Steroid glycosides ofNicotiana tabacum seeds I. The structures of nicotianosides A,B, and E

Two steroid glycosides of the spirostan series — nicotianosides A and B — and one glycoside of the furostan series — nicotianoside E — have been isolated from the seeds ofNicotiana tabacum L. Nicotianoside A is (25S)-5α-spirostan-3β-ol 3-O-β-D-glucopyranoside, nicotianoside B is (25S)-5β-spirostan-3β-ol 3-O-[O-α-L-rhamnopyranosyl-(1→2)-gb-D-glucopyranoside], and nicotianoside E is (25S)-5α-furostan-3β,22α,26-triol 26-O-β-glucopyranoside 3-O-[O-α-L-rhamnopyranosyl-(1→2)-β-D-glucopyranoside].     

Triterpene glycosides of Astragalus and their genins. XXIV. Cycloorbicoside G from Astragalus orbiculatus

A bisdesmosidic glycoside — cycloorbicoside G — has been isolated from the epigeal parts of the plantAstragalus orbiculatus Ledeb. (Leguminosae), and on the basis of chemical transformations and spectral characteristics its structure has been established as (23R,24S)-16β,23;16α,24-diepoxycycloartane-3β,7β,25-triol 25-O-β-D-glucopyranoside 3-O-β-D-xylopyranoside.     

Three new megastigmane glucopyranosides from the Cardamine komarovii

Three new megastigmane glucopyranosides, komaroveside A [(3S,4R,5Z,7E)-3,4-dihydroxy-5,7-megastigmadien-9-one-3-O-β-D-glucopyranoside] (1), komaroveside B [(3S,4S,5S,6R,7E)-5,6-epoxy-3,4-dihydroxy-7-megastigmen-9-one-3-O-β-D-glucopyranoside] (2) and komaroveside C [(3S,4S,5S,6R,7E,9S)-5,6-epoxy-3,4,9-trihydroxy-7-megastigmen-3-O-β-D-glucopyranoside] (3) were isolated, together with eight known compounds, from Cardamine komarovii. The identification of these compounds and the elucidation of their structures were based on 1D- and 2D-NMR spectral data analysis. The isolated compounds were tested for their cytotoxicity against four human tumor cell lines (A549, SK-OV-3, SK-MEL-2, HCT15) in vitro using the sulforhodamine B bioassay.     

3-Hydroxydihydrobenzofuran glucosides from Gnaphalium polycaulon

A new 3-hydroxydihydrobenzofuran glucoside, gnaphaliol 9-O-β-D-glucopyranoside (2), was isolated from the aerial parts of Gnaphalium polycaulon together with 1-{(2R*,3S*-3-(β-D-glucopyranosyloxy)-2,3-dihydro-2-[1-(hydroxyl methyl)vinyl]-1-benzofuran-5-yl}-ethanone or gnaphaliol 3-O-β-D-glucopyranoside (1), (Z)-3-hexenyl O-β-D-glucopyranoside (3) and adenosine (4). The absolute configurations at C-2 and C-3 positions of compound 1 were determined to be 2R and 3R. The structures of these compounds were elucidated on the basis of their physical and spectroscopic data.     

Two new 3-oxo-α-ionol glucosides from Urtica laetevirens Maxim

Two new 3-oxo-α-ionol glucoside isomers, (6R,9R)-3-oxo-α-ionol-9-O-β-D-glucopyranosyl (1?→?2)-β-D-glucopyranoside (1) and (6S,9R)-3-oxo-α-ionol-9-O-β-D-glucopyranosyl (1?→?2)-β-D-glucopyranoside (2) were isolated from the aerial parts of Urtica laetevirens Maxim. Their structures, including stereochemistry, were established by spectral analyses (HR-ESI-MS, NMR and CD). Also, 3-oxo-α-ionol glucosides were isolated from Urtica species for the first time.     

Tomatoside a from the seeds ofLycopersicum esculentum

Results are given which confirm the structure of the furostanol glycoside from tomato seeds forming wastes of the preserving industry. From a butanolic extract of the seeds ofLycopersicum esculentum Mill. we have isolated the furostanol glycoside tomatoside A (I) the structure of which has been established as 25(S)-5α-furostan-3β,22α,26-triol 26-O-β-D-glucopyranoside 3-O-[O-β-D-glucopyranosyl-(1→2)-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside]. At the same time, by enzymatic and chemical transformations three new spirostanol glycosides of neotigogenin have been obtained: tomatoside B (III), which is 25(S)-5α-spirostan-3β-ol 3-O-[O-β-D-glucopyranosyl-(1→2)-β-D-galactopyranoside], 25(S)-5α-spirostan-3β-ol 3-O-[O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside] (V), and 25(S)-5α-spirostan-3β-ol 3-O-β-D-galactopyranoside (IV).     

