Platycoside O, a new triterpenoid saponin from the roots of Platycodon grandiflorum

A new unusual minor triterpenoid saponin, platycoside O (1), was isolated from the 75% EtOH extract obtained from the roots of Platycodon grandiflorum, together with four known saponins: platycoside M-3 (2), platycoside J (3), platycoside F (4) and platycoside B (5). The structure of 1 was determined as 3-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl-2β,3β,16α,23-tetrahydroxyolean-12-en-24-methoxyl, 24-oxo-28-oic acid 28-O-β-D-xylopyranosyl-(1→4)-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside on the basis of spectral analysis and chemical evidence.     

Five new triterpenoid saponins from the roots of Platycodon grandiflorum

Five new triterpenoid saponins, platycoside H [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23-tetrahydroxyolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], platycoside I [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23-tetrahydroxyolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], platycoside J [3-O-beta-D-glucopyranosyl-2beta,3beta,16alpha,23-tetrahydroxyolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], platycoside K [3-O-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23,24-pentahydroxyolean-12-en-28-oic acid], and platycoside L [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23,24-pentahydroxyolean-12-en-28 oic acid], and three known triterpenoid saponins, platycoside F, platycoside B, and platycoside C, were isolated from the roots of Platycodon grandiflorum A. DC. Their chemical structures were elucidated on the basis of their spectral data and chemical evidence.     

Platycoside N: a new oleanane-type triterpenoid saponin from the roots of Platycodon grandiflorum

A new oleanane-type triterpenoid saponin, named platycoside N (1), together with six known saponins, was isolated from the roots of Platycodon grandiflorum. On the basis of acid hydrolysis, comprehensive spectroscopic data analyses and comparison with the spectral data of the known compounds, its structure was elucidated as 3-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranosyl-2β,3β,16α,23-tetrahydroxyolean-12-en-28-oic acid 28-O-β-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranoside. The six known compounds were platycodin D (2), deapioplatycodin D (3), platycodin D3 (4), deapioplatycodin D3 (5), platycoside E (6) and deapioplatycoside E (7).     

Two antifungal active triterpenoid saponins from the seeds of Lathyrus plants

Two novel triterpenoid glycosides have been isolated from butanolic seeds extract of two varieties of Lathyrus plants, i.e. Lathyrus ratan and Lathyrus aphaca. Their structures were elucidated as 3-O-[β-D-glucuronopyranosyl-(1?→?4)-α-L-arabinopyranosyl-(1?→?2)-α-L-arabinopyranosyl]-olean-11,13(18)-dien-28-oic acid (1) and 3-O-{β-D-xylopyranosyl-(1 → 2)-β-D-glcopyranosyl-(1?→?4)-[β-D-glucopyranosyl-(1?→?2)]-β-D-xylopyranosyl}-2,16α-dihydroxy-4-hydroxymethyl urs-12-en-28-oic acid (2) on the basis of spectral evidences, i.e. FTIR, (1)H-NMR, (13)C-NMR, ESI-MS and FAB-MS data. The isolated saponins were tested for their antifungal activity. Compound 1 showed maximum inhibition against Colletotrichum dematium (77.8%), whereas compound 2 showed maximum inhibition against Alternaria alternata (53.9%).     

Preparation and enantiomer separation behavior of selectively methylated β-cyclodextrin-bonded stationary phases for high performance chromatography

Native and three selectively methylated β-cyclodextrin (β-CD)-bonded stationary phases without an unreacted spacer arm for liquid chromatography were prepared, where heptakis(2-O-methyl)-β-CD, heptakis(3-O-methyl)-β-CD and heptakis(2,3-di-O-methyl)-β-CD were used as the methylated β-CDs. The enantiomer separation abilities of the resulting β-CD stationary phases for 12 pairs of dansylamino acid enantiomers and six pairs of N-3,5-dinitrobenzoyl amino acid methyl esters as model solutes were investigated. The effects of pH and methanol content of the mobile phase on the retention and resolution were examined to optimize the mobile phase conditions. The optimum resolution for the dansylamino acids was achieved using a mobile phase consisting of 1.0% triethylammonium acetate buffer (pH 5.0)–methanol (v/v 4/6) on the β-CD stationary phase. Heptakis(3-O-methyl)- and heptakis(2,3-di-O-methyl)-β-CD-bonded stationary phases showed little enantiomer separation abilities for the dansylamino acids. The heptakis(2-O-methyl)-β-CD-bonded stationary phase exhibited no enantioselectivities for those solutes.

