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.     

艾胶算盘子的化学成分研究

目的 对艾胶算盘子Glochidion lanceolarium地上部分进行化学成分研究.方法 采用多种色谱技术进行分离纯化,通过波谱分析技术鉴定化合物的结构.结果 从艾胶算盘子地上部分得到8个羽扇豆烷型三萜和1个甾体,分别鉴定为羽扇豆烷-20(29)-烯-1β,3a,23-三醇(1)、算盘子酮(2)、羽扇豆醇(3)、3-表羽扇豆醇(4)、算盘子酮醇(5)、β-谷甾醇(6)、羽扇豆烷-20(29)-烯-1β,3β-二醇(7)、算盘子二醇(8)、羽扇豆烷-20(29)-烯-3α,23-二醇(9).结论 9个化合物均为首次从该植物中分离得到,其中化合物1为新化合物,命名为算盘子三醇.     

Three new triterpenoids from Peganum nigellastrum

Three new triterpenoids, 3alpha,27-dihydroxylup-20(29)-en-28-oic acid methyl ester, 3alpha-acetoxy-27-hydroxylup-20(29)-en-28-oic acid methyl ester, and 3alpha-acetoxyolean-12-ene-27,28-dioic acid 28-methyl ester, were isolated from the roots of Peganum nigellastrum along with four known lupene-type triterpenoids. The structures of the new triterpenoids were determined by NMR spectroscopic means. The new triterpene, 3alpha, 27-dihydroxylup-20(29)-en-28-oic acid methyl ester is a DNA topoisomerase II inhibitor (IC(50) = 8.9 microM/mL).     

New vibsane diterpenes and lupane triterpenes from Viburnum odoratissimum

Bioassay-directed fractionation of the methanolic extract of the leaves and flowers of Viburnum odoratissimum resulted in the isolation of two new diterpenes, vibsanol A (1) and vibsanol B (2), together with two new triterpenoids, 6beta-hydroxylup-20(29)-en-3-oxo-27,28-dioic acid (3) and 6alpha-hydroxylup-20(29)-en-3-oxo-27,28-dioic acid (4). In addition, the known terpenoids vibsanins B and E, and 6alpha-hydroxylup-20(29)-en-3-oxo-28-oic acid, were also isolated. The structures of the new compounds were established by chemical and spectroscopic means. Vibsanol A (1) and compound 3 exhibited significant cytotoxicity against human gastric (NUGC) tumor cells.     

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.     

Cycloartane and friedelane triterpenoids from the leaves of Caloncoba glauca and their evaluation for inhibition of 11β-hydroxysteroid dehydrogenases

Five new triterpenoids, caloncobic acids A and B (1 and 2), caloncobalactones A and B (3 and 4), and glaucalactone (5), along with the known compounds 3β,21β-dihydroxy-30-nor-(D:A)-friedo-olean-20(29)-en-27-oic acid (6) and acetyltrichadenic acid B (7), were isolated from the leaves of Caloncoba glauca. The structures of 1-5 were elucidated using spectroscopic methods. Compounds 1-7 were evaluated for their inhibitory activities against two isozymes of 11β-hydroxysteroid dehydrogenase (11β-HSD1 and 11β-HSD2). Compounds 1 and 2 exhibited strong inhibitory activities against mouse (EC(50) 132 and 13 nM) and human (EC(50) 105 and 72 nM) 11β-HSD1.     

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.     

