl(1----2)-alpha-L- rhamnopyranosyl-(1----3)-beta-D-xylopyranosyl-(1----4)-[beta-D- xylopyranosyl-(1----3)]-alpha-L-rhamnopyranosyl-(1----2)-[beta-D-apio -D- furanosyl-(1----3)]-beta-D-6-deoxyglucopyranosyl-(1----)]-bayog enin(5),3-O- [beta-D-glucopyranosyl-(1----3)-beta-D-glucopyranosyl]-28-O-[beta-D- galactopyranosyl-(1----2)-alpha-L-rhamnopyranosyl-(1----3)-beta-D- xylopyranosyl-(1----4)-[beta-D-xylopyranosyl-(1----3)]-alpha-L- rhamnopyranosyl-(1----2)-[beta-D-apio-D-furanosyl-(1----3)]- arabinopyranosyl-(1----)]bayogenin(6),3-O-[beta-D-glucopy ran osyl-(1----3)- beta-D-glucopyranosyl]-28-O-[beta-D-galactopyranosyl-(1----2)- alpha-L-rhamnopyranosyl-(1----3)-beta-D-xylopyranosyl-(1----4)-[beta-D- xylopyranosyl-(1----3)]-alpha-L-rhamnopyranosyl-(1----2)-[alpha-L- rhamnopyranosyl-(1----3)]-beta-D-6-deoxyglucopyranosyl-(1----)]-++ +bayogenin (7), and 3-O-[beta-D-glucopyranosyl-(1----3)-beta-D-glucopyranosyl]-28-[O- beta-D-galactopyranosyl-(1----2)-alpha-L-rhamnopyranosyl-(1----3)-beta-D - xylopyranosyl-(1----4)-[beta-D-xylopyranosyl-(1----3)]-alpha-L- rhamnopyranosyl-(1----2)-[alpha-L-rhamnopyranosyl-(1----3)]arabinopyr anosyl - (1----)[-bayogenin (8).     

Saponins from Thinouia coriacea]

The investigation of the stems of Thinouia coriacea Britton (Sapindaceae), an ichthyotoxic plant from South Brazil, afforded eight glycosides of oleanolic acid. Structures were assigned based on data from partial hydrolysis. 13C-NMR and mass spectral procedures as 3-O-alpha-L-arabinopyranoside (1), 3-O-alpha-L-rhamnopyranosyl-(1----2)-alpha-L-arabinopyranoside+ ++ (2), 3-O-beta-D-glucopyranosyl-(1----4)-alpha-L-arabinopyranoside (3), 3-O-beta-D-glucopyranosyl-(1----3)-alpha-L-rhamnopyranosyl-(1----2 )-alpha-L-arabinopyranoside (4), 3-O-alpha-L-rhamnopyranosyl-(1----2)[beta-D-glucopyranosyl-(1----4 )]-alpha-L-arabinopyranoside (5), 3-O-beta-D-xylopyranosyl-(1----3)-alpha-L-rhamnopyranosyl-(1----2) [beta-D-glucopyranosyl-(1----4)[alpha-L-arabinopyranoside (6), 3-O-beta-D-glucopyranosyl-(1----3)-alpha-L-rhamnopyranosyl-(1----2 )[beta-D-glucopyranosyl-(1----4)]-alpha-L-arabinopyranoside (8). Saponin 7 showed the same sugars as 8, but the attachment between the sugars could not be elucidated. The same saponins were present in the roots, but not in the leaves.     

Three new C-flavonoids from Corallodiscus flabellata

Three new C-glycosylflavones, named 5,7,4'-trihydroxy-6-methoxy-8-C-[beta-D-xylopyranosyl- (1 --> 2)]-beta-D-glucopyranosyl flavonoside (1), 5,7,4'-trihydroxy-8-methoxy-6-C-[beta-D-xylopyranosyl-(1 --> 2)]-beta-D-glucopyranosyl flavonoside (2), and 5,3',4'-trihydroxy-7,8-dimethoxy-6-C-[beta-D-xylopyranosyl-(1 --> 2)]-beta-D-glucopyranosyl flavonoside (3), along with two known compounds 5,4'-dihydroxy-7-methoxy-6-C-glucopyranosyl-flavonoside (4), 3-methoxy-4-hydroxymethyl benzoate (5) were isolated from 70% acetone extract of Corallodiscus flabellata. Their structures were identified on the basis of spectroscopic techniques and chemical methods.     

