Saponarioside C, the first alpha-D-galactose containing triterpenoid saponin, and five related compounds from Saponaria officinalis

Six novel triterpenoid saponins, named saponariosides C-H, were isolated from the whole plants of Saponaria officinalis. Their structures were established as saponarioside C (1), 3-O-beta-D-xylopyranosyl-gypsogenic acid-28-O-alpha-D-galactopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-- >6)-[beta-D-glucopyranosyl-(1-->3)]-beta-D-glucopyranoside; saponarioside D (2), 3-O-beta-D-xylopyranosyl-gypsogenic acid-28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->6) -[beta-D-glucopyranosyl-(1-->3)]-beta-D-glucopyranoside; saponarioside E (3), 3-O-beta-D-glucopyranosyl-gypsogenic acid-28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->6) -[beta-D-glucopyranosyl-(1-->3)]-beta-D-glucopyranoside; saponarioside F (4), 3-O-beta-D-xylopyranosyl-16alpha-hydroxygypsogenic acid-28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->6) -[beta-D-glucopyranosyl-(1-->3)]-beta-D-glucopyranoside; saponarioside G (5), 3-O-beta-D-xylopyranosyl-16alpha-hydroxygypsogenic acid-28-O-beta-D-glucopyranosyl-(1-->6)-[beta-D-glucopyranosyl-(1-->3 )]-beta-D-glucopyranoside; and saponarioside H (6), 3-O-beta-D-xylopyranosyl-gypsogenic acid-28-O-beta-D-glucopyranoside, by a combination of extensive NMR (DEPT, COSY, HOHAHA, HETCOR, HMBC, and NOESY) studies and chemical degradation.     

Chionaeosides A-D, triterpene saponins from Paronychia chionaea

Four new triterpenoid saponins, chionaeosides A-D (1-4) were isolated from the roots of Paronychia chionaea. On the basis of their spectroscopic data, the structures of the new saponins were established as 3-O-alpha-L-arabinopyranosylgypsogenic acid 28-O-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside (1), 3-O-alpha-L-arabinopyranosylgypsogenic acid 28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside (2), 3-O-alpha-L-arabinopyranosylgypsogenic acid 28-O-beta-D-glucopyranoside (3), and 3-O-alpha-L-arabinopyranosylgypsogenic acid (4).     

安徽银莲花的化学成分研究

目的 :对安徽银莲花根茎的化学成分进行分离、鉴定。方法 :大孔树脂柱、硅胶柱和ODS柱色谱分离 ,FAB MS和NMR技术确定结构。结果和结论 :分离鉴定了 3个化合物 ,齐墩果酸28-O-α-L-吡喃鼠李糖-(1→4)-β-D-吡喃葡萄糖-(1→6)-β-D-吡喃葡萄糖酯苷 ;3-O-α-L-吡喃鼠李糖 (1→ 2)-β-D-吡喃木糖齐墩果酸-28-O-α-L-吡喃鼠李糖 (1→4)-β-D-吡喃葡萄糖 (1→6)-β-D-吡喃葡萄糖酯苷和-3-O-β-D-吡喃葡萄糖 (1→2)-β-D-吡喃木糖齐墩果酸-28-O-α-L-吡喃鼠李糖 (1→4)-β-D-吡喃葡萄糖 (1→6)-β-D-吡喃葡萄糖酯苷 ;均为首次从本植物中分离得到。     

Steroidal saponins from the rhizomes of Polygonatum sibiricum

Four new steroidal saponins, named neosibiricosides A-D (1-4), were isolated from the rhizomes of Polygonatum sibiricum, along with two known spirostanol glycosides. The structures of the new glycosides were elucidated by spectroscopic methods and acid hydrolysis as (23S,24R,25R)-1-O-acetylspirost-5-ene-1beta,3beta,23,24-tetrol 3-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranoside (1), (25S)-1-O-acetylspirost-5-ene-1beta,3beta-diol 3-O-beta-D-glucopyranosyl-(1-->2)-[beta-D-xylopyranosyl-(1-->3)]-beta-D-glucopyranosyl-(1-->4)-beta-D-galactopyranoside (2), (25S)-spirost-5-en-3beta-ol 3-O-beta-D-glucopyranosyl-(1-->2)-[beta-D-xylopyranosyl-(1-->3)]-beta-D-glucopyranosyl-(1-->4)-2-O-acetyl-beta-D-galactopyranoside (3), and (25R,S)-spirost-5-en-3beta-ol 3-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->4)-beta-D-galactopyranoside (4). The cytotoxic activity of the isolated compounds was evaluated with human MCF-7 breast cancer cells.     

