Acylated protopanaxadiol-type ginsenosides from the root of Panax ginseng

Six new protopanaxadiol-type ginsenosides, named ginsenosides Ra(4) -Ra(9) (1-6, resp.), along with 14 known dammarane-type triterpene saponins, were isolated from the root of Panax ginseng, one of the most important Chinese medicinal herbs. The structures of the new compounds were determined by spectroscopic methods, including 1D- and 2D-NMR, HR-MS, and chemical transformation as (20S)- 3-O-{β-D-6-O-[(E)-but-2-enoyl]glucopyranosyl-(1→2)-β-D-glucopyranosyl}-20-O-[β-D-xylopyranosyl-(1→4)-α-L-arabinopyranosyl-(1→6)-β-D-glucopyranosyl]protopanaxadiol (1), (20S)-3-O-[β-D-6-O-acetylglucopyranosyl-(1→2)-β-D-glucopyranosyl]-20-O-[β-D-xylopyranosyl-(1→4)-α-L-arabinopyranosyl-(1→6)-β-D-glucopyranosyl]protopanaxadiol (2), (20S)-3-O-{β-D-6-O-[(E)-but-2-enoyl]glucopyranosyl-(1→2)-β-D-glucopyranosyl}-20-O-[β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl]protopanaxadiol (3), (20S)-3-O-{β-D-6-O-[(E)-but-2-enoyl]glucopyranosyl-(1→2)-β-D-glucopyranosyl}-20-O-[α-L-arabinopyranosyl-(1→6)-β-D-glucopyranosyl]protopanaxadiol (4), (20S)-3-O-{β-D-4-O-[(E)-but-2-enoyl]glucopyranosyl-(1→2)-β-D-glucopyranosyl}-20-O-[α-L-arabinofuranosyl-(1→6)-β-D-glucopyranosyl]protopanaxadiol (5), (20S)-3-O-{β-D-6-O-[(E)-but-2-enoyl]glucopyranosyl-(1→2)-β-D-glucopyranosyl}-20-O-[α-L-arabinofuranosyl-(1→6)-β-D-glucopyranosyl]protopanaxadiol (6). The sugar moiety at C(3) of the aglycone of each new ginsenoside is butenoylated or acetylated.     

Triterpene saponins from Cyclamen hederifolium

Five triterpene saponins never reported before, hederifoliosides A-E, and four known triterpene saponins were isolated from the tubers of Cyclamen hederifolium. The structures of hederifoliosides A-E were determined as 3β,16α-dihydroxy-13β,28-epoxyolean-30-oic acid 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, 3β,16α-dihydroxy-13β,28-epoxyolean-30-oic acid 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)]-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, 3β,16α-dihydroxy-13β,28-epoxyolean-30-al 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)]-O-[β-D-glucopyranosyl-(1 → 6)]-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, 30-O-β-D-glucopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-3β,16α,30-trihydroxyolean-12-en-28-al 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, 30-O-β-D-glucopyranosyl-(1 → 2)-O-β-D-glucopyranosyl-3β,16α,28,30-tetrahydroxyolean-12-en 3-O-{[β-D-glucopyranosyl-(1 → 2)-O]-β-D-xylopyranosyl-(1 → 2)-O-[β-D-glucopyranosyl-(1 → 3)]-O-β-D-glucopyranosyl-(1 → 4)-O-α-L-arabinopyranoside}, by a combination of one- and two-dimensional NMR techniques, and mass spectrometry. The cytotoxic activity of the isolated compounds was evaluated against a small panel of cancer cell lines including Hela, H-446, HT-29, and U937. None of the tested compounds, in a range of concentrations between 1 and 50 μM, caused a significant reduction of the cell number.     

