Two new triterpenes from Duchesnea indica

Two new triterpenes,2α,3β-dihydroxyurs-12-en-18,19-epoxy-28-oic acid(1)and 18,19-seco,2α,3α-dihydroxyl-19-oxo-urs-11, 13(18)-dien-28-oic acid(2)were isolated from the herbaceous part of Duchesnea indica.Their structures were elucidated by spectroscopic analysis,including 2D NMR technique.The isolated compounds exhibited moderate cytotoxic activities against HeLa and L929 cell lines.     

Constituents of Withania somnifera Dun—XIII : The withanolides of chemotype III

Nine new steroidal lactones of the withanolide series (withanolides E-M) have been isolated from the leaves of Withania somnifera Dun (Solanaceae) growing in the southern coastal plane of Israel. This population of W. somnifera constitutes a new chemotype and is designated as chemotype III. The following structures have been assigned to seven of the above compounds:Withanolide G, 20α-hydroxy-1-oxo-20R,22R-witha-2,5,8(14),24-tetraenolide (1); withanolide H, 20α,27-dihydroxy-1-oxo-20R,22R-witha-2,5,8(14),24-tetraenolide (2); withanolide I, 20α-hydroxy-1-oxo-20R,22R-witha-3,5,8(14),24-tetraenolide (3); withanolide J, 17α,20α-dihydroxy-1-oxo-20S,22R-witha-2,5,8(14),24-tetraenolide (4); withanolide K, 17α,20α-dihydroxy-1-oxo-20S,22R-witha-3,5,8(14),24-tetraenolide (5); withanolide L, 17α,20α-dihydroxy-1-oxo-20S,22R-witha-2,5,14,24-tetraenolide (6); withanolide M, 17α,20α-dihydroxy-1-oxo-14α,15α-epoxy-20S,22R-witha-2,5,24-trienolide (7).     

Glaucasides A-C, three saikosaponins from Atriplex glauca L. var. ifiniensis (Caball) Maire

From the roots of Atriplex glauca L. var. ifiniensis (Caball) Maire (syn. of Atriplex parvifolia Lowe var. genuina Maire), three new saikosaponins designated as glaucasides A-C (1-3) were isolated together with the known 3-O-β-D-glucopyranosyl-(1 → 2)-β-D-galactopyranosyl-saikogenin F (4). The structures of the new compounds were elucidated by extensive analysis of one-dimensional and two-dimensional NMR spectroscopy, FABMS, HR-ESIMS and chemical evidence as 13β,28-epoxy-16β,21β-dihydroxyolean-11-en-3β-yl O-β-D-[2-O-sulfate]-glucopyranosyl-(1 → 2)-α-L-arabinopyranoside (1), 13β,28-epoxy-16β,21β-dihydroxyolean-11-en-3β-yl O-β-D-[2-O-sulfate]-glucopyranosyl-(1 → 2)-α-L-arabinopyranosyl 21-O-{4-(secbutylamido)-butanoyl ester} (2) and 3-O-β-D-glucopyranosyl-(1 → 2)-β-D-galactopyranosyl saikogenin G (3). The cytotoxic activities of these compounds were evaluated against the HT-29 and HCT 116 human colon cancer cell lines.     

Triterpene Saponins from <i>Pleurospermum kamtschaticum</i> and Their Biological Activity

Eleven new triterpene saponins (1-11), together with fourteen known triterpene and triterpene saponins (12-25) were isolated from a MeOH extract of Pleurospermum kamtschaticum HOFFMANN (Umbelliferae). The chemical structures of the new compounds (1-11) were determined by means of MS, ¹H-NMR, ¹³C-NMR, correlated spectroscopy (COSY), heteronuclear multiple bond correlation (HMBC), total correlated spectroscopy (TOCSY) and nuclear Overhauser effect spectroscopy (NOESY) to be pleurosaponin A (1)-K (11). 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 (SRB) assay. All compounds showed little cytotoxicity against tested cell lines (IC50 >30?μM).     

