Silenorubicosides A-D, triterpenoid saponins from Silene rubicunda

Four novel triterpenoid saponins, silenorubicosides A-D (1-4), together with four known saponins were isolated from the roots of Silene rubicunda. Their structures were established on the basis of spectroscopic analysis, including extensive 1D and 2D NMR (DQF-COSY, TOCSY, HETCOR, HMBC, and phase-sensitive NOESY) studies and chemical degradation.     

Junceosides A-C, new triterpene saponins from Arenaria juncea.

Three novel triterpenoid saponins, junceosides A (1), B (2), and C (3), together with two known saponins have been isolated from the roots of Arenaria juncea. Their structures were elucidated using a combination of homo- and heteronuclear 2D NMR techniques (COSY, TOCSY, NOESY, HSQC, and HMBC) and by FABMS. The new compounds were characterized as 3-O-alpha-L-arabinopyranosyl-(1-->2)-[beta-D-galactopyranosyl-(1-->3)]-beta-D-glucuronopyranosylgypsogenin-28-O-beta-D-glucopyranosyl(1-->3)-[beta-D-xylopyranosyl-(1-->4)]-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-fucopyranoside (1), 3-O-alpha-L-arabinopyranosyl-(1-->2)-[beta-D-galactopyranosyl-(1-->3)]-beta-D-glucuronopyranosylgypsogenin-28-O-beta-D-xylopyranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-fucopyranoside (2), and 3-O-beta-D-xylopyranosyl-(1-->3)-[beta-D-galactopyranosyl-(1-->2)]-beta-D-glucuronopyranosylgypsogenin-28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-fucopyranoside (3).     

Six triterpenoid saponins from Mmaesa laxiflora.

Six new triterpenoid saponins, maelaxins A-F (1-6), were isolated from a n-BuOH extract of the leaves of Maesa laxiflora. They possess 22-O-angeloyl-camelliagenin A, 16-O-acetyl, 22-O-angeloyl-camelliagenin A, or 22-O-(2Z)-hexenoyl-camelliagenin A as the aglycon. The pentasaccharide moiety linked to C-3 of the aglycon consists of D-glucuronic acid, L-rhamnose, D-glucose, and/or D-galactose. Their structures were elucidated by extensive NMR experiments including 1H-1H (COSY, 2D HOHAHA, NOESY) and 1H-13C (HMQC and HMBC) spectroscopy and chemical evidence.     

Gleditsiosides N-Q, new triterpenoid saponins from Gleditsia sinensis.

The structures of gleditsiosides N, O, P, and Q (1-4), isolated from anomalous fruits of Gleditsia sinensis, were characterized as novel complex bisdesmosidic triterpenoid glycosides acylated with monoterpenoid units, by means of extensive 1D and 2D NMR studies. The four compounds shared a common structural feature with a trisaccharide [(beta-D-xylopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-be ta- D-glucopyranoside)] affixed to C-3 and a tetrasaccharide [(beta-D-xylopyranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alpha-L-r hamnopyranosyl-(1-->2)-beta-D-glucopyranosyl ester)] attached to C-28. Gleditsioside P (3) is the first saponin of this type found to date bearing three monoterpenoid units.     

Cytotoxic triterpenoid saponins from Symplocos chinensis

Six new triterpenoid saponins were isolated as methyl or butyl esters from an n-BuOH extract of the roots of Symplocos chinensis. Their structures were established as symplocososides A (1), B (2), C (3), D (4), E (5), and F (6), by extensive 1D and 2D NMR as well as HR-MS analysis and chemical methods. Compounds 1, 3, and 6 were cytotoxic against one or more cell lines, and the derivative from 1 (1d) showed significant selectivities between KB cells and normal cells.     