Three new triterpenoid saponins from Dianthus superbus

Three new triterpenoid saponins (1-3) were isolated from the dried aerial parts of Dianthus superbus L. (Caryophyllaceae). Their structures were established as 3-O-β-D-glucopyranosyl gypsogenic acid 28-O-[β-D-6-O-((3S)-3-hydroxyl-3-methylglutaryl)glucopyranosyl(1→6)]-β-D-glucopyranoside (1), 3-O-β-D-glucopyranosyl gypsogenic acid 28-O-[β-D-glucopyranosyl(1→3)][β-D-6-O-((3S)-hydroxyl-3-methylglutaryl)glucopyranosyl(1→6)]-β-D-glucopyranoside (2), 3-O-α-L-arabinopyranosyl-3β,16α-dihydroxyolean-12-en-23,28-dioic acid 28-O-[β-D-glucopyranosyl-(1→6)]-β-D-glucopyranoside (3), on the basis of various spectroscopic analyses and chemical degradations.     

3-Hydroxymethylglutaryl flavonol glycosides from a Mongolian and Tibetan medicine, Oxytropis racemosa

Three new flavonol 3-O-glycosides, rhamnetin 3-O-[(S)-3-hydroxy-3-methyl-glutaroyl(1→6)]-β-D-glucopyranoside (1), rhamnocitrin 3-O-[(S)-3-hydroxy-3-methylglutaroyl(1→6)]-β-D-glucopyranoside (2), and isorhamnetin 3-O-[(S)-3-hydroxy-3-methylglutaroyl(1→6)]-α-L-rhamnopyranosyl(1→2)-β-D-glucopyranoside (3), along with 13 known compounds, were isolated from Oxytropis racemosa TURCZ. Their structures were deduced by means of spectroscopic methods and chemical evidence. 2 and 6 showed cytotoxic activities against HCT-8 (IC?? 6.38 μM) and A549 (IC?? 5.20 μM), respectively.     

Three steroids with unique structural feature of 5β-Spirostan-1β,3β,17α-trihydroxyl from Reineckia carnea

A new spirostanol sapogenin and two spirostanol saponins, tentatively named reineckiagenin A (1), reineckiagenoside A (2), and reineckiagenoside B (3), were isolated from the whole plant of Reineckia carnea. By detailed analysis of their 1D and 2D NMR spectra, chemical methods, and by comparison with spectra data of known compounds, the structures of the new steroids were determined to be 25(S)-5β-spirostan-1β,3β,17α-triol (1), 25(S)-5β-spirostan-1β,3β,17α-triol 1-O-β-D-xylopyranoside (2), 25(S)-5β-spirostan-1β,3β,17α-triol 1-O-α-L-rhamnopyranosyl-(1→2)-β-D-xylopyranoside (3). Compounds 1, 2, and 3 are the first naturally occurring steroids with unique structural feature of 5β-spirostan-1β,3β,17α-trihydroxyl.     

Benzyl 2-β-glucopyranosyloxybenzoate, a new phenolic acid glycoside from Sarcandra glabra

From the whole plant of Sarcandra glabra, a new phenolic acid glycoside, benzyl 2-β-glucopyranosyloxybenzoate (1), together with seven known compounds including eleutheroside B? (2), 5-O-caffeoylshikimic acid (3), (-)-(7S, 8R)-dihydrodehydrodiconiferyl alcohol (4), (-)-(7S, 8R)-dihydrodehydrodiconiferyl alcohol 9-, 9′- and 4-O-α-D-glucopyranoside (5-7), and (-)-(7S, 8R)-5-methoxydihydrodehydrodiconiferyl alcohol 4-O-β-D-glucopyranoside (8) was isolated. Their structures were elucidated by spectral analysis including 1D-, 2D-NMR and HR-ESI-MS. Compound 2 was found to exhibit potent cytotoxic activity against BGC-823 and A2780 cancer cell lines using MTT method with IC?? value of 2.53 and 1.85 μM, respectively.     

Triterpene glycosides ofAstragalus and their genins XLV. The chemical transformation of cycloartanes 1. Synthesis of 25-norglycosides

Literature information is given on the current state of the study of the chemical transformation of cycloartane triterpenoids. A method has been developed for the transformation of the genin part of glycosides of 20,24-epoxycycloartan-25-ols with retention of the carbohydrate constituents. Three 25-norglycosides have been synthesized from natural cyclosieversigenin glycosides, namely 16β-acetoxy-3β,6α-dihydroxy-20R,25-norcycloartan-20,24-olide 3-O-[O-α-L-arabinopyranosyl-(1→2)-β-D-xylopyranoside] 6-O-β-D-xylopyranoside (VIII), sodium 3β,6α,16β,20-tetrahydroxy-20R,25-norcycloartan-24-oate 6-O-β-D-glucopyranoside 3-O-β-D-xylopyranoside (XII), and 20R,25-norcycloartane-3β,6α,16β,20,24-pentaol 6-O-β-D-glucopyranoside 3-O-β-D-xylopyranoside (XIII).     