For the N-3,5-dinitrobenzoyl amino acid methyl esters, the optimum resolution was achieved using a mobile phase consisting of 1.0% triethylammonium acetate buffer (pH 5.0)–methanol (v/v 9/1) on a heptakis(2-O-methyl)-β-CD stationary phase. The heptakis(2,3-di-O-methyl)-β-CD-bonded stationary phases exhibited no enantioselectivities for the N-3,5-dinitrobenzoyl amino acid methyl esters. β-CD and heptakis(3-O-methyl)-β-CD-bonded stationary phases had no enantiomer separation abilities for those solutes except for the N-3,5-dinitrobenzoyl phenylalanine methyl ester.     

Triterpene Glycosides from <Emphasis Type="Italic">Kalopanax septemlobum</Emphasis>. II. Glycosides E,K, and L from Leaves of <Emphasis Type="Italic">Kalopanax septemlobum</Emphasis> var. <Emphasis Type="Italic">maximowiczii</Emphasis> Introduced to Crimea

The known hederagenin 3-O-β-D-glucopyranosyl-(1→4)-O-β-D-xylopyranosyl-(1→ 3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside (sapindoside C) and its 28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl and 28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl esters, new triterpene glycosides, were isolated from leaves of Kalopanax septemlobum var. maximowiczii introduced to Crimea. The structures of these compounds were established using chemical methods and two-dimensional NMR spectroscopy.__________Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 260–262, May–June, 2005.     

New Triterpenes from the Heartwood of Melaleuca leucadendron L.

Fourteen chemical constituents were isolated from the CHCl₃ soluble portion of the heartwood of Melaleuca leucadendron L. These compounds include β-sitosterol (1) , β-sitostenone (2) , 6-hydroxy-4,6-dimethyl-3-hepten-2-one (3) , naphthalene (4) , squalene (5) , 2α3β-dihydroxyurs-12-en-28-oic acid (6) , 3β-hydroxylup-20(29)-en-27,28-dioic acid (7) , 2α,3β-dihydroxyolean-12-en-28-oic acid (8) , 3β,23-dihydroxyolean-12-en-28-oic acid (9) , 2α,3β,23-trihydroxyolean-12-en-28-oic acid (10) , 3β-trans-p-coumaroyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (11) , and three novel oleanane derivatives 23-trans-p-coumaroyloxy-2α,3β-dihydroxyotean-12-en-28-oic acid (12), 3β-trans-caffeoyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (13) , and its isomer 3β-cis-caffeoyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (14) , The three novel compounds were characterized as the two and three O-methylated derivatives, respectively.     

Two new triterpenoid saponins from <Emphasis Type="Italic">Lysimachia davurica</Emphasis>

Two new saponins were isolated from an ethanol extract of the whole plants of Lysimachia davuria. The new saponins were respectively characterized as 3-O-{β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-L-arabinopyranosyl}-3β,28-dihydroxyolean-12-en-30-oic acid-O-[β-D-xylopyranosyl-(1→2)-β-D-glucopyranosyl]-ester (1) and 3-O-{ β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-L-arabinopyranosyl}-3β,28-dihydroxyolean-12-en-30-oic acid-O-β-D-glucopyranosyl-ester (2). Their structures were determined by 1D, 2D NMR and MS techniques. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 466–468, September–October, 2007.     

Triterpene Glycosides from Kalopanax septemlobum. III. Glycosides D2, I1, and K1 from Leaves of Kalopanax septemlobum var. maximowiczii Introduced in Crimea

The new caffeylated triterpene glycosides hederagenin 3-O-(6-O-caffeyl-β-D-glucopyranosyl)-(1→4)-O-β-D-xylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→2)-O-β-L-arabinopyranoside and its 28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl and 28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl esters were isolated from leaves of Kalopanax septemlobum var. maximowiczii introduced in Crimea. The structures of these compounds were established using chemical methods and NMR spectroscopy.__________Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 263–267, May–June, 2005.     

Triterpene Glycosides from Kalopanax septemlobum. 1. Glycosides A, B, C, F, G1, G2, I2, H, and J from Leaves of Kalopanax septemlobum var. Maximowichii Introduced to Crimea

Eight known glycosides of hederagenin and the new triterpene glycoside 3-O-β-D-xylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester of hederagenin were isolated by chromatographic methods from leaves of Kalopanax septemlobum var. maximowichii introduced to Crimea. The known 3-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester of hederagenin was observed for the first time in Kalopanax septemlobum.__________Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 156–159, March–April, 2005.     

Two oleananes from Ammannia auriculata Willd

Two new compounds: 3-β,15-α,23,28-tetrahydroxyolean-12-en-3-O-arabinopyaranoside and 3-β,23,28-trihydroxy-olean-12-en-3-O-β-D-glucopyranoside were isolated from the aerial parts of Ammania auriculata along with the known compounds kaempferol, β-sitosterol-3-O-β- D-glucoside, 2-α,3-β,23-trihydroxyolean-12-en-28-oic acid-28-O-β-D-glucopyranoside, quercetin, kaempferol-3-O-α-L-arabinofuranoside, kaempferol-3-O-β-D-xylopyranoside and ellagic acid. Structures of these compounds were elucidated on the basis of their spectroscopic data (NMR, UV, MS and IR spectra). The antioxidant activities of the total extract, the fractions CH(2)Cl(2), EtOAc and the remaining aqueous together with the compounds 1, 6 and 9 were comparable with that of the standard antioxidant, ascorbic acid.     

