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.     

Antiproliferative triterpenes from the leaves and twigs of Juglans sinensis on HSC-T6 cells

Bioassay-guided fractionation of an 80% MeOH extract of leaves and twigs of Juglan sinensis has resulted in the isolation of four new triterpenes (1-4) and 17 known triterpenes (5-21). The new compounds were determined to be 1-oxo-3β,23-dihydroxyolean-12-en-28-oic acid 28-O-β-D-glucopyranoside (1), 1-oxo-3β-hydroxyolean-18-ene (2), 3β,23-dihydroxyurs-12-en-28-oic acid 28-O-β-D-glucopyranoside (3), and 3β,22α-dihydroxyurs-12-en-28-oic acid 28-O-β-D-glucopyranoside (4) by spectroscopic analysis. Compounds 2, 13, 15, and 21 showed antiproliferative activities (14.2, 14.8, 15.6, and 11.0% at 100 μM, respectively) in HSC-T6 cells. Flow cytometry assays revealed that these compounds inhibited HSC-T6 proliferation by inducing apoptosis.     

Oleanane-type triterpenes from the flowers and roots of Saussurea muliensis

Six new oleanane-type triterpenes (1- 6), along with five known compounds, were isolated from the flowers and roots of Saussurea muliensis. On the basis of spectroscopic methods, with special emphasis on 1D and 2D NMR techniques, the structures of the new compounds were characterized as 3beta,22alpha-dihydroxyolean-12-en-30-oic acid (1), 3alpha-(E)-caffeoyloxyolean-12-en-30-oic acid (2), 3alpha-(E)-coumaroyloxyolean-12-en-30-oic acid (3), 3alpha,22alpha-diacetoxy-20beta,21alpha,29-trihydroxy-30-norolean-12-ene (4), 3alpha,22alpha-diacetoxy-21alpha,29-dihydroxy-20beta-methoxy-30-norolean-12-ene (5), and 3alpha,22alpha-diacetoxy-20beta,21alpha-dihydroxy-29-palmityloxy-30-norolean-12-ene (6). The isolated compounds (1- 6) were not active against Staphylococcus aureus, Escherichia coli, Bacillus cereus, and Candida albicans.     

Monoterpene glycosides and triterpene acids from Eriobotrya deflexa

A phytochemical study on a methanolic extract of leaves of Eriobotrya deflexa led to the isolation and characterization of nine terpenoid compounds. Four of these are new chemical entities, including two monoterpene glycosides, (3S)-O-alpha-L-rhamnopyranosyl-(1-->3)-[4-O-(E)-coumaroyl]-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyl-linalool (1) and (3S)-O-alpha-L-rhamnopyranosyl-(1-->3)-[4-O-(Z)-coumaroyl]-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyl-linalool (2), and two triterpene acids, 1beta,2alpha,19alpha-trihydroxy-3-oxo-12-ursen-28-oic acid (3) and 2alpha,3alpha,19alpha-trihydroxy-12-oleanen-28-oic acid (4). Their structures were elucidated on the basis of spectroscopic analysis. The activities of these isolates in an in vitro antiproliferation test were also determined.     

Silenosides A-C, triterpenoid saponins from Silene vulgaris.

Three new triterpenoid saponins named silenosides A-C (1-3) were obtained from the roots of Silene vulgaris. Their structures were elucidated by spectral and chemical methods as beta-D-galactopyranosyl(1-->2)-beta-D-glucuronopyranosyl-3beta- hydrox y-23-oxoolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl(1-->3)-beta-D-xylopyranosyl(1-->4)-alpha-L- rhamnopyranosyl(1-->2)-beta-D-fucopyranoside; 3-O-beta-D-galactopyranosyl(1-->2)-beta-D-glucuronopyranosyl-3beta , 16alpha-dihydroxy-23-oxoolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl(1-->4)-[beta-D-glucopyranosyl(1-->2)]-alpha -L-rhamnopyranosyl(1-->2)-beta-D-fucopyranoside; and 3-O-alpha-L-arabinopyranosyl(1-->3)-[beta-D-galactopyranosyl(1-->2 )]- beta-D-glucuronopyranosyl-3beta, 16alpha-dihydroxy-23-oxoolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl(1-->4)-[beta-D-glucopyranosyl(1-->2)]-alpha -L-rhamnopyranosyl(1-->2)-beta-D-fucopyranoside, respectively.     

