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].     

Yemuoside I, a new nortriterpenoid glycoside from Stauntonia chinensis.

A new nortriterpenoid glycoside, named yemuoside [I] was isolated from Stauntonia chinensis. On the basis of chemical and spectral evidence, it structure was determined as 3-O-[alpha-L-arabinopyranosyl-(1----3)-alpha-L-rhamnopyranosyl-(1- ---2)-alpha-L-arabinopyranosyl]-30-noroleana-12,20(29)-di en-28-oic acid 28-O-[beta-D-glucopyranosyl-(1----6)-beta-D-glucopyranosyl] ester.     

A new saponin from Deeringia amaranthoides

A new triterpenoid saponin, 3-O-[alpha-L-rhamnopyranosyl (1----3)-beta-D-glucuronopyranosyl]-28-O-[beta-D-xylopyranosyl (1----2)-beta-D-glucopyranosyl]-3 beta-hydroxyolean-12-en-28-oate [3] has been isolated together with two known saponins, 3-O-[alpha-L-rhamnopyranosyl (1----3)-beta-D-glucuronopyranosyl]-3 beta- hydroxyolean-12-en-28-oic acid [1] and 3-O-[alpha-L-rhamnopyranosyl (1----3)-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-3 beta- hydroxyolean-12-en-oate [2], from the fruits of Deeringia amaranthoides.     

Abrusosides A-D, four novel sweet-tasting triterpene glycosides from the leaves of Abrus precatorius

In addition to abrusoside A [1], abrusosides B [2], C [3], and D [4], three further sweet glycosides based on the novel cycloartane-type aglycone, abrusogenin [5], were isolated from an n-BuOH-soluble extract of the leaves of Abrus precatorius. Using a combination of spectral methods, the structures of compounds 1-4 were assigned, respectively, as the 3-O-beta-D-glucopyranosyl, the 3-O-beta-D-glucopyranosyl-(1----2)-beta-D-6-methylglucuronopyranosyl+ ++, the 3-O-beta-D-glucopyranosyl-(1----2)-beta-D-glucopyranosyl, and the 3-O-beta-D-glucopyranosyl-(1----2)-beta-D-glucuronopyranosyl derivatives of compound 5. After it established that compounds 1-4 were neither acutely toxic with mice nor mutagenic with Salmonella typhimurium strain TM677, they were found by a human taste panel to exhibit sweetness potencies in the range 30-100 times greater than sucrose.     

A new triterpenoidal saponin from Acacia auriculiformis.

A new triterpenoidal saponin has been isolated from an aqueous EtOH extract of the legumes of Acacia auriculiformis and characterized as 3-O-([beta-D-xylopyranosyl(1----3)-beta-D-xylopyranosyl(1----4)-alpha-L- rhamnopyranosyl(1----2)]-[alpha-L-rhamnopyranosyl(1----4)]-beta-D- glucopyranosyl)-3,16,21-trihydroxyolean-12-en-28-oic acid [1] by chemical studies and spectral data.     

Chemical studies on immunologically active polysaccharides of Ganoderma lucidum(Leyss. ex Fr.) Karst]

BN3B, the polysaccharide component of the fruit of Ganoderma lucidum, has been shown to have immune activity. From BN3B four homogeneous polysaccharides were separated and purified. Chemical studies on the main components BN3B1 and BN3B3 indicated that BM3B1 contained only glucose and should be a glucan containing beta-(1----6) and (1----3)glycoside bonds and that BN3B3 was an arabinogalactan containing beta-(1----6) and (1----3)glycoside bonds.     