Activity of triterpenoid glycosides from the root bark of Mussaenda macrophylla against two oral pathogens.

Four new triterpenoid glycosides were isolated from the root bark of Mussaenda macrophylla. Their structures were determined as 3-O-beta-D-glucopyranosyl-28-O-alpha-L-rhamnopyranosyl-16alpha- hydrox y-23-deoxyprotobassic acid (1), 28-O-beta-D-glucopyranosyl-16alpha-hydroxy-23-deoxyprotobassic+ ++ acid (2), 3-O-beta-D-glucopyranosyl-28-O-alpha-L-rhamnopyranosyl-16alpha- hydrox yprotobassic acid (3), and 3-O-?[beta-D-glucopyranosyl-(1-->6)]-O-alpha-L-rhamnopyranosyl-(1-->2 )-O-beta-D-glucopyranosyl-(1-->2)?-O-beta-D-glucopyranosyl-(1-->3)-O- beta-D-glucopyranosyl-cycloarta-22,24-dien-27-oic acid (mussaendoside W, 4). Four known triterpenoids [3-O-acetyloleanolic acid (5), 3-O-acetyldaturadiol (6), rotundic acid (7), and 16alpha-hydroxyprotobassic acid (8)] were also isolated. The structures of 1-4 were determined by several spectroscopic techniques including 2D NMR methods. Compounds 1-6 showed inhibitory activity against a periodontopathic bacterium, Porphyromonas gingivalis, but were inactive against the cariogenic organism, Streptococcus mutans.     

A new pregnane glycoside from Dioscorea collettii var. hypoglauca

During further bioactivity-guided fractionation, a new pregnane glycoside, hypoglaucin G (1), and a known compound, pregna-5, 16-dien-3beta-ol-20-one 3-O-alpha-L-rhamnopyranosyl-(1-->2)- [alpha-L-rhamnopyranosyl-(1-->4)] -beta-D-glucopyranoside (2), were isolated from the EtOH extract of Dioscorea collettii var. hypoglauca rhizomes, which induced morphological deformation of Pyricularia oryzae mycelia with minimum morphological deformation concentration values of 135 microM and 236 microM, respectively. The structure of 1 was established as 16beta-(4'-methyl-5'-O-beta-D-glucopyranosyl- pentanoxyl)-pre gn-5-en-3 beta-ol-20-one 3-O-alpha-L- rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-D- glucopyranoside on the basis of chemical evidence and spectral analysis, especially by 2D NMR techniques.     

Triterpene glycosides from the roots of Astragalus flavescens

Six new triterpene saponins, 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-xylopyranosyl-(1-->2)-beta-D-glucuronopyranosyl-21-epi-kudzusapogenol A (1), 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->2)-beta-D-glucuronopyranosyl-21-epi-kudzusapogenol A (2), 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-xylopyranosyl-(1-->2)-beta-D-glucuronopyranosyl-22-O-beta-D-glucopyranosyl-21-epi-kudzusapogenol A (3), 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->2)-beta-D-glucuronopyranosyl-22-O-beta-D-glucopyranosyl-21-epi-kudzusapogenol A (4), 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-xylopyranosyl-(1-->2)-beta-D-glucuronopyranosyl-22-O-alpha-L-arabinopyranosyl-21-epi-kudzusapogenol A (5), and 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->2)-beta-D-glucuronopyranosyl-22-O-alpha-L-arabinopyranosyl-21-epi-kudzusapogenol A (6), were isolated from the roots of Astragalus flavescens, together with the known trajanoside B, azukisaponin V, and astragalosides IV, VII, and VIII. Their structures were established mainly by 2D NMR techniques and mass spectrometry.     