New triterpenoid saponins from Stelmatocrypton khasianum

Four new triterpenoid saponins, designated as stelmatotriterpenosides E-H (1-4), together with three known compounds, asterbatanoside B (5), 2alpha,3beta,19alpha,23-tetrahydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (6) and 2alpha,3beta,19alpha,23-tetrahydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (7), were isolated from the stems of Stelmatocrypton khasianum. On the basis of chemical and spectral evidence, the structures of 1-4 were established as 2alpha,3beta,23-trihydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (1), 2alpha,3beta,23-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (2), 2alpha,3beta,19alpha-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl ester (3), and 2beta,3beta,19alpha-trihydroxy-urs-12-en-24,28-dioic acid-24-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl diester (4).     

Triterpene glycosides from the stems of Akebia quinata

The stems of Akebia quinata have been analyzed for their triterpene glycoside constituents, resulting in the isolation of six new triterpene glycosides, along with 19 known ones. On the basis of extensive spectroscopic analysis, including 2D NMR data, and chemical evidence, the structures of the new compounds were deter-mined to be 3beta-[(O-beta-D-glucuronopyranosyl-(1-->3)-alpha-L-arabinopyranosyl)oxy]olean-12-en-28-oic acid O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3beta-[(O-beta-D-glucuronopyranosyl-(1-->3)-O-[alpha-L-rhamnopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl)oxy]olean-12-en-28-oic acid O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3beta-[(O-beta-D-glucuronopyranosyl-(1-->3)-alpha-L-arabinopyranosyl)oxy]-23-hydroxyolean-12-en-28-oic acid O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3beta-[(O-beta-D-glucuronopyranosyl-(1-->3)-O-[alpha-L-rhamnopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl)oxy]-23-hydroxyolean-12-en-28-oic acid O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3beta-[(O-beta-D-glucopyranosyl-(1-->3)-O-[alpha-L-rhamnopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl)oxy]-29-hydroxyolean-12-en-28-oic acid, and 3beta-[(O-beta-D-glucopyranosyl-(1-->3)-O-[alpha-L-rhamnopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl)oxy]-23,29-dihydroxyolean-12-en-28-oic acid, respectively. The main triterpene glycosides contained in the stems of A. quinata were found to have two sugar units at C-3 and C-28 of the aglycone in this study, whereas those of Akebia trifoliate were reported to possess one sugar unit at C-28 of the aglycone. It may be possible to distinguish between A. quinata and A. trifoliate chemically by comparing their triterpene glycoside constituents.     

New triterpene glucosides from the roots of Rosa laevigata Michx

Two new ursane-type triterpene glucosides, 2alpha,3alpha,24-trihydroxyurs-12,18-dien-28-oic acid beta-D-glucopyranosyl ester (1) and 2alpha,3alpha,23-trihydroxyurs-12,19(29)-dien-28-oic acid beta-D-glucopyranosyl ester (2), were isolated from the roots of Rosa laevigata, together with three known compounds: 2alpha,3beta,19alpha-trihydroxyurs-12-en-28-oic acid beta-Dglucopyranosyl ester (3), 2alpha,3alpha,19alpha-trihydroxyurs-12-en-28-oic acid beta-D-glucopyranosyl ester (4) and 2alpha,3beta,19alpha,23-tetrahydroxyurs-12-en-28-oic acid beta-D-glucopyranosyl ester (5). The structures of new compounds were established on the basis of detailed 1D and 2D NMR spectroscopic analyses. Compounds 2 and 5 exhibited modest in vitro antifungal activities against Candida albicans and C. krusei.     

Two new noroleanane-type triterpenoid saponins from the stems of Stauntonia chinensis

Two new noroleanane-type triterpenoid saponins, 3β,20α,24-trihydroxy-29-norolean-12-en-28-oic acid 24-O-β-L-fucopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucopyranoside (1) and 3β,20α,24-trihydroxy-29-norolean-12-en-28-oic acid 24-O-β-D-glucopyranosyl-(1→2)-[α-L-arabinopyranosyl-(1→3)]-β-D-glucopyranoside (2) were isolated from the stems of Stauntonia chinensis DC., together with three known compounds, brachyantheraoside B₂ (3), eupteleasaponin Ⅷ (4) and fargoside B (5). Their structures were elucidated by spectroscopic and chemical methods. The cytotoxic activities of compounds 1 and 2 were evaluated against five human tumor cell lines (HCT-116, HepG2, BGC-823, NCI-H1650, and A2780). Compounds 1 and 2 showed moderate cytotoxic activities toward the tested cell lines with IC₅₀ values ranging from 12.71 to 32.04 μM.     