The cytotoxic principles of Solanum incanum

In continuation of work on Solanum incanum a new steroidal alkaloid glycoside has been isolated from the fresh berries, which is named incanumine, and characterized as O(3)-[beta-D-xylopyranosyl-(1----3glu)-[beta-D-xylopyranosyl-(1--- -4rha)- alpha-L-rhamnopyranosyl-(1----4)]-beta-D-glucopyranosyl)-solasodine++ +. Solamargine, solasodine, ursolic acid, and ursolic acid derivatives (3-O-palmitoyl ursolic acid, 3-O-crotonyl ursolic acid, 3-O-propionyl ursolic acid) exhibited significant cytotoxic effects against human PLC/PRF/5 cells in vitro. Esterification of ursolic acid with aliphatic acids clearly enhanced the cytotoxic effects against human PLC/PRF/5 cells in vitro.     

Polypodoside A, an intensely sweet constituent of the rhizomes of Polypodium glycyrrhiza

Polypodoside A, a novel intensely sweet constituent of the rhizomes of Polypodium glycyrrhiza, was established by spectral and chemical methods as 26-O-alpha-L-rhamnopyranosyl-polypodogenin-3-O-alpha-L-rhamnopyran osyl- (1----2)-beta-D-glucopyranoside [1]. At the doses tested, this isolate was not acutely toxic for mice and was nonmutagenic with Salmonella typhimurium strain TM677. This compound was rated by a human taste panel as exhibiting 600 times the sweetness intensity of a 6% w/v aqueous sucrose solution.     

New tetrasaccharide flavonol glycoside from Epimedium acuminatum.

A new tetrasaccharide flavonol glycoside was isolated from the aerial parts of Epimedium acuminatum, along with three known flavonoids. The structure of the new compound, named acuminatoside [1], was established to be anhydroicaritin-3-O-alpha-L-rhamnopyranosyl(1----2)-alpha-L-rhamno pyranoside-7- O-beta-D-glucopyranosyl-(1----2)-beta-D-glucopyranoside by means of spectroscopic techniques (uv, eims, fdms, fabms, 1H nmr, 1H-1H COSY, 2D-J, 13C nmr, APT, and 1H-13C HETCOR) and chemical methods (acid hydrolysis, enzymatic hydrolysis, and tlc-densitometry). The known compounds were identified as icariin, epimedoside A, and kaempferitrin.     

Isoscutellarein-7-O-[allosyl (1----2) glucoside] from Sideritis leucantha

In continuation with our work on the flavonoids of Sideritis species, we have now isolated and identified from Sideritis leucantha extracts, the novel flavonoid compound, isoscutellarein-7-O-[allosyl (1----2) glucoside].     

Additional toxic, bitter saponins from the seeds of Chenopodium quinoa

Quinoa (Chenopodium quinoa) is an important Native American food grain. Prior to consumption, the seeds must be washed with H2O to remove bitterness and improve nutritive value. From the warm-H2O extract of quinoa seeds from Mexico, saponins 1-4 were isolated by monitoring the fractionation with brine shrimp lethality and a taste test for bitterness. By chemical, spectral, and enzymatic methods, 1-4 were identified as glycosides of oleanolic acid. Saponin 4, 3-O-[(beta-D-xylopyranosyl)(1----3)]-beta-D-glucuronopyranosyl-6-O -methyl ester]-oleanolic acid, is a new natural compound.     