猫耳刺中三萜类化合物的结构研究

目的：研究猫耳刺Ilex pernyi叶的化学成分。方法：应用硅胶及Sephadex LH-20凝胶柱色谱法对其化学成分进行分离,并利用NMR和MS等方法鉴定分离得到的化合物。结果：从猫耳刺的干燥叶中分离得到8个三萜化合物,分别鉴定为熊果酸(1),羽扇豆醇(2),α-香树脂醇(3),熊果醇(4),3β-羟基-乌索-11-烯-28,13β-内酯(5),坡模酸(6),羽扇-20(29)-烯-3β,24-二醇(7),3β,23-二羟基乌索-12-烯-28-酸(8),结论：该8个化合物均为首次从猫耳刺中分离得到。     

Bioactive steroids from the whole herb of Euphorbia chamaesyce

Three new ergostane-type steroids, 3beta-hydroxy-4alpha, 14alpha-dimethyl-5alpha-ergosta-8,24(28)-dien-11 -one (1); 3beta, 11alpha-dihydroxy-4alpha,14alpha-dimethyl-5alpha -ergosta-8, 24(28)-dien-7-one (2); and 3beta,7alpha-dihydroxy-4alpha, 14alpha-dimethyl-5alpha-ergosta-8,24(28)-dien-11 -one (3), were isolated, together with two known triterpenoids, wrightial and lup-20(30)-ene-3beta,29-diol from the whole herb of Euphorbia chamaesyce. Compound 3 showed a potent inhibitory effect on Epstein-Barr virus early antigen activation induced by the tumor promoter 12-O-tetradecanoylphorbol 13-acetate (TPA).     

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.     

Four new trisnorlanostene-type triterpenoids from the stem bark of Pinus luchuensis

Four new 25,26,27-trisnorlanostene-type triterpenoids were isolated from the stem bark of Pinus luchuensis, together with five known compounds. These new compounds were characterized as 25,26, 27-trisnor-3 alpha-hydroxy-lanost-9(11)-en-24-oic acid (1), 25,26, 27-trisnor-3 alpha-methoxy-lanost-9(11)-en-24-oic acid (2), 25,26, 27-trisnor-3 beta-methoxy-lanost-9(11)-en-24-oic acid (3), and 25,26, 27-trisnor-3-oxo-lanost-9(11)-en-24-oic acid (4) on the basis of MS and NMR evidence.     

Differentiation- and apoptosis-inducing activities by pentacyclic triterpenes on a mouse melanoma cell line

In a study to investigate the relationship between the chemical structure and the differentiation-inducing activity of pentacyclic triterpenes, several lupane, oleanane, and ursane triterpenes were prepared and their effects on B16 2F2 melanoma cell differentiation and growth were examined. Eleven lupane triterpenes used in this study acted on the melanoma cells as a melanogen, but no induction of melanogenesis of B16 2F2 cells by oleanane and ursane was detected. The differences at C-17 of the lupane series and acetylation of the OH group at C-3 did not markedly influence their activities. However, the ED(50) value for up-regulation of melanin biosynthesis was markedly decreased by the oxidation of the OH group at C-3 of lupeol (1). Betulinic acid (11), its methyl ester (12), lup-28-al-20(29)-ene-3beta-ol (9), and lup-28-al-20(29)-en-3-one (10) inhibited B16 2F2 cell proliferation by induction of apoptosis. These findings suggested that the carbonyl group at C-17 might be essential for the apoptotic effects of these compounds on B16 2F2 cells.     

Antimicrobial triterpenoids from Vladimiria muliensis

A new triterpenoid with a rearranged ursane skeleton, 3beta-acetoxyl-11alpha-methoxybauer-8-en-7alpha-ol ( 1), two new ursane triterpenoids, 1alpha,5alpha-dioxy-11alpha-hydroxyurs-12-en-3-one ( 2) and urs-3beta,13alpha,18beta-triol ( 3), together with three known ursane triterpenoids ( 4- 6) were isolated from the rhizome of Vladimiria muliensis. Their structures were elucidated on the basis of spectroscopic methods (IR, EIMS, HRESIMS, 1D and 2D NMR, and X-ray crystallography diffraction). Compounds 2 and 4 exhibited modest antimicrobial activity against Escherichia coli, Candida albicans, Pseudomonas aeruginosa, Enterococcus faecalis, Bacillus cereus, and Staphylococcus aureus.     