New triterpenoid saponins from Maesa japonica

New triterpenoid saponins, maejaposides A, B, C, D, and E, were isolated from the roots of Maesa japonica and were, respectively, defined to be 3-O-[beta-D-xylopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->2)-bet a-D-galactopyranosyl-(1-->3)] [beta-D-galactopyranosyl-(1-->2)]beta-D-glucuronopyranosides of 22alpha-[(Z)-2-hexenoyloxy]-13beta,28-oxido-olean++ +-16alpha, 28alpha-diol (1); 22alpha-[2'-methylbutanoyl]-13beta, 28-oxido-olean-16alpha,28alpha-diol (2a) and 22alpha-angeloyloxy-13beta,28-oxido-olean-16a lpha,28alpha-diol (2b); 21beta,22alpha-diangeloyloxy-13beta,28-oxido- olean-16alpha, 28alpha-diol (3); 21beta-angeloyloxy, 22alpha-(2'-methylbutanoyl)-13beta,28-oxido-olean++ +-16alpha, 28alpha-diol (4), and 21beta-angeloyloxy, 22alpha-[(Z)-2'-hexenoyl]-13beta,28-oxido-olean- 16alpha,28alpha-diol (5). Their structures were established on the basis of extensive NMR (DEPT, COSY, HOHAHA, HETCOR, HMBC, and NOESY) and ESIMS/MS studies, along with chemical degradation.     

Cytotoxic triterpenoid saponins from Lysimachia clethroides

Seven oleanane-type triterpenoid saponins, named clethroidosides A-G (1-7), an ursane-type triterpenoid saponin, clethroidoside H (8), and six known saponins were isolated from the aerial parts of Lysimachia clethroides. The structures of the saponins were elucidated on the basis of physical data analysis (1D and 2D NMR, HR-ESIMS) and chemical evidence. The cytotoxic activities of compounds 1-14 were evaluated against five human tumor cell lines (HT-29, HePG2, BGC-823, A549, and A375). Compounds 3, 4, 6, and 11-13 exhibited moderate cytotoxic activity, with IC50 values of 0.75-2.62 μM, while compound 5 showed selective cytotoxic activity.     

New triterpenoid saponins from the sponge Erylus nobilis.

Erylosides G--J (1--4), four new triterpenoid saponins, were isolated from the sponge Erylus nobilis collected from Jaeju Island, Korea. On the basis of the results of combined chemical and spectral analyses, the structures of the aglycones were determined to be lanostane-based, modified penasterols. The oligosaccharide portions were composed of one unit each of L-arabinose, D-galactose, and 2-N-acetyl-D-glucosamine (1 and 3) or two units of L-arabinose and one unit of 2-N-acetyl-D-glucosamine (2 and 4). These compounds exhibited moderate cytotoxicty against a human leukemia cell line.     

Cytotoxic oxygenated triterpenoid saponins from Symplocos chinensis

A n-butanol-soluble fraction of an ethanolic extract from the roots of Symplocos chinensis showed cytotoxic activity against several cancer cell lines. Bioassay-guided purification led to the isolation and characterization of eight new triterpenoid saponins, symplocososides L-S (1-8). The structures of 1-8 were elucidated as glycosides based on oxygenated aglycons by spectroscopic and chemical methods. These compounds and their hydrolytic products, along with some additional analogues obtained earlier from S. chinensis roots, were evaluated for cytotoxicity in a small cancer cell panel.     

Three new triterpenoid saponins from Aralia echinocaulis

Objective: To study the active ingredients in the root bark of Aralia echinocaulis. Methods: Three triterpenoid saponins were separated from the 70% ethanol extracts and purified by column chromatography and their structures were determined by spectroscopic analysis. Compound 1 and 3 were evaluated for antioxidant activity by the in vitro DPPH free radical scavenging ability and the protective effect of OH- induced DNA oxidative damage. Results: Compound 1 was a new type of triterpenoid saponin, named as echinocaulisaglycone 3-O-β-D-glucopyranoside (echinocaulisaponin A), and it had good antioxidant activity. Compound 2 was similar to compound 1, named as 1-hydroxyl-echinocaulisaglycone 3-O-β-D-glucopyranoside (echinocaulisaponin B). Compound 3 was also a new type of triterpenoid saponin, named as echinocaulisaglycone II 3-O-α-L-arabinopyranosyl-(1”→4’)-β-D-glucopyranosiduronic acid (echinocaulisaponin C), and its antioxidant activity was weaker than compound 1. Conclusion: In this study, three new compounds were discovered and two of them were carried out in vitro anti-oxidation studies, laying the foundation for further research on the treatment of related diseases (cardiovascular disease, arthritis, age-related macular degeneration, etc.) through anti-oxidation or quenching free radical function.     