Flavonoid glycosides from Rhazya orientalis

Six new flavonoid glycosides, quercetin 3-O-alpha-L-rhamnopyranosyl(1-->6)-[alpha-L-rhamnopyranosyl(1-->2)]-(4-O-trans-p-coumaroyl)-beta-D-galactopyranoside-7-O-alpha-L-rhamnopyranoside (1), quercetin 3-O-alpha-L-rhamnopyranosyl(1-->6)-[alpha-L-rhamnopyranosyl(1-->2)]-(3-O-trans-p-coumaroyl)-beta-D-galactopyranoside-7-O-alpha-L-rhamnopyranoside (2), isorhamnetin 3-O-alpha-L-rhamnopyranosyl(1-->6)-[alpha-L-rhamnopyranosyl(1-->2)]-(4-O-trans-p-coumaroyl)-beta-D-galactopyranoside-7-O-alpha-L-rhamnopyranoside (3), isorhamnetin 3-O-alpha-L-rhamnopyranosyl(1-->6)-[alpha-L-rhamnopyranosyl(1-->2)]-(3-O-trans-p-coumaroyl)-beta-D-galactopyranoside-7-O-alpha-L-rhamnopyranoside (4), isorhamnetin 3-O-alpha-L-rhamnopyranosyl(1-->6)-[alpha-L-rhamnopyranosyl(1-->2)]-(4-O-cis-p-coumaroyl)-beta-D-galactopyranoside-7-O-alpha-L-rhamnopyranoside (5), and isorhamnetin 3-O-alpha-L-rhamnopyranosyl(1-->6)-[alpha-L-rhamnopyranosyl(1-->2)]-(4-O-trans-feruloyl)-beta-D-galactopyranoside-7-O-alpha-L-rhamnopyranoside (6), were isolated from the dried aerial parts of Rhazya orientalis. The structures of 1-6 were determined by spectroscopic and chemical means.     

Four new flavonol glycosides from the leaves of Astragalus caprinus

Four new flavonol 3-O-glycosides were isolated from the leaves of Astragalus caprinus. Their structures were elucidated by spectroscopic methods as rhamnocitrin-3-O-[3-hydroxy-3-methylglutaroyl(1-->6)][beta-D-apiofuranosyl(1-->2)]-beta-D-galactopyranoside (1), rhamnetin-3-O-[3-hydroxy-3-methylglutaroyl(1-->6)][beta-D-apiofuranosyl(1-->2)]-beta-D-galactopyranoside (2), kaempferol-3-O-[beta-D-xylopyranosyl(1-->3)-alpha-L-rhamnopyranosyl(1-->6)]-beta-D-galactopyranoside (3), and quercetin-3-O-[beta-D-xylopyranosyl(1-->3)-alpha-L-rhamnopyranosyl(1-->6)][beta-D-apiofuranosyl(1-->2)]-beta-D-galactopyranoside (4).     

Kinmoonosides A-C, three new cytotoxic saponins from the fruits of Acacia concinna, a medicinal plant collected in myanmar

Three genuine saponins, named kinmoonosides A-C (1-3), have been isolated, together with a new monoterpenoid (4), from a methanolic extract of the fruits of Acacia concinna. The structures of kinmoonosides A-C were elucidated on the basis of spectral analysis as 3-O-?alpha-L-arabinopyranosyl(1-->6)-[beta-D-glucopyranosyl(1-->2) ]-b eta-D-glucopyranosyl?-21-O-?(6R, 2E)-2-hydroxymethyl-6-methyl-6-O-[4-O-(2'E)-6'-hydroxyl-2'-hydroxymet hyl-6'-methyl-2',7'-octadienoyl-beta-D-quinovopyranosyl]-2, 7-octadienoyl?acacic acid 28-O-alpha-L-arabinofuranosyl(1-->4)-[beta-D-glucopyranosyl(1-->3)]-a lpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl ester (1); 3-O-?alpha-L-arabinopyranosyl(1-->6)-[beta-D-glucopyranosyl(1-->2) ]-b eta-D-glucopyranosyl?-21-O-?(6S, 2E)-2-hydroxymethyl-6-methyl-6-O-[4-O-(2'E)-6'-hydroxyl-2'-hydroxymet hyl-6'-methyl-2',7'-octadienoyl-beta-D-quinobopyranosyl]-2, 7-octadienoyl?acacic acid 28-O-alpha-L-arabinofuranosyl(1-->4)-[beta-D-glucopyranosyl(1-->3)]-a lpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl ester (2); and 3-O-?alpha-L-arabinopyranosyl(1-->6)-[beta-D-glucopyranosyl(1-->2) ]-b eta-D-glucopyranosyl?-21-O-[(2E)-6-hydroxyl-2-hydroxymethyl-6-methyl- 2,7-octadienoyl]acacic acid 28-O-alpha-L-arabinofuranosyl(1-->4)-[beta-D-glucopyranosyl(1-->3)]-a lpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl ester (3), respectively. The new monoterpenoid 4 was determined as 4-O-[(2E)-6-hydroxyl-2-hydroxymethyl-6-methyl-2, 7-octadienoyl]-D-quinovopyranose. Compounds 1-3 showed significant cytotoxicity against human HT-1080 fibrosarcoma cells.     

