Two new bioactive triterpene glycosides from the sea cucumber Pseudocolochirus violaceus

By activity-guided fractionation, two new triterpene glycosides, violaceusides A (1) and B (2), were isolated from the sea cucumber Pseudocolochirus violaceus as active compounds causing morphological abnormality of Pyricularia oryzae mycelia. By extensive 2D NMR techniques and chemical evidence, the structures of the two new glycosides were established as 16β-acetoxy-3-O-[3-O-methyl-β-d-glucopyranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)-β-d-quinovopyranosyl-(1 → 2)-4-O-sodiumsulphate-β-d-xylopyranosyl]-holosta-7,24-diene-3β-ol (1) and 16β-acetoxy-3-O-[3-O-methyl-β-d-glucopyranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)-β-d-glucopyranosyl-(1 → 2)-4-O-sodiumsulphate-β-d-xylopyranosyl]-holosta-7,24-diene-3β-ol (2), respectively. The two glycosides also exhibited significant cytotoxicity against HL-60 and BEL-7402 cancer cell lines.     

New tirucallane-type triterpenoid saponins from Sapindus mukorossi Gaetn

Two new tirucallane-type triterpenoid saponins, sapimukoside C (1) and sapimukoside D (2), have been isolated from the roots of Sapindus mukorossi Gaetn. Their structures have been determined, on the basis of spectral and chemical analysis, as 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L- arabinopyranosyl-(1-->3)]-beta-D-glucopyranosyl (21,23R)-epoxyl tirucalla-7,24-diene-(21S)-ethoxyl-3 beta-ol (1) and 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-arabinopyranosyl-(1-->3)]- beta-D-glucopyranosyl (21,23R)-epoxyl tirucall-7,24-diene-(21S)-methoxyl-3 beta-ol (2).     

Furostanol oligoglycosides from Asparagus cochinchinensis

Three new furostanol oligoglycosides, named aspacochioside A (1), B (2) and C (3), together with the known compound 3-O-[(alpha-L-rhamnopyranosyl-(1 --> 4))(beta-D-glucopyranosyl)]-26-O[beta-D-glucopyranosyl]-(25S)-5beta-spirostane-3beta-ol were isolated from the roots of Asparagus cochinchinensis. Their structures were elucidated by spectroscopic techniques (IR, HR-ESIMS, ESIMS/MS, ID and 2D NMR) and chemical methods as 3-O-[(alpha-L-rhamnopyranosyl-(1 --> 4))(beta-D-glucopyranosyl)]-26-O-[beta-D-glucopyranosyl]-(25S)-5beta-furostane-3beta,22alpha,26-triol (1), 3-O-[(alpha-L-rhamnopyranosyl-(1 --> 4))(beta-D-glucopyranosyl)]-26-O-[beta-D-glucopyranosyl]-22alpha-methoxy-(25S)-5beta-furostane-3beta,26-diol (2), and 3-O-[(alpha-L-rhamnopyranosyl-(1 --> 4))(beta-D-glucopyranosyl)]-26-O-[beta-D-glucopyranosyl]-(25S)-5beta-furost-20(22)-en-3beta,26-diol (3).     

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.     

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).     

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.     

Anticomplement activities of oleanolic acid monodesmosides and bisdesmosides isolated fromTiarella polyphylla

Seven known oleanolic acid glycosides (1-7) were isolated from the MeOH extract of Tiarella polyphylla. The structures were identified to be 3-O-(beta-D-glucopyranosyl) oleanolic acid (1), 3-O-[beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl] oleanolic acid (2), 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl] oleanolic acid (3), 3-O-[beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester (4), 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester (5), 3-O-[a-L-rhamnopyranosyl-(1-->3)-beta-D-glucuronopyranosyl] oleanolic acid (6), and 3-O-[alpha-L-rhamnopyranosyl-(1-->3)-beta-D-glucuronopyranosyl] oleanolic acid 28-O-beta-D-glucopyranosyl ester (7) on the basis of physicochemical and spectral data. These triterpene glycosides were tested for the anticomplement activity and hemolytic activity. Bisdesmosidic saponins, 4, 5, and 7, showed anticomplement activity; in contrast, monodesmosidic saponins, 1-3, and 6, showed direct hemolytic activity. Methyl esterified monodesmosidic saponins showed anticomplement activity at a low concentration and hemolytic activity at a high concentration.     

New acylated triterpene saponins from Polygala tenuifolia willd

Two new acylated presenegenin glycosides E-onjisaponin H (5) and Z-onjisaponin (6) together with seven known saponins were isolated from the roots of Polygala tenuifolia Willd. Compounds 5 and 6 were obtained as a pair of isomers due to trans and cis-p-methoxycinnamoyl. Their structures were elucidated mainly by 2D-NMR techniques including 1H-1HCOSY, TOCSY, HSQC, HMBC as 3-O-(beta-D-glucopyranosyl) presenegenin 28-[O-beta-D-apiofuranosyl-(1 --> 3)-O-[beta-D-xylopyranosyl-(1 --> 4)]-O-alpha-L-rhamnopyranosyl-(1 --> 2)-O-[alpha-L-rhamnopyranosyl-(1 --> 3)]-4-O-[(E)-p-methoxycinnamoyl]-beta-D-fucopyranosyl] ester (5) and its (Z)-isomer (6).     