Triterpene saponins in the defensive secretion of a chrysomelid beetle, Platyphora ligata

The secretion of the defensive glands of adults of the chrysomelid beetle Platyphora ligata from Panama has been shown to contain, besides chlorogenic acid (1) and a mixture of phosphatidylcholines, two new oleanane triterpene saponins, named ligatosides A and B. Their structures were established as 3-O-beta-D-glucuronopyranosyl-16alpha,23-dihydroxyoleanol ic acid-28-O-2-(3,4-dimethoxybenzoyl)-beta-D-glucopyranoside (2) and 3-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucuronopyranosyl-16a lpha, 23-dihydroxyoleanolic acid-28-O-2-(3, 4-dimethoxybenzoyl)-beta-D-glucopyranoside (3), respectively, by a combination of extensive 1D and 2D NMR methods (COSY, HMQC, HMBC, and TOCSY) and FABMS. This is the first report of triterpene saponins in the defensive secretion of an insect.     

藏药五脉绿绒蒿中非生物碱成分

目的:研究藏药五脉绿绒蒿Meconopsis quintuplinervia的化学成分。方法:应用色谱技术分离纯化,用波谱学方法确定化合物结构。结果:从乙醇提取物中分离得到12个化合物,分别鉴定为:槲皮素-3-O-β-D-葡萄糖苷(Ⅰ),槲皮素-3-O-[β-D-半乳糖(1→6)]-β-D-葡萄糖苷(Ⅱ),山柰素-3-O-[β-D-葡萄糖(1→2)]-β-D-葡萄糖苷(Ⅲ),异鼠李黄素-3-O-[β-D-半乳糖苷(1→6)]-β-D-葡萄糖(Ⅳ),咖啡酸(Ⅴ),原儿茶酸(Ⅵ),对羟基肉桂酸(Ⅶ),2-(3,4-二羟苯基)-乙醇β-D-吡喃葡萄糖苷(Ⅷ),对羟基苯甲酸β-D-吡喃葡萄糖酯苷(Ⅸ),肉桂酸4-O-β-D-吡喃葡萄糖苷(Ⅹ),5,7-二羟基色原酮(Ⅺ),胡萝卜苷(Ⅻ)。结论:除Ⅵ和Ⅻ外,其余10个化合物均为首次从该属植物中发现。     

Triterpenoid saponins from the roots of Pulsatilla koreana

Six new saponins, five lupanes (1-5) and one oleanane (6), along with 11 known saponins, were isolated from the roots of Pulsatilla koreana. The structures of the new saponins were found to be 23-hydroxy-3beta-[(O-alpha-L-rhamnopyranosyl-(1-->2)-O-[O-beta-D-glucopyranosyl-(1-->4)]-alpha-L-arabinopyranosyl)oxy]lup-20(29)-en-28-oic acid (1), 23-hydroxy-3beta-[(O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl)oxy]lup-20(29)-en-28-oic acid (2), 3beta-[(O-alpha-L-rhamnopyranosyl-(1-->2)-O-[O-beta-D-glucopyranosyl-(1-->4)]-alpha-L-arabinopyranosyl)oxy]lup-20(29)-en-28-oic acid (3), 3beta-[(O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl)oxy]lup-20(29)-en-28-oic acid (4), 23-hydroxy-3beta-[(O-beta-D-glucopyranosyl-(1-->4)-alpha-L-arabinopyranosyl)oxy]lup-20(29)-en-28-oic acid (5), and hederagenin 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside (6). Their structures were determined on the basis of 1D and 2D NMR ((13)C NMR, (1)H NMR, (1)H-(1)H COSY, HMQC, and HMBC) methods, FABMS, and hydrolysis. All isolated compounds were evaluated for their cytotoxic activity against A-549 human lung carcinoma cells.     