Triterpenoid saponins of Acanthopanax nipponicus leaves

Five new triterpenoid saponins, nipponosides A-E (1, 3-6), were isolated from Acanthopanax nipponicus leaves, along with a known saponin, kalopanaxsaponin G (2). Nipponosides A-E were characterized as the 28-O-alpha-L-rhamnopyranosyl(1-->4)-beta-D-glucopyranosyl(1-->6)-beta -D-glucopyranosyl ester of 3-oxohederagenin, oleanolic acid 3-O-beta-D-glucopyranoside, gypsogenin 3-O-beta-D-glucopyranoside, 3beta,23,29-trihydroxyolean-12-en-28-oic acid, and 3beta,20alpha, 23-trihydroxy-30-nor-olean-12-en-28-oic acid, respectively. The structures of these new compounds were based on chemical and spectral methods.     

Bioactive constituents from Boswellia papyrifera

Phytochemical investigation of the stem bark extract of Boswellia papyrifera afforded two new stilbene glycosides, trans-4',5-dihydroxy-3-methoxystilbene-5-O-{alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->6)]-beta-D-glucopyranoside (1), trans-4',5-dihydroxy-3-methoxystilbene-5-O-[alpha-L-rhamnopyranosyl-(1-->6)]-beta-D-glucopyranoside (2), and a new triterpene, 3alpha-acetoxy-27-hydroxylup-20(29)-en-24-oic acid (3), along with five known compounds, 11-keto-beta-boswellic acid (4), beta-elemonic acid (7), 3alpha-acetoxy-11-keto-beta-boswellic acid (8), beta-boswellic acid (9), and beta-sitosterol (10). The stilbene glycosides exhibited significant inhibition of phosphodiesterase I and xanthine oxidase. The triterpenes (3-9) exhibited prolyl endopeptidase inhibitory activities.     

Antitubercular activity of triterpenoids from Lippia turbinata

Assay-guided fractionation of the antitubercular MeOH-CH(2)Cl(2) extract obtained from Lippia turbinata led to the isolation of four novel triterpenoids-3beta,25-epoxy-3alpha,21alpha-dihydroxy-22beta-(3-methylbut-2-en-1-oyloxy)olean-12-ene-28-oic acid (1); 3beta,25-epoxy-3alpha,21alpha-dihydroxy-22beta-angeloyloxyolean-12-ene-28-oic acid (2); 3beta,25-epoxy-3alpha,21alpha-dihydroxy-22beta-tigloyloxyolean-12-ene-28-oic acid (3); and 3beta,25-epoxy-3alpha-hydroxy-22beta-(2-methylbutan-1-oyloxy)olean-12-ene-28-oic acid (4)-together with the known triterpenoids lantanilic acid (5), camaric acid (6), lantanolic acid (7), and rehmannic acid (8). The MIC values of 1-8 for growth inhibition of Mycobacterium tuberculosis were determined in the radiorespirometric BACTEC system.     

Three new triterpenes from Nerium oleander and biological activity of the isolated compounds