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。     

Cytotoxic triterpenoid saponins from Vaccaria segetalis

By the guidance of bioassay, one new cytotoxic triterpenoid saponin, 3-O-[beta-D-galactopyranosyl-(1-->2)-beta-D-glucuronopyranosyl] quillaic acid 28-O-beta-D-glucopyranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-[beta-D-fucopyranosyl-(1-->4)]-beta-D-fucopyranoside (1), and five known cytotoxic triterpenoid saponins, vaccaroside E (2), vaccaroside G (3), vaccaroside B (4), segetoside H (5) and segetoside I (6), were isolated from Vaccaria segetalis. Their structures were established on the basis of ESI-MS, IR, extensive NMR ((1)H NMR, (13)C NMR, TOCSY, (1)H-(1)H COSY, DEPT, HMQC, HMBC and ROESY) analyses, chemical degradation, and by comparing with previously reported data. Compounds 1-6 showed moderate cytotoxic activities against LNcap, P-388 and A-549 cell lines with IC(50) values in the range 0.1-12.9 microM.     

Triterpenoid saponins and anti-inflammatory activity of Codonopsis lanceolata

The ethanolic root extract of Codonopsis lanceolata were evaluated for anti-inflammatory activity using the carrageenan induced rat hind paw edema model and displayed a significant activity of 51.82% inhibition at 200 mg/kg at 3 h (p < 0.05). Further isolation of the extract yielded two new triterpenoid saponins, named codonolaside I (1) and codonolaside II (2). The spectroscopic and chemical data revealed their structures to be 3-O-[beta-D-xylopyranosyl (1->3)-(6'-O-methyl)-beta-D-glucuronopyranosyl]-30, 16a-dihydroxyolean-12-ene-28-oic acid 28-O-[P-D-xylopyranosyl (1-->4)-alpha-L-rhamnpyranosyl (1-->2)-alpha-L-arabinopyranosyl] ester (1), and 3beta, 16alpha-dihydroxyolean-12-ene-28-oic acid 28-O-[beta-D-xylopyranosyl (1-->3)-beta-D-xylopyranosyl (1-->4)-alpha-L-rhamnpyranosyl (1-->2)-alpha-L-arabinopyranosyl] ester (2).     

太白楤木根皮的齐墩果酸皂甙

从太白楤木(Aralia taibaiensis Z.Z.Wang et H.C.Zheng)根皮中首次分离到5个齐墩果酸皂甙,根据理化性质和光谱数据,分别鉴定为木皂甙A(1),3-O-[α-L-呋喃阿拉伯糖(1→4)-β-D-吡喃葡萄糖醛酸丁酯]-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(2),3-O-[α-L-呋喃阿拉伯糖(1→4)-β-D-吡喃葡萄糖醛酸乙酯]-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(3),屏边三七甙R₂(4)和3-O-｛β-D-吡喃葡萄糖(1→3)[α-L-呋喃阿拉伯糖(1→4)]-β-D-吡喃葡萄糖醛酸乙酯｝-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(5)。2,3和5为新化合物,分别命名为太白楤木皂甙I(taibaienoside I)、太白楤木皂甙II(taibaienoside II)和太白楤木皂甙III(taibaienoside III)。     

New sesquiterpene lactone and neolignan glycosides with antioxidant and anti-inflammatory activities from the fruits of Illicium oligandrum

Phytochemical investigations of the fruits of Illicium oligandrum resulted in a new sesquiterpene lactone, 3 beta-benzoyloxy-10-deoxyfloridanolide (1), and three new neolignan glycosides, including two dihydrobenzofuran neolignan glycosides, (7 R,8 S)-9-O-beta-D-xylopyranosyl-9'-O-alpha- L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyldihydrodehydrodiconiferyl alcohol (2) and (7 R,8 S)-9-O-shikimoyl-4-O-beta-D-glucopyranosyldihydrodehydrodiconiferyl alcohol (3) and one 8- O-4' neolignan glycoside, (7 S,8 R)-1-[4-O-(beta-D-glucopyranosyl)-3-methoxyphenyl]-2-[4-(3-hydroxypropyl)-2,6-dimethoxyphenoxy]-1,3-propanediol (4), together with three known sesquiterpene lactones (5 - 7) and two known neolignan glycosides (8 and 9). Their structures were elucidated on the basis of 1D, 2D NMR, HR-MS and chemical evidence. Compounds 3 and 4 showed moderate antioxidant activity with the inhibitory rates 13.30% and 9.30% at 1.0 x 10(-5) M, respectively. Compounds 3 and 9 exhibited anti-inflammatory activity with the inhibitory rates 67.0% and 51.0% at 1.0 x 10(-5) M, respectively.     