Steroid glycosides of the seeds ofPetunia hybrida II. The structures of petuniosides I,L, and N

Three new steroid glycosides of the furostan series, petuniosides L L, and N, have been isolated from the seeds of Petunia hybrida L. Petunioside 1is (25 R)-5ot~-furostan-3ß, 22ot~, 26-triol 3-O-ß-D-galactopyranoside 26-O-ß-D-glucopyranoside, petunioside L. (25R)-5ot-furostan-3ß,22ot~,6-triol 3-O-[O-ß-D-glucopyranosyl-(1--,4)-ß-D-galactopyranoside] 26-O-ß-D-glucopyranoside, andpetunioside N is (25R)-5ot~-furostan-3ß,22ot,26-triol 3-0-[0-ß-D-glucopyranosyl- (1 --,2)-O-ß-D-glucopyranosyl- (1 --,4)-ß-D-galactopyranoside] 26-O-ß-D-glucopyranoside.Institute of Genetics, Academy of Sciences of the Republic of Moldova, 277002, Kishinev, ul. Desnaya, 20. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 247–252, March-April, 1995. Original article submitted August 29, 1994.     

Three new flavonoid glycosides, byzantionoside B 6'-O-sulfate and xyloglucoside of (Z)-hex-3-en-1-ol from Ruellia patula

Three new flavonoid glycosides, demethoxycentaureidin 7-O-β-D-galacturonopyranoside, pectolinarigenin 7-O-α-L-rhamnopyranosyl-(1?→4″)-β-D-glucopyranoside and 7-O-α-L-rhamnopyranosyl-(1?→4″)-β-D-glucuronopyranoside, a new megastigmane glucoside, byzantionoside B 6'-O-sulfate, and a new (Z)-hex-3-en-1-ol O-β-D-xylopyranosyl-(1″→2')-β-D-glucopyranoside, were isolated from leaves of Ruellia patula JACQ., together with 12 known compounds, β-sitosterol glucoside, vanilloside, bioside (decaffeoyl verbascoside), acteoside (verbascoside), syringin, benzyl alcohol O-β-D-xylopyranosyl-(1″→2')-β-D-glucopyranoside, cistanoside E, roseoside, phenethyl alcohol O-β-D-xylopyranosyl-(1″→2')-β-D-glucopyranoside, (+)-lyoniresinol 3α-O-β-D-glucopyranoside, isoacteoside and 3,4,5-trimethoxyphenol O-α-L-rhamnopyranosyl-(1″→6')-β-D-glucopyranoside. Their structures were elucidated by means of spectroscopic analyses.     

A new flavonol glycoside from the seeds of Nigella glandulifera

A new flavonol glycoside, kaempferol 3-O-α-L-rhamnopyranosyl (1?→?6)-O-[β-D-glucopyranosyl (1?→?2)-O-β-D-galactopyranosyl (1→2)]-O-β-D-glucopyranoside (1), together with a known compound, kaempferol 3-O-β-D-glucopyranosyl (1?→?2)-O-β-D-galactopyranosyl (1?→?2)-O-β-D-glucopyranoside (2) was isolated from the seeds of Nigella glandulifera. Their structures were elucidated on the basis of spectral analysis, including ESI-MS, ESI-MS/MS, HR-ESI-MS, DQF-COSY, TOCSY, HSQC and HMBC techniques.     

A new steroidal glycoside from the Ophiopogon japonicus Ker-Gawler (Liliaceae)

A new steroidal glycoside (1), (25R)-14α, 17α-hydroxyspirost-5-en-3β-yl 3-O-α-L-rhamnpyranosyl-(1 → 2)-β-D-glucopyranosyl-(1 → 3)-β-D-glucopyranoside, together with three known steroidal glycosides, (25R)-3β-hydroxyspirost-5-en-1β-yl-3-O-α-L-rhamnopyranosyl-(1 → 2)-O-β-D-xylopyranosyl-(1 → 3)-α-L-arabinopyranoside (2), Cixi-ophiopogon B (3) and Cixi-ophiopogon A (4), were obtained from the tuberous roots of Ophiopogon japonicus (Liliaceae). Compound 2 was isolated from the Ophiopogon genus for the first time. Their structures were identified on the basis of extensive mass and nuclear magnetic resonance spectroscopic analysis.     