Isolation and identification of antioxidants from Sophora japonica

A new flavonol triglycoside, kaempferol 3-O-alpha-L-rhamnopyranosyl-(1 --> 6)-beta-D-glucopyranosyl-(1 --> 2)-beta-D-glucopyranoside (1), as well as two known kaempferol 3-O-[alpha-L-rhamnopyranosyl-(1 --> 6)]-[beta-D-glucopyranosyl-(1 --> 2)]-beta-D-glucopyranoside (2) and kaempferol 3-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-glucopyranoside-7-O-alpha-L-rhamnopyranoside (3), were isolated from the n-BuOH extract of the pericarps of Sophora japonica by bioassay-guided fractionation. The structure of compound 1 was established by UV, IR, MS, and one- and two-dimensional NMR spectroscopy, including DEPT, NOESY, DQF-COSY, TOCSY, HMQC, and HMBC experiments. Compounds 1-3 showed antioxidative activity in DPPH and cytochrome-c assay using HL-60 cell system.     

Two new phenylpropanoid glycosides from the stem bark of<Emphasis Type="Italic">Acanthopanax trifoliatus</Emphasis>

Two new phenylpropanoid glycosides, 1-beta-D-glucopyranosyl-2,6-dimethoxy-4-propenylphenol (1) and 1-[beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl]-2,6-dimethoxy-4-propenylphenol (2) were isolated from the stem bark of Acanthopanax trifoliatus along with four known compounds (3-6). Their structures were established on the basis of spectral and chemical evidences.     

薤中抗凝和抗癌活性成分的结构鉴定

从百合科葱属植物薤(Alium chinense)鳞茎的抗凝和抗癌活性部位中,分离得到了6个化合物。经过化学方法和光谱分析(IR,EI-MS,¹HNMR,¹³HNMR,¹H-¹HCOSY,HMBC,HMQC和NOESY谱),鉴定它们的结构分别为(25R,S)-5α-spirostane-3β-ol 3-O-｛β-D-glucopyranosyl-(1→2)-[β-D-glucopyra-nosyl-(1→3)]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside｝(1),(25R,S)-5α-spirostane-3β-ol 3-O-｛β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→3)](6-acetyl-β-D-glucopyranosyl)-(1→4)-β-D-galac-topyranoside｝(2),(25R,S)-5α-spirostane-2α,3β-diol3-O-｛β-D-glucopyranosyl-(1→2)-O-β-D-glucopyra-nosyl-(1→4)-β-D-galactopyranoside｝(3),(25S)-24-O-β-D-glucopyranosyl 3β,24β-dihydroxy-5α-spirost-3-O-α-arabinopyranosyl-(1→6)-β-D-glucopyranoside(4),chinenosideI(5)及2,3,4,9-tetrahydro-1-methyl-1H-pyrido[3,4-b]indole-3-carboxylicacid(6)。化合物4为一新的甾体皂甙,命名为chinenosideVI。化合物1～3为3对甾体皂甙差向异构体。其中,化合物2的25S型异构体为首次报道;25R型异构体和化合物6为首次从本种植物中分得。此外,通过NOESY谱还首次确定了化合物6的相对构型,并对其C和H信号进行了确切归属。     

Pregnane glycosides from Solanum nigrum

Two new pregnane saponins, solanigroside A (1) and solanigroside B (2), along with two known compounds (3 and 4), were isolated from 60% ethanolic extract of the dried herb of Solanum nigrum L. The structures of 1 and 2 were elucidated as 5alpha-pregn-16-en-3beta-ol-20-one 3-O-beta-D-xylopyranosyl-(1 --> 3)-O-[alpha-L-arabinopyranosyl-(1 --> 2)]-O-beta-D-glucopyranosyl-(1 --> 4)-O-[alpha-L-rhamnopyranosyl-(1 --> 2)]-O-beta-D-galactopyranoside (1) and 5alpha-pregn-16-en-3beta-ol-20-one 3-O-beta-D-glucopyranosyl-(1 --> 2)-O-[beta-D-glucopyranosyl-(1 --> 3)]-O-beta-D-glucopyranosyl-(1 --> 4)-O-beta-D-galactopyranoside (2), respectively, on the basis of extensive spectroscopic analysis as well as comparison with reported spectroscopic data of related compounds. This paper deals with the isolation and structural characterisation of pregnane glycosides from S. nigrum L.     