Two new triterpenoid saponins from Platycodon grandiflorum.

Two new triterpenoid saponins, platycoside D [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->6)-beta-D- glucopyranosyl-2 beta, 3 beta, 16 alpha, 23-tetrahydroxyolean-12-ene-28-oic acid 28-O-beta-D- apiofuranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnop yranosyl- (1-->2)-alpha-L-arabinopyranoside] and platycoside E [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl- (1-->6)-beta-D-glucopyranosyl-2 beta,3 beta,16 alpha,23,24-pentahydroxyolean-12-ene-28-oic acid 28-O-beta-D-apiofuranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alp ha-L- rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside] were isolated from the roots of Platycodon grandiflorum. Structural determination is based on spectral and chemical evidence.     

Triterpene Glycosides from Cussonia paniculata. I. Isolation and Structure Determination of Glycosides A, B1, B2, C, D, G2, H1, and H2 from Leaves of Cussonia paniculata

The 3-O-β-D-glucopyranoside of β-sitosterol (1) and the known triterpene glycosides 3-O-α-L-arabinopyranosides of oleanolic (2a) and ursolic (2b) acids and hederagenin (3), 3-O-β-D-glucopyranosyl-(1→2)-α-L-arabinopyranosideofoleanolic acid (4), 3-O-α-L-arabinopyranosyl-28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosides of oleanolic (5a) and ursolic (5b) acids and the newglycoside 28-O-α-L-rhamnopyranosyl-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranoside of 23-hydroxyursolic acid (6) were isolated from leaves of Cussonia paniculata (Araliaceae). Their structures were established using chemical methods and NMR spectroscopy.__________Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 160–163, March–April, 2005.     

白山毛桃根抗脑胶质瘤活性成分及其纳米胶束的制备

采用溶剂提取和萃取方法得到白山毛桃根乙酸乙酯、 正丁醇和水层萃取物. 通过噻唑蓝(MTT)比色法考察了各萃取物对脑胶质瘤细胞U87MG活性的抑制作用. 采用高效液相色谱(HPLC)指纹图谱法比对确认活性部位的主要化学成分为2α,3α,24-三羟基-12-烯-28-乌苏酸. 采用溶剂挥发法制备了2α,3α,24-三羟基-12-烯-28-乌苏酸纳米胶束, 对其包封率、 粒径及ζ电位等进行了表征, 并考察了其抗肿瘤活性. 体外细胞实验结果表明, 白山毛桃根乙酸乙酯萃取物对脑胶质瘤细胞U87MG具有抑制作用, 通过与标准品比对确认2α,3α,24-三羟基-12-烯-28-乌苏酸为乙酸乙酯部位的主要成分, 且该成分对脑胶质瘤细胞活性具有较强抑制作用. 通过溶剂挥发法制备的2α,3α,4-三羟基-12-烯-28-乌苏酸纳米胶束包封率为64.7%, 粒径为20 nm, 粒径分布宽度(PDI)为0.246, ζ电位为-5.7 mV. 细胞实验结果进一步证明, 与单体化合物相比, 2α,3α,24-三羟基-12-烯-28-乌苏酸纳米胶束对脑胶质瘤细胞活性具有更强的抑制作用, 为白山毛桃根在脑胶质瘤治疗中的应用提供了实验依据.     

The triterpenes of commiphora—II The structures of commic acid C and commic acid D

Evidence is presented to show that commic acid C is probably 2β,3β-dihydroxyolean-12-ene-23-oic acid (I); commic acid D is shown to be the ursane analogue, 2β,3β-dihydroxyurs-12-ene-23-oic acid (II).     

A new triterpene from the plant of uncaria macrophylla

Our ongoing investigations on the stem bark of Uncaria macrophylla afforded a new ursolic triterpene, 3β,6β,19α-trihydroxy-urs-12-en-28-oic acid-24-carboxylic acid methyl ester (1), named uncariursanic acid, and three known ursolic triterpenes including 3β,6β,19α-trihydroxy-23-oxo-urs-12-en-28-oic acid (2), 3β,6β,19α-trihydroxy-urs-12-en-28-oic acid (3) and ursolic acid (4). Their structures were elucidated by extensive spectral methods, including 1D and 2D NMR and HR-ESI-MS. The cytotoxicities of the four compounds were evaluated against two cancer cell lines (MCF-7 and HepG2) by the MTT method, and only compound 4 exhibited potent activity.