黄花远志的新齐墩果烷型三萜皂甙

从云南产远志科药用植物黄花远志(PolygalaarillataBuchHamexDDon)茎皮的乙醇提取物中分离得到4个新的齐墩果烷型三萜皂甙,命名为黄花远志皂甙(arillatanoside)A～D。同时还分离得到1个已知的三萜皂甙远志甙(polygalasaponin)XXXV。它们的结构通过波谱方法推定。     

New pregnane glycosides from Brucea javanica and their antifeedant activity

Three new pregnane glycosides, 3-O-β-D-glucopyranosyl-(1→2)-α-L-arabinopyranosyl-(20R)-pregn-5-ene-3β,20-diol (1), 3-O-α-L-arabinopyranosyl-(20R)-pregn-5-ene-3β,20-diol-20-O-β-D-glucopyranoside (2), 3-O-α-L-arabinopyranosyl-(20R)-pregn-5-ene-3β,20-diol-20-O-β-D-glucopyranosyl-(1→2)-β-D-glucopyranoside (3) were isolated along with four known compounds, 4-7, from the leaves and stems of Brucea javanica. Their structures were determined by detailed analyses of 1D- and 2D-NMR spectroscopic data. All of the compounds isolated from Brucea javanica were tested for the antifeedant activities against the larva of Pieris rapae. Compounds 1, 3, and 5 showed significant antifeedant activities after 72 h incubation.     

金铁锁的新三萜皂甙

从金铁锁（Psammosilene tunicoides W.C.Wu et C.Y.Wu)根部分离得到5个齐墩果烷型五环三萜皂苷,它们的结构通过波谱和化学方法分别鉴定为：3-O-β-D-galactopyranosyl-(1→2)-β-D-glucuronopyranosyl-gypsogenin(1),3-O-β-D-galactopyranosyl-(1→2)-[β-D-galactopyranosyl-(1→3)-β-D-glucuronopyranosyl-gypsogenin(2),3-O-β-D-galactopyranosyl-(1→2)-β-D-glucuronopyra-nosyl-gypsogenin-28-O-β-D-xylopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→3)]-α-L-rhamnopyranosyl(1→2)-β-D-fucopyranoside(LobatosideI,3),3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)-β-D-glucuronopyranosylgypsogenin-28-O-β-D-xylopyranosyl-(1→4)-[β-D-glucopyranosyl-(1→3)]-α-L-rhamnopyranosyl(1→2)-β-D-fucopyranoside(4),3-O-β-D-galactopyranosyl-(1→）-β-D-glucuro-nopyranosyl-grpsogenin-28-O-β-D-xylopyranosyl-(1→4)-[β-D-6-O-acetylglucopyranosyl-(1→3)-β-D-glucuro-nopyranosyl-gypsogenin-28-O-β-D-xylopyranosyl-(1→4)-[β-D-6-O-acetylglucopyranosyl-(1→3)]-α-L-rh-amnopyranosyl(1→2)-β-D-fucopyranoside(5),其中5为新化合物,1和2为首次从自然界中分离得到。     

Haemolytic activity and immunological adjuvant effect of a new steroidal saponin from Allium ampeloprasum var. porrum

A new steroidal saponin was isolated from the bulbs of Allium ampeloprasum L. var. porrum. On the basis of chemical evidence, comprehensive spectroscopic analyses, and comparison with known compounds, its structure was established as (3β,5α,6β,25R)-3-{(O-β-D-glucopyranosyl-(1→3)-β-D-glucopyranosyl-(1→2)-O-[O-β-D-glucopyranosyl-(1→3)]-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranosyl)oxy}-6-hydroxyspirostan-2-one (1). Results of the present study indicated that 1 exhibited haemolytic activity in the in vitro assays, and immunological adjuvant activity on the cellular immune response against ovalbumin antigen.     