New ursane-type triterpene 1, oleanane-type triterpene 2, and dammarane-type triterpene 15 were isolated from the leaves of Nerium oleander together with 12 known triterpenes, 3beta-hydroxy-12-ursen-28-oic acid (ursolic acid, 3), 3beta,27-dihydroxy-12-ursen-28-oic acid (4), 3beta,13beta-dihydroxyurs-11-en-28-oic acid (5), 3beta-hydroxyurs-12-en-28-aldehyde (6), 28-norurs-12-en-3beta-ol (7), urs-12-en-3beta-ol (8), urs-12-ene-3beta,28-diol (9), 3beta-hydroxy-12-oleanen-28-oic acid (oleanolic acid, 10), 3beta,27-dihydroxy-12-oleanen-28-oic acid (11), 3beta-hydroxy-20(29)-lupen-28-oic acid (betulinic acid, 12), 20(29)-lupene-3beta,28-diol (betulin, 13), and (20S,24R)-epoxydammarane-3beta,25-diol (14). On the basis of their spectroscopic data, the structures of the new compounds 1, 2, and 15 were established as 3beta,20alpha-dihydroxyurs-21-en-28-oic acid, 3beta,12alpha-dihydroxyoleanan-28,13beta-olide, and (20S,24S)-epoxydammarane-3beta,25-diol, respectively. The anti-inflammatory activity of the seven isolated compounds and methyl esters of ursolic acid and oleanoic acid in vitro was examined on the basis of inhibitory activity against the induction of the intercellular adhesion molecule-1 (ICAM-1). The anticancer activity of the 14 isolated compounds, including 1, 2, 15, and methyl esters of ursolic acid and oleanolic acid in vitro was examined on the basis of the cell growth inhibitory activities toward three kinds of human cell lines.     

红花芒毛苣苔化学成分研究

目的:研究红花芒毛苣苔Aeschynanthus moningeriae的化学成分。方法:利用Diaion HP-20,Toyopearl HW-40,Sephadex LH-20,MCI-Gel CHP-20,RP18及硅胶等柱色谱法对红花芒毛苣苔中的化学成分进行分离纯化,根据理化性质和波谱技术鉴定化合物的结构。结果:从中分离鉴定了12个化合物,分别为5,7-二羟基-8-C-β-D-葡萄糖色酮碳苷(1),5-羟基-7,4’-二甲氧基黄酮(2),2,3,19,24-四羟基-12-烯-28-乌苏酸(3),2,3,19,24-四羟基-12-烯-28-乌苏酸-28-O-β-D-葡萄糖苷(4),5-羟基-6,4’-二甲氧基-7-[α-L-鼠李糖-1→6]-O-β-D-葡萄糖黄酮苷(5),5,7,3’,4’-四羟基-6-C-β-D-葡萄糖黄酮醇碳苷(6),5,7-二羟基-6-C-β-D-葡萄糖二氢黄酮碳苷(7);5,7,3’,4’-四羟基-6-C-β-D-葡萄糖二氢黄酮醇碳苷(8),胡萝卜苷(9),豆甾醇(10),β-谷甾醇(11),3-O-β-D-葡萄糖豆甾醇苷(12)。结论:化合物1为新化合物,其他化合物均为首次从该植物中分离得到。     

广西产美味猕猴桃根正丁醇部位化学成分研究

目的：研究广西产美味猕猴桃根正丁醇部位的化学成分。方法：应用色谱技术分离纯化，根据理化性质和波谱数据鉴定化合物结构。结果：从美味猕猴桃根正丁醇部位中分离并鉴定了6个化合物，分别为毛花猕猴桃酸B(1)，2α，3β，24 -三羟基-12-烯-28-乌苏酸(2)，2α，3α，24 -三羟基-12-烯-28-乌苏酸(3)，2α，3α，23-三羟基-12，20(30)-二烯-28-乌苏酸(4)，2α，3α，24-三羟基-12，20(30)-二烯-28-乌苏酸(5)，正丁基-O-β-D-吡喃果糖苷(6)。结论：化合物1～4，6均为首次从该植物中分离得到，其中化合物6为首次从猕猴桃属植物中分得。     

Ursane- and oleanane-type triterpenes from Ternstroemia gymnanthera callus tissues

An investigation on the constituents of the callus tissues of Ternstroemia gymnanthera has led to the isolation of five phytosterols, 15 known triterpenoids, and four new triterpenoids (1-4). The new compounds were characterized by spectroscopic study as 3-epi-corosolic acid lactone (2 alpha,3 alpha-dihydroxyurs-11-en-13 beta,28-olide) (1), 3-epi-ternstroemic acid (2 alpha,3 alpha-dihydroxyurs-12-en-11-on-28-oic acid) (2), ternstroemic acid (2 alpha,3 beta-dihydroxyurs-12-en-11-on-28-oic acid) (3), and gymnantheraic acid (2 alpha,3 alpha-dihydroxy-11 alpha-methoxyurs-12-en-28-oic acid) (4). The isolated triterpenes were compared with those from actinidiaceous plant callus tissues from a chemotaxonomic point of view.     