Steroids of the spirostan and furostan series of plants of the Allium genus. XXIII. Structure of cepagenin and of alliospirosides C and D from Allium cepa

Two new steroid glycosides of the spirostan series have been isolated from the fruit ofAllium cepa L. (family Liliaceae): alliospirosides C and D. On the basis of chemical transformations and spectral characteristics it has been established that the aglycon of both glycosides is a new steroid sapogenin — cepagenin — having the structure of (24S,25R)-spirost-5-ene-1β,3β,24-triol. Alliospirosides C and D are cepagenin 1-O-[O-α-L-rhamnopyranosyl-(1→2)α-L-arabinopyranoside] and 1-O-[O-α-L-rhamnopyranosyl-(1→2)-O-β-D-galactopyranoside], respectively.     

New cytotoxic cerebroside from Gynura divaricata

A new cerebroside,gynuraoside(1),was isolated from the aerial parts of Gynura divaricata DC.It was determined to be 1-O-β- D-glucopyranosyl-(2S,3S,4R,10E)-2-[(2′R)-2′-hydroxyldocosanoyl-amino]-10-octadecene-1,3,4-triol on the basis of chemical and spectroscopic evidence.This compound showed strong cytotoxicity against L1210 leukemia cell line in vitro.     

A new eudesmane sesquiterpene glucoside from Liriope muscari fibrous roots

The screening of several Chinese medicinal herbs for nematocidal properties showed that the ethanol extract of Liriope muscari fibrous roots possessed significant nematocidal activity against the pine wood nematode (Bursaphelenchus xylophilus). From the ethanol extract, a new constituent (1,4-epoxy-cis-eudesm-6-O-β-D-glucopyranoside) and three known glycosides [1β,6α-dihydroxy-cis-eudesm-3-ene-6-O-β-D-glucopyranoside (liriopeoside A), 1β,6β-dihydroxy-cis-eudesm-3-ene-6-O-β-D-glucopyranoside, and 1α,6β-dihydroxy-5,10-bis-epi-eudesm-4(15)-ene-6-O-β D-glucopyranoside] were isolated by bioassay-guided fractionation. The structures were elucidated by 1D and 2D NMR and MS techniques. 1,4-Epoxy-cis-eudesm-6-O-β-D-glucopyranoside possessed moderate nemato-cidal activity against B. xylophilus with a LC(50 )value of 339.76 μg/mL, while liriopeoside A (LC(50) = 82.84 μg/mL) and 1β,6β-dihydroxy-cis-eudesm-3-ene-6-O-β-D-glucopyranoside (LC(50) = 153.39 μg/mL) also exhibited nematocidal activity against B. xylophilus. The crude extract of L. muscari fibrous roots exhibited nematocidal activity against the pine wood nematode with a LC(50) value of 182.56 μg/mL.     

Antioxidant, anti-glycation and anti-inflammatory activities of phenolic constituents from Cordia sinensis

Nine compounds have been isolated from the ethyl acetate soluble fraction of C. sinensis, namely protocatechuic acid (1), trans-caffeic acid (2), methyl rosmarinate (3), rosmarinic acid (4), kaempferide-3-O-β-D-glucopyranoside (5), kaempferol-3-O-β-D-glucopyranoside (6), quercetin-3-O-β-D-glucopyranoside (7), kaempferide-3-O-α-L-rhamnopyranosyl (1→6)-β-D-glucopyranoside (8) and kaempferol-3-O-α-L-rhamno-pyranosyl (1→6)-β-D-glucopyranoside (9), all reported for the first time from this species. The structures of these compounds were deduced on the basis of spectroscopic studies, including 1D and 2D NMR techniques. Compounds 1-9 were investigated for biological activity and showed significant anti-inflammatory activity in the carrageen induced rat paw edema test. The antioxidant activities of isolated compounds 1-9 were evaluated by the DPPH radical scavenging test, and compounds 1, 2, 4 and 7-9 exhibited marked scavenging activity compared to the standard BHA. These compounds were further studied for their anti-glycation properties and some compounds showed significant anti-glycation inhibitory activity. The purity of compounds 2-5, 8 and 9 was confirmed by HPLC. The implications of these results for the chemotaxonomic studies of the genus Cordia have also been discussed.     

Two new monoterpene glycosides from Doellingeria scaber

Two new methane-type monoterpene glycosides were isolated from the roots of Doellingeria scaber.Their structures wereidentified as trans-p-menthane-1α,2β,8-triol 8-O-β-D-(3',6'-diangeloyloxy)-glucopyranoside and trans-p-menthane-1α,2β,8-triol 8-O-β-D-(3'-angeloyloxy,6'-isobutyloxy)-glucopyranoside based on 1D and 2D NMR spectroscopy.