Four new oleanane type saponins from Morina nepalensis var. alba

Four new oleanane type saponins, monepalosides G-J (1-4), were isolated from the water-soluble part of the whole plant of Morina nepalensis var. alba Hand-Mazz. On the basis of chemical and spectroscopic evidence, their structures were determined as 3-O-alpha-L-arabinopyranosyl-(1 --> 3)-alpha-L-arabinopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranoside (monepaloside G, 1), 3-O-alpha-L-arabinopyranosyl-(1 --> 3)-beta-D-xylopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranoside (monepaloside H, 2), 3-O-alpha-L-arabinopyranosyl-(1 --> 3)-[beta-D-glucopyranosyl-(1 --> 2)]-alpha-L-arabinopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranoside (monepaloside I, 3), 3-O-beta-D-glucopyranosyl-(1 --> 4)-beta-D-glucopyranosyl-(1 --> 3)]-alpha-L-arabinopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranoside (monepaloside J, 4), respectively. Two-dimensional NMR spectra, including H-H COSY, HMQC, 2D HMQC-TOCSY, HMBC and ROESY were utilized in the structure elucidation and complete assignments of 1H and 13C NMR spectra.     

Two new isoflavone glycosides from Pueraria lobata

Two new isoflavone diglycosides, formononetin 8-C-[beta-D-apiofuranosyl-(1 --> 6)]-beta-D-glucopyranoside (1) and formononetin 8-C-[beta-D-xylopyranosyl-(1 --> 6)]-beta-D-glucopyranoside (2), were isolated from the roots of Pueraria lobata, together with four known compounds, 4'-methoxypuerarin (3), daidzin (4), genistin (5), and daidzein (6). The structures of these compounds were elucidated by the spectroscopic methods.     

朝鲜白头翁的三萜皂苷成分研究

目的　研究朝鲜白头翁［Pulsatilla cernua(Thunb.) Bercht. et Opiz.］ 根茎的化学成分。 方法　朝鲜白头翁根茎的乙醇提取物经大孔树脂、硅胶、ODS柱以及HPLC分离得到6个化合物, 通过波谱(1H,¹³CNMR,FAB-MS等)分析和化学方法进行结构鉴定。结果　6个化合物分别被鉴定为pulsatilla saponin A(1), 常春藤皂苷元3-O-β-D-吡喃葡糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖苷(2), pulsatilla saponin D(3), dipsacoside B(4), 3-O-α-L-吡喃鼠李糖(1→2)［β-D-吡喃葡糖(1→4)］-α-L-吡喃阿拉伯糖常春藤皂苷元28-O-β-D-吡喃葡糖酯苷(5)和胡萝卜苷(6)。 结论　5为新化合物, 命名为朝鲜白头翁丙苷(cernuoside C)。 2,4和6为首次从朝鲜白头翁中分离获得。     

Four new glycosides from Pleurospermum franchetianum

Four new glycosides, pleurofranosides I-IV, together with eight known compounds were isolated from the whole plants of Pleurospermum franchetianum Hemsl. Based on the spectral data and chemical evidence, the structures of pleurofranosides 1, II, III and IV were elucidated to be 16beta, 21beta, 23, 28-tetrahydroxyolean-12-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-glucopyranoside, 13beta, 28-epoxy-16beta, 23-dihydroxyolean-11-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-glucopyranosyl-(1 --> 2)]-beta-D-fucopyranoside, 13beta, 28-epoxy-16beta, 23-dihydroxyolean-11-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 4)-[beta-D-fucopyranosyl-(1 --> 2)]-beta-D-glucopyranoside and 12beta, 28-epoxy-16beta, 23-dihydroxyolean-11-ene-3beta-yl-O-beta-D-glucopyranosyl-(1 --> 3)-[beta-D-glucopyranosyl-(1 --> 2)]-beta-D-glucopyranoside. The known compounds identified were octadecyl caprate, beta-sitosterol, (22E, 20S, 24R)-5alpha, 8alpha-epidioxy-ergosta-6, 22-dien-3-beta-ol, daucosterol, alpha-spinasterol-3-O-beta-D-glucopyranoside, quercetin-3, 7-di-O-beta-D-glucopyranoside, kaempferol-3, 7-di-O-alpha-L-rhamnopyranoside and kaempferol-3-O-beta-D-glucopyranosyl-7-O-alpha-L-rhamnopyranoside, respectively.     