Naphthopyranone glycosides from Paepalanthus microphyllus

Three new naphthopyranone glycosides, paepalantine-9-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside (1), paepalantine-9-O-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranoside (2), and paepalantine-9-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (3), along with the known paepalantine-9-O-beta-D-glucopyranoside (4) were isolated from aerial parts of Paepalanthus microphyllus. These compounds were characterized by spectrometric methods, including electrospray mass spectrometry and 1D and 2D NMR experiments. As a part of our program for screening natural compounds for anti-HIV activity, compounds 1-4 were tested in C8166 cells infected with HIV-1MN.     

Phenolic glycosides from berries of Pimenta dioica

Four new phenolic glycosides, (2-hydroxy-3-methoxy-5-allyl)phenyl beta- d-(6-O-E-sinapoyl)glucopyranoside (1), (1' R,5' R)-5-(5-carboxymethyl-2-oxocyclopentyl)-3 Z-pentenyl beta-D-(6-O-galloyl)glucopyranoside (2), (S)-alpha-terpinyl [alpha-L-(2-O-galloyl)arabinofuranosyl]-(1-->6)-beta-D-glucopyranoside (3), and (R)-alpha-terpinyl [alpha-L-(2-O-galloyl)arabinofuranosyl]-(1-->6)-beta-D-glucopyranoside (4), were isolated from the berries of Pimenta dioica together with eight known flavonoids. The structures of 1-4 were elucidated on the basis of MS and NMR data and enzymatic hydrolysis. All four glycosides showed radical-scavenging activity against 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals.     

Isolation of cytochrome P450 inhibitors from strawberry fruit, Fragaria ananassa

A new glycoside, 2-beta-d-glucopyranosyloxy-4,6-dihydroxyisovalerophenone (3), was isolated from strawberry fruit along with kaempferol-3-beta-D-(6-O-trans-p-coumaroyl)glucopyranoside (1) and kaempferol-3-beta-D-(6-O-cis-p-coumaroyl)glucopyranoside (2). Compounds 1 and 2 inhibited activity of a drug-metabolizing enzyme, CYP3A4.     

Antioxidant and free-radical scavenging activity of constituents of the leaves of Tachigalia paniculata

Two new myricetin glycosides, myricetin 7-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside (1) and myricetin 7-O-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranoside (2), together with the known compounds quercetin 3-O-beta-D-glucopyranoside (3), quercetin 3-O-alpha-L-rhamnopyranoside (4), quercetin 3-O-beta-D-galactopyranoside (5), methyl gallate (6), isovanillin (7), 4-hydroxymethylbenzoate (8), 3,4-dihydroxymethylbenzoate (9), and caffeoyl aldehyde (10) were isolated from the leaves of Tachigalia paniculata. The structures of these compounds were determined by spectroscopic methods. Their antioxidant activity was determined by measuring free-radical scavenging effects using three different assays, namely, the Trolox Equivalent Antioxidant Capacity (TEAC) assay, the coupled oxidation of beta-carotene and linoleic acid (autoxidation assay), and the inhibition of xanthine oxidase activity. Compounds 1, 2, and 6 showed activity in the TEAC test, compounds 5-7 and 10 were moderately active in the autoxidation assay, while compounds 1 and 2 were the most potent of the isolates in the xanthine oxidase test.     

New steroidal glycosides from the fruits of Tribulus terrestris

Three new steroidal saponins (1-3) were isolated from the fruits of Tribulus terrestris. Their structures were assigned by spectroscopic methods (IR, HRESIMS, 1D- and 2D-NMR) as 26-O-beta-D-glucopyranosyl-(25S)-5beta-furost-20(22)-en-3bet a, 26-diol-3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl- (1-->4)]-beta-D-glucopyranoside (1), 26-O-beta-D-glucopyranosyl-(25S)-5beta-furost-20(22)-en-3bet a, 26-diol-3-O-alpha-L-rhamnopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1 -->4)]-beta-D-galactopyranoside (2), and 25(S)-5beta-spirostan-3beta-ol-3-O-alpha-L-rhamnopyranosyl-( 1-->2)-[b eta-D-glucopyranosyl-(1-->4)]-beta-D-galactopyranoside (3). Compound 3 showed cytotoxicity against a human malignant melanoma cell line (SK-MEL).     