Major terpenoids from Telekia speciosa flowers and their cytotoxic activity in vitro

In addition to known constituents of Telekia speciosa, an acetone extract from ray florets of the plant yielded: 5,5?-dibutoxy-2,2?-bifuran (1), 5,5?-diisobutoxy-2,2?-bifuran (2), α-tocopherol (3), β-tocopherol (4), loliolide palmitate (5), a mixture of calenduladiol esters - 16β-hydroxylupeol-3-O-palmitate (7) and 16β-hydroxylupeol-3-O-myristate (8), 1-epiinuviscolide (12), inuviscolide (13), 3-epiisotelekin (16), 4α-hydroxy-9β,10β-epoxy-1β(H)-11(13)-guaien-8α,12-olide (17), 4α-hydroxy-1β(H)-9(10),11(13)-guaiadien-8α,12-olide (18), loliolide (19) and 4β,10β-dihydroxy-1α(H),5α(H)-11(13)-guaien-8α,12-olide (20). Calenduladiol esters and asperilin (14) were the major constituents of the extract. Their cytotoxic effect on human normal prostate epithelial cells (PNT-2), human prostate carcinoma cell lines, human skin fibroblasts (HSF) and human melanoma cell lines was examined in vitro. Triterpene esters showed no cytotoxicity against nearly all cell lines tested, except for Du145 prostate carcinoma cells (IC₅₀ – 62.0 μΜ). Asperilin displayed activity against the cell lines under study, especially against three tested lines of melanomas (A375, IC₅₀ – 17.6 μΜ, WM793, IC₅₀ – 28.2 μΜ and Hs 294T, IC₅₀ – 29.5 μΜ).     

巴戟天内生真菌Trichoderma spirale A725中两个新的聚酮类化合物(英文)

综合运用硅胶柱色谱、反相硅胶柱色谱、Sephadex LH-20凝胶柱色谱以及制备型高效液相色谱技术对药用植物巴戟天内生真菌Trichoderma spirale A725的次生代谢产物进行分离纯化,得到6个聚酮类化合物,采用多种现代波谱技术确定其结构,分别为:6-羟基-4-异丙基-1,8-二甲基螺环[4.5]癸-1,8-二烯-7-酮(1),2-羟基-2,5-二甲基-7-氧代-5,7-二氢-2H-呋喃[3,4-b]吡喃-4-羧酸(2), 3-乙基-4-羟基-6-甲基-二氢-吡喃-2-酮(3),苯乙内酯A (4), 3-羟基-5-(4-羟基苄基)二氢呋喃-2(3H)-酮(5), 4-乙酰-3-羟基-6-甲基吡喃-2-酮(6).其中化合物1和2为新化合物,化合物3为新天然产物.此外,利用四株肿瘤细胞株(Hep G-2、MCF-7、SF-268及A549)对化合物1~6细胞毒活性进行评估,结果表明化合物1~6对上述肿瘤细胞均无明显的细胞毒活性.     

Design, Synthesis and Anticancer Activities of Diaryl Urea Derivatives Bearing <i>N</i>-Acylhydrazone Moiety

A new series of diaryl urea derivatives bearing N-acylhydrazone moiety were designed and synthesized. All the target compounds were evaluated for their cytotoxic activities in vitro against human lung adenocarcinoma epithelial cell line (A549), human breast cancer cell line (MDA-MB-231) and human leukemia cell line (HL-60) by standard 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. Several compounds (1a, 1f and 1h) were further evaluated against human embryonic fibroblast, lung-derived cell line (WI38). The pharmacological results indicated that some compounds exhibited promising anticancer activities. In particular, compound 1f showed the most potent cytotoxicity against the tested three cell lines with IC50 values of 0.41?μM, 0.24?μM and 0.23?μM, respectively.     