两头尖的化学成分研究

目的研究两头尖的化学成分。方法通过硅胶柱色谱,大孔树脂柱色谱及高压液相色谱等方法分离两头尖各部分提取物,根据理化性质和光谱分析鉴定化学结构。结果从两头尖根茎中分离得到9个化合物,分别鉴定为:27-hydroxyolean-12(13)-en-28-oic-acid-3-o-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside (1),五加苷K(eleutheroside K, 2),oleanolic acid-3-O-α-L-rhamnopyranosyl-(1→2)-［β-D-glucopyranosyl-(1→4)］-α-L-arabinopyranoside (3),桦树脂醇(betulin, 4),桦树脂酸(betulic acid, 5),乙酰齐敦果酸(acetyloleamolic acid, 6),卫矛醇(evonymitol, 7),齐敦果酸(oleamolic acid, 8),薯蓣皂苷元(diosgenin, 9)。结论化合物1为新化合物,命名为raddeanoside 12。化合物3～7为首次自该植物中得到。     

Two new prosapogenins from Albizia adianthifolia

Two new triterpenoidal prosapogenins 1 and 2 were obtained from the mild alkaline hydrolysate of the crude saponin fraction of Albizia adianthifolia (Mimosaceae) roots. Their structures were mainly determined by spectral analyses as acacic acid 3-O-beta-D-xylopyranosyl-(1-->2)-beta-D-fucopyranosyl-(1-->6)- 2-acetylamino-2-deoxy-beta-D-glucopyranoside (1) and acacic acid 3-O-(beta-D-xylopyranosyl-(1-->2)-beta-D-fucopyranosyl-(1-->6)- [beta-D-glucopyranosyl-(1-->2)]-beta-D-glucopyranosyl)-21-O-(6(S)-2- hydroxymethyl-6-methyl-6-O-(beta-D-quinovopyranosyl)-2,7-octadienoyl) ester (2). Furthermore, the known julibroside A3 was isolated from the crude saponin mixture. Compounds 1 and 2 did not show any ability to potentiate in vitro cisplatin cytotoxicity in a human colon cancer cell line.     

A pair of isomeric saponins with cytotoxicity from Albizzia julibrissin

Two new saponins have been isolated from the stem barks of Albizzia julibrissin Durazz, and their structures identified as 3-O-[beta-D-xylopyranosyl-(1 --> 2)-beta-D-fucopyranosyl-(1 --> 6)-beta-D-2-deoxy-2-acetoamidoglucopyranosyl]-21-O-{(6S)-2-trans-2-hydroxymethyl-6-methyl-6-O-[4-O-((6S)-2-trans-2-hydroxymethyl-6-hydroxy-6-methyl-2,7-octadienoyl)-beta-D-quinovopyranosyl]-2,7-octadienoyl}-acacic acid-28-O-beta-D-glucopyranosyl-(1 --> 3)-[alpha-L-arabinofuranosyl-(1 --> 4)]-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl ester (1) and 3-O-[beta-D-xylopyranosyl-(1 --> 2)-beta-D-fucopyranosyl-(1 --> 6)-beta-D-2-deoxy-2-acetoamidoglucopyranosyl]-21-O-{(6S)-2-trans-2-hydroxymethyl-6-methyl-6-O-[3-O-((6S)-2-trans-2-hydroxymethyl-6-hydroxy-6-methyl-2,7-octadienoyl)-beta-D-quinovopyranosyl]-2,7-octadienoyl}acacic acid 28-O-beta-D-glucopyranosyl-(1 --> 3)-[alpha-L-arabinofuranosyl-(1 --> 4)]-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl ester (2), based on chemical and spectral evidences, named as julibroside J19 and julibroside J18, respectively. Both compounds show significant inhibition action against HeLa, Bel-7402 and MDA-MB-435 cancer cell lines in vitro.     

Xanthone glycosides from Swertia franchetiana

A new xanthone glycoside (1) has been isolated from Swertia franchetiana together with five known xanthone glycosides. Their structures were elucidated as 7-O-[beta-D-xylopyranosyl-(1-->2)-beta-D-xylopyranosyl]-1,7,8-trihydroxy-3-methoxyxanthone (1), 7-O-[alpha-L-rhamnopyranosyl-(1-->2)-beta-D-xylopyranosyl]-1,7,8-trihydroxy-3-methoxyxanthone (2), 8-O-beta-D-glucopyranosyl-1,3,5,8-tetrahydroxyxanthone (3), 1-O-beta-D-glucopyranosyl-1-hydroxy-3,7,8-trimethoxyxanthone (4), 1-O-[beta-D-xylopyranosyl-(1-->6)-beta-D-glucopyranosyl]-1-hydroxy-2,3,5-trimethoxyxanthone (5) and 1-O-[beta-D-xylopyranosyl-(1-->6)-beta-D-glucopyranosyl]-1-hydroxy-3,5-dimethoxyxanthone (6) on the basis of spectroscopic evidence.