Isolation and structure of cytostatic steroidal saponins from the African medicinal plant Balanites aegyptica.

Bioactivity-guided separation of a CH2Cl2/MeOH extract of Balanites aegyptica afforded four new cytostatic saponins, named balanitins 4 [1], 5 [2], 6 [3], and 7 [4]. On the basis of enzymatic hydrolyses and glycosidation nmr chemical shifts employing the peracetates, structures 1-4 were established as yamogenin 3 beta-O-beta-D-glucopyranosyl-(1----3)-beta-D-glucopyranosyl-(1----4)-[al pha- L-rhamnopyranosyl-(1----2)]-beta-D-glucopyranoside [1], yamogenin 3 beta-O-alpha-L-rhamnopyranosyl-(1----3)-beta-D-glucopyranosyl-(1----4)- [alpha-L-rhamnopyranosyl-(1----2)]-beta-D-glucopyranoside [2], yamogenin 3 beta-O-beta-D-glucopyranosyl-(1----4)-[alpha-L- rhamnopyranosyl-(1----2)]-beta-D-glucopyranoside [3], and diosgenin 3 beta-O-beta-D-xylopyranosyl-(1----3)-beta-D-glucopyranosyl-(1----4)-[alp ha- L-rhamnopyranosyl-(1----2)]-beta-D-glucopyranoside [4].     

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.     

Madhucosides A and B, protobassic acid glycosides from Madhuca indica with inhibitory activity on free radical release from phagocytes

The structures of madhucosides A (1) and B (2), isolated from the bark of Madhuca indica, were established as 3-O-beta-D-apiofuranosyl(1-->2)-beta-D-glucopyranosyl-28-O-[beta-D-xylopyranosyl(1-->2)-[alpha-L-rhamnopyranosyl(1-->4)]-beta-D-glucopyranosyl(1--> 3)-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranosyl]protobassic acid and 3-O-beta-D-apiofuranosyl(1-->2)-beta-D-glucopyranosyl-28-O-[beta-D-xylopyranosyl(1-->2)-[alpha-L-rhamnopyranosyl(1-->4)]-beta-D-glucopyranosyl(1-->3)-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranosyl]protobassic acid, respectively. These two compounds showed significant inhibitory effects on both superoxide release from polymorphonuclear cells in a NBT reduction assay and hypochlorous acid generation from neutrophils assessed in a luminol-enhanced chemiluminescence assay.     

New 3,4-seco-lupane-type triterpene glycosides from Acanthopanax senticosus forma inermis

Four new 3,4-seco-lupane-type triterpene glycosides (1-4) were isolated from the leaves of Acanthopanax senticosus forma inermis. The structures of 1-4 were established as 11alpha-hydroxy-3, 4-seco-lup-4(23),20(30)-dien-3-oic acid methyl ester 28-oic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-be ta-D-glucopyranoside, designated as inermoside (1); 1-deoxychiisanoside (2); 24-hydroxychiisanoside (3); and 11-deoxyisochiisanoside (4) by (1)H-(1)H COSY and (1)H-(13)C COSY(HMBC, HMQC) methods and FABMS.     

Rivalosides A and B, two 19-Oxo triterpenoid saponins from Galium rivale

Two new oleanene-type triterpene glycosides, rivaloside A (2alpha-acetoxy-3alpha-hydroxy-19-oxo-olean-12-en-28-o ic acid 28-O-beta-glucopyranosyl-(1-->6)-beta-D-glucopyranoside) (1) and rivaloside B (2alpha,3alpha-dihydroxy-19-oxo-olean-12-en-28-oic acid 28-O-beta-glucopyranosyl-(1-->6)-beta-D-glucopyranoside) (2), were isolated from aerial parts of Galium rivale. The structures were determined on the basis of spectroscopic data and chemical transformations. Under alkaline or acid hydrolysis, rivalosides A and B undergo allylic rearrangement with migration of the double bond. These compounds are the first representatives of 19-oxo substituted oleanenes, and they seem to be promising as taxonomic markers for G. rivale.