Natural products inhibiting Candida albicans secreted aspartic proteases from Lycopodium cernuum

Activity-guided fractionation of an ethanol extract of Lycopodium cernuum for Candida albicans secreted aspartic proteases (SAP) inhibition resulted in the identification of six new (1-6) and four known (7-10) serratene triterpenes, along with the known apigenin-4'-O-(2' ',6' '-di-O-p-coumaroyl)-beta-D-glucopyranoside (11). On the basis of spectroscopic analysis, the structures of 1-10 were established as 3beta,14alpha,15alpha,21beta,29-pentahydroxyserratane-24-oic acid (lycernuic acid C, 1), 3beta,14alpha,15alpha,21beta-tetrahydroxyserratane-24-oic acid (lycernuic acid D, 2), 3beta,14beta,21beta-trihydroxyserratane-24-oic acid (lycernuic acid E, 3), 3beta,21beta,29-trihydroxy-16-oxoserrat-14-en-24-methyl ester (lycernuic ketone A, 4), 3alpha,21beta,29-trihydroxy-16-oxoserrat-14-en-24-methyl ester (lycernuic ketone B, 5), 3alpha,21beta,24-trihydroxyserrat-14-en-16-one (lycernuic ketone C, 6), 3beta,21beta-dihydroxyserrat-14-en-24-oic acid (lycernuic acid A, 7), 3beta,21beta,29-trihydroxyserrat-14-en-24-oic acid (lycernuic acid B, 8), serrat-14-en-3beta,21beta-diol (9), and serrat-14-en-3beta,21alpha-diol (10). The 13C NMR data for the known compounds 7 and 8 are reported for the first time. Compounds 1 and 11 showed inhibitory effects against C. albicans secreted aspartic proteases (SAP) with IC50 of 20 and 8.5 microg/mL, respectively, while the other compounds were inactive.     

Triterpenoids from the resin of Styrax tonkinensis and their antiproliferative and differentiation effects in human leukemia HL-60 cells

Four new triterpenoids, 6beta-hydroxy-3-oxo-11alpha,12alpha-epoxyolean-28,13beta-olide (1), 3beta,6beta-dihydroxy-11alpha,12alpha-epoxyolean-28,13beta-olide (2), 3beta,6beta-dihydroxy-11-oxo-olean-12-en-28-oic acid (3), and 3beta-hydroxy-12-oxo-13Halpha-olean-28,19beta-olide (4), and five known triterpenes, 19alpha-hydroxy-3-oxo-olean-12-en-28-oic acid (5), 6beta-hydroxy-3-oxo-olean-12-en-28-oic acid (6), sumaresinolic acid (7), siaresinolic acid (8), and oleanolic acid (9), were isolated from the resin of Styrax tonkinensis. The structures of these triterpenoids were determined by physicochemical and spectroscopic methods. The configuration of compound 4 was confirmed by X-ray crystallographic analysis. All these triterpenoids inhibited HL-60 cell growth with IG(50) values ranging from 8.9 to 99.4 microM. Oleanolic acid (9) was the most effective antiproliferative agent, with an IG(50) value of 8.9 microM. While 3beta,6beta-dihydroxy-11-oxo-olean-12-en-28-oic acid (3) exhibited the least effective growth inhibition among these triterpenoids, it induced HL-60 cells to undergo differentiation as measured by an NBT reduction assay.     