Norlanostane and lanostane glycosides from the bulbs of Chionodoxa luciliae and their cytotoxic activity

Ten lanostane glycosides (1-10), including two new norlanostane glycosides (2 and 7) and a new lanostane glycoside with a spirolactone ring system (9), were isolated from the fresh bulbs of Chionodoxa luciliae (Liliaceae). The structures of the new compounds were determined on the basis of extensive spectroscopic analysis and the results of hydrolytic cleavage to be (23S)-3beta-[(O-beta-D-apiofuranosyl-(1-->2)-O-[beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosyl)oxy]-17alpha,23-epoxy-28,29-dihydroxy-27-norlanost-8-en-24-one (2), (23S)-17alpha,23-epoxy-29-hydroxy-3beta-[(O-alpha-L-rhamnopyranosyl-(1-->2)-O-[O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosyl)oxy]-27-norlanost-8-ene-15,24-dione (7), and (23S,25R)-17alpha,23-epoxy-29-hydroxy-3beta-[(O-alpha-L-rhamnopyranosyl-(1-->2)-O-[beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosyl)oxy]lanost-8-en-23,26-olide (9), respectively. The cytotoxic activity of the isolated compounds against HSC-2 human oral squamous cell carcinoma cells are also reported.     

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.     

Investigation of steroids. XLII. Transformation of 17-alpha-pseudostrophanthidins to 19-hydroxy-8,19-epoxy-14-beta,17-alpha-cortexone and 8-hydroxy-19-nor-14-beta,17-alpha-cortexone

The synthesis of a structural isomer of aldosterone, viz. 19-hydroxy-8, 19-epoxy-(11-) de(s)oxycorticosterone (= 19-hydroxy-8, 19-epoxy-cortexone), and a number of related compounds was reported earlier from this laboratory [1]. It appeared desirable to prepare the corresponding compounds of the 17α-series also, such as 19-hydroxy-8, 19-epoxy-14 β, 17 (βH)-deoxycorticosterone ( 28 ). 17 α-Pseudostrophanthidin ( 2 ), which has not yet been described in the literature, was considered as starting material for the synthesis of 28. 2 has now been prepared by heating a solution of pseudostrophanthidin ( 1 ) in dimethylformamide in the presence of sodium p-toluenesulfonate and anhydrous sodium acetate. 2 was characterized as the 3, 19-diacetate ( 7 ), the 19-methylal ( 8 ) and the 3-monoacetat ( 9 ). 9 was also obtained by acetylating the methylal 8 and demethylating the resulting reaction product 10. To support the structures assigned to 9 and, by implication, to 2 , a series of further reactions were carried out.     

Cytotoxicity of triterpenes isolated from Aceriphyllum rossii

Bioassay-guided fractionation of a MeOH extract of the whole plant of Aceriphyllum rossii (Saxifragaceae) led to the isolation of two new triterpenes, 3alpha,23-isopropylidenedioxyolean-12-en-27-oic acid (1) and 23-hydroxy-3-oxoolean-12-en-27-oic acid (2), together with six known triterpenes, 3-oxoolean-12-en-27-oic acid (3), 3alpha-hydroxyolean-12-en-27-oic acid (4), beta-peltoboykinolic acid (5), aceriphyllic acid A (6), oleanolic acid (7), and gypsogenic acid (8). The structures of these compounds were elucidated on the basis of physicochemical and spectroscopic analyses. These compounds were evaluated for in vitro cytotoxicity against the K562 and HL-60 cell lines. Olean-12-en-27-oic acid derivatives (1-6) exhibited considerable cytotoxicity against K562 and HL-60 cell lines with IC(50) values ranging from 12.2 to 28.7 microM and from 12.1 to 25.8 microM, respectively.     