Three new asterosaponins from the starfish Culcita novaeguineae and their bioactivity

Bioassay-guided fractionation of the active n-BuOH extract of the starfish Culcita novaeguineae resulted in the isolation of three new sulfated steroidal glycosides (asterosaponins) 1, 2 and 3, as active compounds causing morphological abnormality of Pyricularia oryzae mycelia. Compounds 1-3 possess the same pentasaccharide moiety, beta-D-fucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->4)-[beta-D-quinovopyranosyl-(1-->2)]-beta-D-xylopyranosyl-(1-->3)-beta-D-quinovopyranosyl, linked to C-6 of 3beta-sulfated steroidal aglycones and differ from each other in the side chains. Their structures were elucidated by extensive spectral studies and chemical evidences. Saponins 1 and 3 showed significant cytotoxicity against two cancer cell lines (IC50 values for 1:3.57 microg/mL [K-562], 2.55 microg/mL [BEL-7402]; for 3:3.75 microg/mL [K-562], 1.89 microg/mL [BEL-7402]), as well as hemolytic activity to rabbit erythrocytes (ED50 values: 16 and 31 microg/mL, respectively), while 2 was inactive in these bioassays.     

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.     

A triterpenoid saponin from Albizia julibrissin

A triterpenoid saponin (1) was obtained from the stem barks of Albizia julibrissin Durazz. Its structure was elucidated as 3-O-[beta-D-xylopyranosyl-(1 --> 2)-alpha-L-arabinopyranosyl-(1 --> 6)-beta-D-glucopyranosyl]-21-O-[(6S)-2-trans-2-hydroxymethyl-6-methyl-6-O-beta-D-quinovopyranosyl-2, 7-octadienoyl]-16-deoxy-acacic acid 28-O-beta-D-glucopyranosyl-(1 --> 3)-[alpha-L-arabinofuranosyl-(1 --> 4)]-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl ester (1), named as Julibroside J26, based on the chemical and spectral methods.     

Steroidal saponins from Dioscorea panthaica and their cytotoxic activity

A new steroidal saponin, dioscoreside E (1), and a known compound, protodioscin (2), were isolated from an ethanol extract of the rhizomes of Dioscorea panthaica. The structure of 1 was established as 3-O-[bis-alpha-L-rhamnopyranosyl-(1 --> 2 and 1 --> 4)-beta-D-glucopyranosyl]-26-O-beta-D-glucopyranosyl-20(R)-methoxy-25(R)-furosta-5,22(23)-diene-3beta,26-diol, on the basis of spectral and chemical evidence. Compounds 1 and 2 showed cytotoxic activity against a panel of tumor cell lines.     

Anti-complement activity of norlignans and terpenes from the stem bark of Styrax japonica

A new norlignan, styraxlignolide A (1), and two new terpenes, styraxosides A (2) and B (3), were isolated from the MeOH-soluble fraction of Styrax japonica Sieb. et Zucc. (Styracaceae) stem bark, together with two known compounds, egonol (4) and masutakeside I (5). The new compounds were determined as 5-(3'-hydroxypropyl)-7-methoxy-2-(3',4'-dimethoxyphenyl)-benzofuran 3'- O-[beta-D-xylopyranoside-(1-->6)-beta- D-glucopyranoside] (1), 3beta,7beta-dihydroxy-4alpha,4beta,8beta,10beta,14alpha-pentamethyl-5alpha-gon-16-en-2-one 3-O-[beta-D-glucopyranoside-(1-->2)-beta-D-glucopyranoside] (2), and 3beta,17beta-dihydroxy-28-norolean-12-en-16-one 3-O-[alpha-L-rhamopyranoside-(1-->2)-beta-D-glucuronopyranoside] (3) by spectroscopic means including 2D-NMR. The five compounds were tested in vitro for anti-complement activity against the complement system. Compounds 1, 3, 4, and 5 displayed inhibitory activity in the anti-complement assay, with IC50 values of 123, 65, 33, and 166 microM, respectively. Compound 1a and camellenodiol (3a), obtained from acid hydrolysis of 1 and 3, respectively, did not affect the hemolytic activity of human serum against sensitized erythrocytes. This shows that a sugar seems to play a role of enhancing significantly anti-complement activity.     

川续断中皂甙Ⅸ和Ⅹ的结构研究

从川续断(Dipsacus asper Wall.)根的乙醇提取物中得到二个新三萜皂甙(Ⅸ和Ⅹ),根据光谱分析和化学反应,其结构分别确定为3-O-[β-D-吡喃木糖(1→4)-β-D-吡喃葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-常春藤皂甙元(Ⅸ)及其28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙(Ⅹ)。