Flavanone glycosides from Miconia trailii

Assay-guided fractionation of the ethanol extract of the twigs and leaves of Miconia trailii yielded two new flavanone glycosides, matteucinol 7-O-alpha-l-arabinopyranosyl(1-->6)-beta-d-glucopyranoside (miconioside A, 1) and farrerol 7-O-beta-d-apiofuranosyl(1-->6)-beta-d-glucopyranoside (miconioside B, 2), along with the known compounds matteucinol 7-O-beta-d-apiofuranosyl(1-->6)-beta-d-glucopyranoside (3), matteucinol (4), 2alpha,3beta,19alpha-trihydroxyolean-12-ene-24,28-dioic acid (bartogenic acid, 5), 2alpha,3beta,23-trihydroxyolean-12-ene-28-oic acid (arjunolic acid, 6), 2alpha,3alpha,19alpha, 23-tetrahydroxyurs-12-ene-28-oic acid (myrianthic acid, 7), and stigmast-4-ene-3,6-dione (8). The structures of 1-8 were elucidated by spectroscopic methods, including 2D NMR.     

理肺散化学成分研究

目的研究理肺散原植物攀援耳草Hedyotis scandens的化学成分。方法采用硅胶、ODS、Sephadex LH-20及RP-HPLC等色谱技术对理肺散的化学成分进行分离纯化,根据理化性质及波谱数据鉴定化合物结构。结果从理肺散的醋酸乙酯部位分离得到了13个化合物,分别鉴定为齐墩果酸(1)、2α,3α,24-三羟基-12-烯-28-齐墩果酸(2)、2α,3β,24-三羟基-12-烯-28-齐墩果酸(3)、2α,3β-二羟基-12-烯-28-乌苏酸(4)、2α,3β,19α-三羟基-12-烯-28-乌苏酸(5)、白桦酸(6)、山柰酚-3-O-β-D-葡萄糖苷(7)、槲皮素(8)、芹菜素(9)、芹菜素-7-O-β-D-葡萄糖苷(10)、木犀草素(11)、木犀草素-7-O-β-D-葡萄糖苷(12)和胡萝卜苷(13)。结论化合物1～13均为首次从该植物中分离得到。     

A new triterpene saponin from Pittosporum viridiflorum from the Madagascar rainforest.

A novel triterpenoid saponin, pittoviridoside (1), which possesses an unusual 2,3,4-trisubstituted glycosidic linkage, has been isolated from Pittosporum viridiflorum using the engineered yeast strains 1138, 1140, 1353, and Sc-7 for bioactivity-guided fractionation. The structure of this compound was determined to be 3-O-[beta-D-glucopyranosyl(1-->2)]-[alpha-D-arabinopyranosyl(1-->3)],[alpha-l-arabinofuranosyl(1-->4)-beta-D-glucuronopyranosyl-21-angeloyl-22-senecioylolean-12-en-3beta,15alpha,16alpha,21beta,22alpha,28-hexol by spectral, chemical, and GC analyses. This compound showed weak cytotoxicity against the A2780 human ovarian cancer cell line.     

New cytotoxic oleanane-type triterpenoids from the cones of Liquidamber styraciflua

Two new oleanane-type triterpenoids (1 and 2), together with two known compounds, 6beta-hydroxy-3-oxo-lup-20(29)-en-28-oic acid (3) and 3,11-dioxoolean-12-en-28-oic acid (4), were isolated from the stem bark of Liquidamber styraciflua. The structures of 1 and 2 were determined to be 25-acetoxy-3alpha-hydroxyolean-12-en-28-oic acid (1) and 3alpha,25-dihydroxyolean-12-en-28-oic acid (2) on the basis of spectroscopic methods and chemical conversion. Compound 1 showed strong cytotoxicity against a disease-oriented panel of 39 human cancer cell lines, although compounds 2, 3, and 4 showed weaker activity compared to 1.     

Chemical investigation and anti-inflammatory activity of Vitex negundo seeds.

The CHCl3 extract of the defatted seeds of Vitex negundo exhibited anti-inflammatory activity and yielded four triterpenoids: 3 beta-acetoxyolean-12-en-27-oic acid [1], 2 alpha, 3 alpha-dihydroxyoleana-5,12-dien-28-oic acid [2], 2 beta,3 alpha-diacetoxyoleana-5,12-dien-28-oic acid [3], and 2 alpha,3 beta-diacetoxy-18-hydroxyoleana-5,12-dien-28-oic acid [5]. This is the first report of the isolation of compounds 2, 3, and 5 from a natural source.