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.     

Cytotoxic oleanane-type saponins from Albizia inundata

Bioassay-guided fractionation of a CH(2)Cl(2)-MeOH extract of the aerial parts of Albizia inundata resulted in the isolation of two new natural oleanane-type triterpene saponins {3-O-[α-L-arabinopyranosyl(1→6)]-2-acetamido-2-deoxy-β-D-glucopyranosyl oleanolic acid (1) and 3-O-[α-L-arabinopyranosyl(1→2)-α-L-arabinopyranosyl(1→6)]-2-acetamido-2-deoxy-β-D-glucopyranosyl acacic acid lactone (2)} along with seven known saponins {3-O-[α-L-arabinopyranosyl(1→6)]-2-acetamido-2-deoxy-β-D-glucopyranosyl echinocystic acid (3), 3-O-[β-D-xylopyranosyl (l→2)-α-L-arabinopyranosyl(l→6)]-2-acetamido-2-deoxy-β-D-glucopyranosyl acacic acid lactone (concinnoside D) (4), 3-O-[β-D-glucopyranosyl(l→2)]-β-D-glucopyranosyl oleanolic acid (5), 3-O-[α-L-arabinopyranosyl(1→2)-α-L-arabinopyranosyl(l→6)]-β-D-glucopyranosyl oleanolic acid (6), 3-O-[β-D-xylopyranosyl(1→2)-α-L-arabinopyranosyl(l→6)]-β-D-glucopyranosyl oleanolic acid (7), 3-O-[α-L-arabinopyranosyl(l→2)-α-L-arabinopyranosyl(1→6)-[β-D-glucopyranosyl(l→2)]-β-D-glucopyranoside echinocystic acid (8), and 3-O-[β-D-xylopyranosyl(l→2)-α-L-arabinopyranosyl(1→6)-[β-D-glucopyranosyl(l→2)]-β-D-glucopyranoside echinocystic acid (9)}. The structures of 1 and 2 were established on the basis of extensive 2D NMR ((1)H-(1)H COSY or DQF-COSY, HSQC, HMBC, TOCSY, and HSQC-TOCSY) spectroscopic, ESIMS, and chemical methods. Saponins 1, 3, 6, and 7 showed cytotoxicity against human head and neck squamous cells (JMAR, MDA1986) and melanoma cells (B16F10, SKMEL28) with IC(50) values in the range 1.8-12.4 μM, using the MTS assay.     

Minor sesquiterpenes with new carbon skeletons from the brown alga Dictyopteris divaricata