Biologically active triterpenoid saponins from Acanthopanax senticosus

Three new triterpenoid saponins, acanthopanaxosides A (1), B (7), and C (13), were isolated from the leaves of Acanthopanax senticosus, together with 12 known saponins. The structures of these new saponins were established as 3-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-30-nor-olean-12,20(29)-dien-28-oic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-6-O-acetyl-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (1), 3-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl oleanolic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-6-O-acetyl-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (7), and 3-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-3beta-hydroxyolean-12-ene-28,29-dioic acid (13), on the basis of spectroscopic analysis and chemical degradation. Among the known compounds, sessiloside and tauroside H1 are reported for the first time from A. senticosus. The biological activity of compounds 1-15 was examined against pancreatic lipase. Ciwujianoside C1 (6), tauroside H1 (11), 3-O-alpha-rhamnopyranosyl-(1-->2)-alpha-arabinopyranosyl mesembryanthemoidigenic acid (12), acanthopanaxoside C (13), sessiloside (14), and chiisanoside (15) inhibited pancreatic lipase activity in vitro. In turn, ciwujianosides C2 (3), D2 (5), C4 (8), and C3 (10) and hederasaponin B (9) enhanced this enzyme.     

New oleanene triterpenoid saponins from Madhuca longifolia

Four new oleanane-type triterpene glycosides, madlongisides A-D (1-4), were isolated from the seeds of Madhuca longifolia, and their structures were elucidated on the basis of extensive NMR experiments and chemical methods. Also obtained in this investigation were the known compounds mimusopside A, Mi-saponins A, B, and C, and 3-O-beta-D-glucopyranosyl protobassic acid.     

Biologically active triterpenoid saponins from Ardisia japonica

Eleven new triterpenoid saponins, ardisianosides A (1), B (2), C (4), D (5), E (6), F (7), G (15), H (16), I (17), J (18), and K (19), together with 10 known saponins, were isolated from the whole plants of Ardisia japonica. The structures of the new saponins were established on the basis of extensive 1D and 2D NMR and MS studies coupled with chemical degradations. The cytotoxic activities of saponins 1-21 are reported against three human cancer cell lines, namely, HL-60 myeloid leukemia, KATO-III stomach adenocarcinoma, and A549 lung adenocarcinoma cells.     

Four new triterpenoid saponins from Conyza blinii

Three new bisdesmosidic saponins named conyzasaponins A, B, and C (1-3) and one new monodesmosidic saponin, conyzasaponin G (4), were isolated from the aerial parts of Conyza blinii. Their structures were elucidated on the basis of extensive NMR (DEPT, DQF-COSY, HOHAHA, HMQC, HMBC, and NOESY) and MS studies. Compounds 1-3 share a common prosapogenin, bayogenin 3-O-beta-D-xylopyranosyl-(1-->3)-beta-D-glucopyranoside, which is identical with conyzasaponin G (4), and differ in the structures of the ester-linked sugar moieties at C-28. Conyzasaponin A (1) is the 28-O-beta-D-apiofuranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl ester, conyzasaponin B (2), the 28-O-beta-D-apiofurano- syl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-[alpha-L-arabinopyranosyl-(1-->3)]-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl ester, and conyzasaponin C (3), the 28-O-alpha-L-rhamnopyranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-[beta-D-apiofuranosyl-(1-->3)]-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl ester of the prosapogenin, respectively.     

Petersaponins III and IV, triterpenoid saponins from Petersianthus macrocarpus

Two new triterpenoid saponins, petersaponins III and IV (1 and 2), were isolated from an n-butanol extract of the bark of Petersianthus macrocarpus. They possess 21-O-benzoyl-22-O-acetylbarringtogenol C and 21-O-2-furoxyl-22-O-tigloylbarringtogenol C as the aglycon, respectively. For both 1 and 2, the trisaccharide moiety linked to C-3 of the aglycon consists of D-glucuronic acid, D-xylose, and D-galactose, while a L-rhamnose unit is linked to C-28. The structures of 1 and 2 were elucidated by extensive NMR experiments including (1)H-(1)H (COSY, HOHAHA, NOESY) and (1)H-(13)C (HMQC and HMBC) spectroscopy and by chemical evidence.     