大叶吊兰中一个新的甾体皂甙

从百合科植物大叶吊兰（Ｃｈｌｏｍｐｈｙｔｕｍ ｍａｌａｙｅｎｓｅ）根茎中分离得到１个新的呋甾烷型甾体皂甙,命名为大叶吊兰甙Ｅ（ｃｈｌｏｒｏｍａｌｏｓｉｄｅ Ｅ）。经波谱和化学方法证明明其结构为：２６－０－β－Ｄ－ｇｌｕｃｏｐｙｒａｎｏｓｙｌ－２２－ｈｙｄｒｏｘｙ－２５（Ｓ）－５ａ－ｆｕｒｏｓｔａｎ－１２－ｏｘｏ－３β,２６－ｄｉｏｌ－３－β－Ｄ－ｘｙｌｏｐｙｒａｎｏｓｙｌ（１→３）〖α－Ｌ－ａｒａ     

龙舌兰发酵叶汁中的一个新甾体皂苷

从龙舌兰（Agave americana)的发酵叶汁中分离到一个新甾体皂苷。结合波谱和化学方法,新化合物的结构鉴定为替告皂苷元3－O－α－L－鼠李吡喃糖基－（1→3)－β-D-葡萄吡喃糖基－（1→2）-[β-D-葡萄吡喃糖基－（1→3)-β－D－葡萄吡喃糖基－（1→4）－β－D－半乳吡喃糖苷。     

Isolation and Identification of Steroidal Saponins from Dioscorea panthaica Prain et Burkill

Two steroidal saponins have been isolated from the rhizomes of Dioscorea panthaica Prain et Burkill. collected from Sichuan province. They were identified as 3-0-{α-L- rhamnopyranosyl (1→4)- [α-L-rhamnopyranosyl (1→2) ]-β-D-glucopyranosyl } -diosgenin (dioscin) and 3-O-{β-D-glucopyranosyl (1→3)-[α-L-rhamnopyranosyl (1→2)]-β-D-glucopyranosyl}-diosgenin (gracillin) on the basis of mp., m. mp., TLC. acetylation, acid hydrolysis, IR, MS, and 13C NMR.     

Isolation and Indentification of Protosaponins from Fresh Rhizomes of Dioscorea zingiberensis Wright

Five steroidal chemical compounds were isolated from the fresh rhizomes of Dioseorea zingiberensis Wright gathered from Sichuan Province. Their chem ieal structures have been elucidated as diosgenin palmitate [Ⅰ]; β-sitosterol [Ⅱ]; gra- cillin [Ⅲ]; protogracillin [Ⅳ] and 3-O-{α-L-rhamnopyranosyl (1→3)-[β-D-glucopy- ranosyl (1→2)]-β-D-glucopyranosyl}-26-O-{β-D-glucopyranosyl}-diosgenin [Ⅴ]. [Ⅴ]is a new steroidal saponin, named protozingiberensissaponin.     

Isolation and Indentification of Steroidal Saponins from Dioscorea zingiberensis Wright

Four known steroidal compounds were isolated from the rhizomes of Dioscorea zingiberensis Wright gathered from Hubei Province. Their structures were identified by means of spectroscopic analyses as Epi-smilagenin[Ⅰ]; 3-O-(β-D glucopyranosyl) diosgenin[Ⅱ]; 3-O-[β-D-glucopyranosyl (1→ 4)-β-D-glucopyranosyl-diosgenin[Ⅲ]; 3-O {β-D glucopyranosyl (1→ 3)-[α-L-rhamnopyranosyl (1 →2)]-β-D glucopyranosyl} diosgenin [Ⅳ].     

Triterpene Glycosides in the Leaves of Acanthopanax giraldii

Five triterpene glycosides have been isolated from the leaves of Acanthopanax giraldii Harms (Araliaceae), which are elucidated as: hederagenin-3-O-α-L-rhamnopyranosyl (1→2) -α-L-arabinopyranoside ( Ⅰ ), hederagenin-28-α-L-rhamnopyranosyl- (1→4) -β -D-glu- copyranosyl-(1→6)-β -D-glucopyranosylester ( Ⅱ ), 3-O-α-L-arabinopyranosyl-hederagenin- 28-β -D-glucopyranosyl- ( 1→6 ) -β -D-glucopyranosylester ( Ⅲ ), 3-O-α-L-arabinopyranosyl- hederagenin-28-α-L-rhamnopyranosyl- ( 1→4 ) -β -D-glucopyranosyl- ( 1→6 ) -β -D-glucopyra-nosylester ( Ⅳ ) and 3-O-α-L-rhamnopyranosyl- (1→2) -α-L-arabinopyranosyl-hederagenin-28-α-L-rhamnopyranosyl-( 1→4 )-β -D-glucopyranosyl-( 1→6 )-β -D-glucopyranosylester ( Ⅴ ). All of them are reported in this genus for the first time. Perhaps the findings are valuable for chemotaxonomy of Acanthopanax genus.     