Five minor sesquiterpenes (1-5) with two novel carbon skeletons, together with a minor new oplopane sesquiterpene (6), have been isolated from the brown alga Dictyopteris divaricata. By means of spectroscopic data including IR, HRMS, 1D and 2D NMR, and CD, their structures including absolute configurations were assigned as (+)-(1R,5S,6S,9R)-3-acetyl-1-hydroxy-6-isopropyl-9-methylbicyclo[4.3.0]non-3-ene (1), (+)-(1R,3S,4S,5R,6S,9R)-3-acetyl-1,4-dihydroxy-6-isopropyl-9-methylbicyclo[4.3.0]nonane (2), (+)-(1R,3R,4R,5R,6S,9R)-3-acetyl-1,4-dihydroxy-6-isopropyl-9-methylbicyclo[4.3.0]nonane (3), (+)-(1S,2R,6S,9R)-1-hydroxy-2-(1-hydroxyethyl)-6-isopropyl-9-methylbicyclo[4.3.0]non-4-en-3-one (4), (-)-(5S,6R,9S)-2-acetyl-5-hydroxy-6-isopropyl-9-methylbicyclo[4.3.0]non-1-en-3-one (5), and (-)-(1S,6S,9R)-4-acetyl-1-hydroxy-6-isopropyl-9-methylbicyclo[4.3.0]non-4-en-3-one (6). Biogenetically, the carbon skeletons of 1-6 may be derived from the co-occurring cadinane skeleton by different ring contraction rearrangements. Compounds 1-6 were inactive (IC(50) > 10 mug/mL) against several human cancer cell lines.     

Acylated preatroxigenin glycosides from Atroxima congolana

Six new acylated bisdesmosidic preatroxigenin saponins named atroximasaponins E1, E2 (1, 2), F1, F2 (3, 4), and G1, G2 (5, 6) were isolated as three inseparable mixtures of the trans- and cis-p-methoxycinnamoyl derivatives, from the roots of Atroxima congolana. Their structures were established through extensive NMR spectroscopic analysis as 3-O-beta-D-glucopyranosylpreatroxigenin-28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->3)]-[4-O-trans-p-methoxycinnamoyl]-beta-D-fucopyranoside (atroximasaponin E1, 1), and its cis-isomer, atroximasaponin E2 (2), 3-O-beta-D-glucopyranosylpreatroxigenin-28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-[6-O-acetyl-beta-D-glucopyranosyl-(1-->3)]-[4-O-trans-p-methoxycinnamoyl]-beta-D-fucopyranoside (atroximasaponin F1, 3), and its cis-isomer, atroximasaponin F2 (4), 3-O-beta-D-glucopyranosylpreatroxigenin-28-O-beta-D-apiofuranosyl-(1-->3)-[alpha-l-rhamnopyranosyl-(1-->2)]-[4-O-trans-p-methoxycinnamoyl]-beta-D-fucopyranoside (atroximasaponin G1, 5), and its cis-isomer, atroximasaponin G2 (6), respectively.     

Phytochemical investigation of Turnera diffusa

A phytochemical investigation of Turnera diffusa afforded 35 compounds, comprised of flavonoids, terpenoids, saccharides, phenolics, and cyanogenic derivatives, including five new compounds (1-5) and a new natural product (6). These compounds were characterized as luteolin 8-C-E-propenoic acid (1), luteolin 8-C-beta-[6-deoxy-2-O-(alpha-l-rhamnopyranosyl)-xylo-hexopyranos-3-uloside] (2), apigenin 7-O-(6' '-O-p-Z-coumaroyl-beta-d-glucopyranoside) (3), apigenin 7-O-(4' '-O-p-Z-coumaroylglucoside) (4), syringetin 3-O-[beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranoside] (5), and laricitin 3-O-[beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranoside] (6). Their structures were determined by spectroscopic and chemical methods.     

白花丹参的化学成分研究(Ⅱ)

目的 研究白花丹参的化学成分.方法 采用色谱法分离,波谱学数据分析鉴定结构.结果 从白花丹参根的乙醇提取物中分离得到4个化合物,分别鉴定为8,9-dihydro-1,6-dimethylfuro[3,2-c] naphtha[2,1-e]oxepine-10,12-dione(I)、丹参二醇C(II)、鼠尾草酚酮(Ⅲ)和1,2,6,7,8,9-hexahydro-1,6,6-trimethyl-3,11-dioxanaphtho[2,1-e]azulene-10,12一dione(IV).结论 化合物I为新化合物,命名为白花丹参酮(salmilalba-none),化合物Ⅱ～Ⅳ为首次从白花丹参中分离获得.