Constituents of leguminous plants, XIII. New triterpenoid saponins from Wistaria brachybotrys

Two new triterpenoid saponins, wistariasaponins D [1] amd G [2], and the known saponin dehydrosoyasaponin I [3] were isolated from the knots of Wistaria brachybotrys. The Structures of 1 and 2 were determined from their chemical and physicochemical evidence. The inhibitory effects of these saponins on the activation of Epstein-Barr virus early antigen that was induced by a tumor promoter were also tested for the primary screening of antitumor-promoting activities.     

New biologically active triterpenoid saponins from Scabiosa tschiliensis

Eleven new triterpenoid saponins, scabiosaponins A-K (1-11), and hookerosides A (12) and B (13) were isolated from the whole plants of Scabiosa tschiliensis. The structures of the new compounds were established on the basis of extensive NMR (DEPT, DQF-COSY, HETCOR, TOCSY, HMQC, HMQC-TOCSY, HMBC, and NOESY) and MS studies coupled with chemical degradations. The biological activity of compounds 1-10, 12, and 13 and prosapogenin 1b were examined against pancreatic lipase. Scabiosaponins E, F, G, I (5, 6, 7, 9), hookerosides A, B (12, 13), and prosapogenin 1b all exhibited strong inhibition of pancreatic lipase in vitro.     

New triterpenoid saponins and sapogenins from Saponaria officinalis

Five new triterpenoid saponins, named saponariosides I-M, were isolated from the whole plants of Saponario officinalis. Their structures were established as saponarioside I (1) 3-O-beta-D-xylopyranosyl-16 alpha-hydroxygypsogenic acid 28-O-alpha-D-galactopyranosyl-(1-->6)-beta-D- glucopyranosyl-(1-->3)[-beta-D-glucopyranoside[, saponarioside J (3) 3-O-beta-D-xylopyranosylolean-11,13(18)-diene-23,28-dioic acid 28-O-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->6)[- beta-D-glucopyranoside[, saponarioside K (4) 3,4-seco-16 alpha-hydroxygypsogenic acid 28-O-beta-D-glucopyranosyl- (1-->3)-beta-D-glucopyranosyl-(1-->6)[-beta-D-glucopyranoside[, saponarioside L (5) 3-O-beta-D-xylopyranosylgypsogenic acid 28-O-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->6)[-beta- D- glucopyranoside[, and saponarioside M (6) 3-O-beta-D-glucopyrano-sylgypsogenic acid 28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1--6)-beta-D- glucopyranoside[ by NMR studies and chemical degradations. The aglycons of saponariosides J (3) and K (4) are new sapogenins.     

西南银莲花的活性三萜皂苷

目的 研究西南银莲花Anemone davidii根状茎和地上部分的活性三萜皂苷。方法 用甲醇室温提取,大孔树脂D101、硅胶及反相硅胶柱层析分离纯化,NMR分析并结合化学降解鉴定结构,体外抑菌和人癌细胞生长抑制实验测试抗菌和抗癌活性。结果 从该植物根状茎中分离鉴定出三萜皂苷Ⅰ～Ⅶ,从地上部分分离鉴定出三萜皂苷Ⅴ～Ⅷ,其中Ⅱ～Ⅳ对人癌细胞体外生长有抑制作用,Ⅴ,Ⅵ和Ⅷ有一定的抗菌活性。结论上述化学成分均为首次从该植物中分离得到,并首次进行抗癌活性测试,其中Ⅱ,Ⅳ和Ⅵ在该属植物中为首次报道。     

New triterpenoid saponins from the sponge Melophlus isis

Four new triterpenoid saponins were isolated, along with two known 30-norlanostane-type saponins- sarasinosides A(1) (1) and A(3) (2)-from the sponge Melophlus isis collected from Guam. The structures of these new compounds (3-6) proved to be 30-norlanosta-8(14),24-dien-23-ones bearing two hydroxyl groups or the corresponding methoxy groups at the 9alpha,15alpha- and 9alpha, 15beta-positions and the pentasaccharide portion identical with those of 1 and 2 at the 3beta position, by spectral, chemical, and GC analyses.