菜头肾的化学成分研究

 目的 研究菜头肾的化学成分。方法 应用色谱技术对石油醚、乙醇提取物进行分离,根据理化性质和波谱数据鉴定结构。结果 从中分离鉴定了9种成分,分别为hop-22(29)-ene（Ⅰ）、lupeo1（Ⅱ）、lup-20(29)-en-11,3β-diol（Ⅲ）、lup-20(29)-en-3-one（Ⅳ）、betulinic acid（Ⅴ）、(24R)-stigmast-7,22（E）-dien-3α-ol（Ⅵ）、(24R)-5α-stigmast-3,6-dione（Ⅶ）、β-sitosterol（Ⅷ）、3α-hydroxyhop-22(29)-ene（Ⅸ）。结论 这些化合物为首次从该植物中分离得到。     

Acinospesigenin-A, -B,and -C: three new triterpenoids from Phytolacca acinosa

Three new triterpenoids, designated as acinospesigenin-A (1), -B (2), and -C (3), isolated from the berries of Phytolacca acinosa, have been characterized as 3 beta-acetoxy-11 alpha,23-dihydroxytaraxer-14-en-28-oic acid, olean-12-en-23-al-2 beta,3 beta-dihydroxy-30-methoxycarbonyl-28-oic acid and olean-12-en-23-al-2 beta,3 beta,11 alpha-trihydroxy-30-methoxycarbonyl-28-oic acid, respectively. The compounds have shown antiedemic activity (LD(50) 10-15 mg/kg mass) in albino rats.     

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.     

白背叶根化学成分研究

目的 研究白背叶Mallotus apelta根的化学成分.方法 通过各种柱色谱进行分离纯化,根据理化性质和波谱数据进行结构鉴定.结果 分离得到了9个化合物,分别鉴定为β-香树脂醇乙酸酯(1)、高根二醇(2)、羽扇豆-20 (29)-烯-3β,30-二醇(3)、对羟基苯甲酸-2α-羟基油桐酸酯(4)、α-香树脂醇乙酸酯(5)、油桐酸(6)、槲皮素(7)、3-甲氧基-4-O-β-D-葡萄糖基苯甲酸(8)、勾儿茶素(9).结论 化合物1～4、6、8、9为首次从野桐属植物中分离得到.     

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.     

A novel NO-production-inhibiting triterpene and cytotoxicity of known alkaloids from Euonymus laxiflorus

A new triterpene, laxifolone A (1), four known sesquiterpene alkaloids, ebenifoline E-II (2), carigorinine E (3), euojaponine C (4), and emarginatine E (5), and six triterpenoids, 3-hydroxyolean-12-en-22,29-gamma-lactone, 3,11-dioxo-beta-amyrene, 3beta,22alpha-dihydroxyolean-12-en-29-oic acid, 28,29-dihydroxyfriedelan-3-one, 29-hydroxy-3-oxo-D:A-friedooleanan-28-oic acid, and putranjivadione, were isolated from the stems and leaves of Euonymus laxiflorus. Structural elucidations of these compounds were established by spectral analysis. Compound 1 displayed significant nitric oxide (NO) inhibitory effect.     

Serratene-type triterpenoids from Huperzia serrata

Seven new and 15 known serratene-type triterpenoids were isolated from the whole plant of Huperzia serrata. The structures of these new triterpenoids were elucidated as 21alpha-hydroxyserrat-14-en-3beta-yl p-dihydrocoumarate (1), 21alpha-hydroxyserrat-14-en-3beta-yl dihydrocaffeate (2), 21alpha-hydroxyserrat-14-en-3beta-yl propanedioic acid monoester (3), 3alpha,21alpha-dihydroxyserrat-14-en-24-oic acid (4), 16-oxo-3alpha,21beta-dihydroxyserrat-14-en-24-al (5), 16-oxo-3alpha,21beta-dihydroxyserrat-14-en-24-oic acid (6), and 16-oxo-21beta-hydroxyserrat-14-en-3alpha-yl acetate (7), respectively, by means of spectroscopic analysis.