Structure of desacylsaponins obtained from the bark of Quillaja saponaria

A triterpenoid saponin mixture (so-called quillajasaponin) obtained from the bark of Quillaja saponaria was treated with weak alkali and two major desacylsaponins were isolated. On the basis of chemical and spectral evidence, they were determined as 3-O-β-D-galactopyranosyl-(1 → 2)-[β-D-xylopyranosyl-(1 → 3)]-β-D-glucuronopyranosyl quillaic acid 28-O-β-D-apiofuranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 4)-α-L-rhamnopyranosyl-(1 → 2)-β-D-fucopyranoside and 28-O-β-D-apiofuranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 4)-[β-D-glucopyranosyl-(1 → 3)]-α-L-rhamnopyranosyl-(1 → 2)-β-D-fucopyranoside. Diazomethane degradation providing selectively the 28-O-glycoside from the 3,28-O-bisglycoside was a useful method for the structure elucidation.     

西南远志中皂苷类成分的分离与鉴定

采用乙醇回流提取,通过硅胶柱、HPD100大孔树脂、Sephadex LH-20、半制备HPLC分离方法,运用现代谱学方法从西南远志中分离并鉴定了4个齐墩果酸型皂苷类化合物,均为顺反异构体,所用实验方法并不能有效分开。他们分别是:(E/Z)-PolygalasaponinXLIV(1),3-O-β-D-glucopyranosyl presenegenin 28-O-β-D-galactopyr-anosyl-(1→4)-β-D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-[6-O-acetyl-β-D-glucopyranosyl-(1→3)]-{4-O-([E/Z)-3,4-dimethoxycinnamoyl}]-β-D-fucopyranosyl ester(2),(E/Z)-PolygalasaponinXXX(3)(,E/Z)-senegasaponin C(4),均为首次从该种植物中分离得到。     

羽叶鬼灯檠中的单萜二糖苷

从羽叶鬼灯檠 (RodgersiapinnataFranch .)的根茎中分离得到 6个单萜二糖苷 ,它们的结构通过波谱方法分别鉴定为 :(E ) 3,7 dimethyl 1 O [α L rhamnopyranosyl (1→ 6 ) β D glu copyranosyl] oct 2 en 7 ol (1) ,(E ) 3,7 dimethyl 1 O [α L arabinofuranosyl (1→ 6 ) β D glucopy ranosyl] oct 2 en 7 ol (2 ) ,geranyl 1 O α L arabinofuranosyl (1→ 6 ) β D glucopyranoside (3) ,gera nyl 1 O α L rhamnopyranosyl (1→ 6 ) β D glucopyranoside (4 ) ,geranyl 1 O β D xylopyranosyl (1→6 ) β D glucopyranoside (5 ) ,geranyl 1 O α L arabinopyranosyl (1→ 6 ) β D glucopyranoside (6 )。其中化合物 1为新化合物 ,单萜二糖苷类化合物系首次在该属中发现。     

金铁锁的两个新三萜皂苷

从石竹科植物金铁锁(Psammosilene tunicoides W．C．Wu et C．Y．Wu)根部分离得到4个齐墩果酸型五环三萜皂苷。它们的结构通过波谱和化学方法分别鉴定为：3-O-β-D-galac-topyranosyl-(1→2 )-β-D-6-O-methylgtucuronopymnosyl-quillaic acid (1),3-O-β-D-galactopymnosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-gtucuronopyranosyl-quillaic acid (2),3-O-β-D-galactopyrano-syl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-6-O-methylgtucuronopyranosyl-quillaic acid(3),3-O-β-D-galactopymnosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-6-O-ethylgtucuronopyranosyl-quillaic acid(4)。其中1为木鳖子中发现的次甙,3和4为新化合物。     

小花草玉梅化学成分研究

目的：研究银莲花属植物小花草玉梅的化学成分。方法：采用硅胶柱色谱,凝胶柱色谱,反相柱色谱并结合制备高效液相色谱等技术分离纯化单体化合物,并根据理化性质及光谱数据鉴定结构。结果：分离并鉴定了4个化合物,分别是常春藤皂苷元-28-O-β-D-吡喃葡萄糖酯苷（1）、3-O-β-D-吡喃葡萄糖-（1→2）-α-L-吡喃阿拉伯糖-齐墩果酸皂苷元-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（2）、3-O-β-D-吡喃葡萄糖-（1→2）-α-L-吡喃阿拉伯糖-常春藤皂苷元-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）和3-O-β-D-吡喃核糖-（1→3）-α-L-吡喃鼠李糖-（1→2）-α-L-吡喃阿拉伯糖-常春藤皂苷元-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（4）。结论：化合物1为首次从银莲花属植物中分离得到,2-4为首次从小花草玉梅中分离得到。     

New Cytotoxic Saponins from Lysimachia davurica Ledeb.

To investigate the saponins from whole plants of Lysimachia davurica Ledeb., two new saponins named davuricoside I （compound 1） and E （compound 2） were isolated. Their chemical structures were elucidated as 3β, 16α, 28, 29-tetrihydroxy-olean-12-en-3-O-β-D-glucopyranosyl-（1→2）-β-D-glucuronopyranoside （compound 1） and 3β, 16α, 29-trihydroxy-13, 28-epoxy-oleanane-3-O-β-D-glucopyranosyl-（1→2）-β-D-glucuronopyranoside （compound 2） on the basis of their one- and two-dimensional nuclear magnetic resonance and mass spectrometry data, and chemical methods. Compound 1 showed significant cytotoxic activity against human A2780 cells.     

广东冬青中的三萜及三萜皂甙成分

从广东冬青（Ｉｌｅｘ ｋｗａｎｇｔｕｎｇｅｎｓｉｓ）的叶中分离得到四个三萜皂甙和三个三萜成分,通过光谱解析及化学方法,三个三萜成分分别鉴定为齐墩果酸（１）、熊果酸（２）和常春藤皂甙元（３）;四个三萜皂甙成分分别鉴定为齐墩果酸３－Ｏ－β－Ｄ－吡喃葡萄糖基－（１→３）－α－Ｌ－吡喃阿拉伯糖甙（４）、齐墩果酸３－Ｏ－β－Ｄ－吡喃葡萄糖基－（１→２）－α－Ｌ－吡喃阿拉伯糖甙（５）、齐墩果酸３－Ｏ－β－Ｄ－     

Triterpenoid Saponins from Pulsatilla cernua (Thunb.)

To investigate saponins from the roots of Pulsatilla cernua (Thunb.) Bercht. et Opiz., two new compounds together with five known triterpenoid saponins were isolated. The structures of the two new triterpenoid saponins, named cernuasides A and B, were elucidated as 3-O-[β-D-xylopyranosyl(1→2)]-[α-L-rhamnopyranosyl(1→4)]-α-Larabinopyranosyl hederagenin 28-O-β-D-glucopyranosyl ester (compound 1) and 3-O-[α-L-arabinopyranosyl(1→3)]-[α-L-rhamnopyranosyl (1→2)]-α-L-arabinopyranosyl hederagenin 28-O-β-D-glucopyranosyl ester (compound 2) by 1D, 2D-NMR techniques, ESIMS analysis, as well as chemical methods.