Silvestrol and episilvestrol, potential anticancer rocaglate derivatives from Aglaia silvestris

Two cytotoxic rocaglate derivatives possessing an unusual dioxanyloxy unit, silvestrol (1) and episilvestrol (2), were isolated from the fruits and twigs of Aglaia silvestris by bioassay-guided fractionation monitored with a human oral epidermoid carcinoma (KB) cell line. Additionally, two new baccharane-type triterpenoids, 17,24-epoxy-25-hydroxybaccharan-3-one (3) and 17,24-epoxy-25-hydroxy-3-oxobaccharan-21-oic acid (4), as well as eleven known compounds, 1beta,6alpha-dihydroxy-4(15)-eudesmene (5), ferulic acid (6), grasshopper ketone (7), apigenin, cabraleone, chrysoeriol, 1beta,4beta-dihydroxy-6alpha,15alpha-epoxyeudesmane, 4-hydroxy-3-methoxyacetophenone, 4-hydroxyphenethyl alcohol, ocotillone, and beta-sitosterol 3-O-beta-D-glucopyranoside, were also isolated and characterized. The structures of compounds 1-4 were elucidated by spectroscopic studies and by chemical transformation. The absolute stereochemistry of silvestrol (1) was established by a X-ray diffraction study of its di-p-bromobenzoate derivative, and the structure of 3 was also confirmed by single-crystal X-ray diffraction. The isolates and chemical transformation products were evaluated for cytotoxicity against several human cancer cell lines, and silvestrol (1) and episilvestrol (2) exhibited potent in vitro cytotoxic activity. Silvestrol (1) was further evaluated in vivo in the hollow fiber test and in the murine P-388 leukemia model.     

藤黄化学成分的研究

传统中药藤黄通过各种色谱方法分离纯化, 得到15个化合物, 根据其理化性质和光谱方法鉴定其结构分别为: 2α-羟基-3β-乙酰氧基白桦酯酸(1), 10α-羟基表藤黄酸(2), 藤黄酸(3), 异藤黄酸(4), gambogin (5), gambogoic acid B (6), desoxymorellin (7), isomorellin (8), gambogenic acid (9), isogambogenin (10), gambogellic acid (11), desoxygambogenin (12), morellic acid (13), isomorellic acid (14), 30-hydroxygambogic acid (15). 其中化合物1和2为新化合物.     

Photochemical Rearrangement of a Steroidal α, β-Epoxylactam. Photochemical reactions,XII [1]

The UV. irradiation of 17β-hydroxy-4α, 5α-epoxy-2-azaandrostan-3-one ( 1 ) yields 17β-hydroxy-2-aza-10 (5 → 4-abeo)-4ζ (H)-androsta-3,5-dione ( 3 ).     

Cytotoxic and antimicrobial aporphine alkaloids from Fissistigma poilanei (Annonaceae) collected in Vietnam

Two new aporphine alkaloids: 8-hydroxy-9-methoxy-1,2-methylenedioxyaporphine (1) and 8-hydroxy-3,9-dimethoxy-1,2-methylenedioxyaporphine (2) were isolated from the ethyl acetate extract of Fissistigma poilanei along with five known compounds: oxocrebanine (3), kuafumine (4), (2R,3R)-3',4',5,7-tetrahydroxydihydroflavonol-3-O-α-L-rhamnopyranoside (5), (+)-catechin 3-O-α-L-rhamnopyranoside (6) and quercetine 3,7-dimethoxy-3'-O-α-L-rhamnopyranosyl-(1?→?2)-β-D-glucopyranoside (7). These two new aporphine alkaloids exhibited a moderate cytotoxic activity against four human cancer cell lines (KB, Hep-G2, MCF-7, LU) as well as antimicrobial activity against Lactobacillus fermentum, Enterococcus faecium, Staphylococcus aureus and Bacillus subtillis.     

Systematic phytochemical investigation of Abies spectabilis

Systematical phytochemical investigations on Abies spectabilis afforded 72 chemical constituents. On the basis of physical and spectroscopic data, including 1D and 2D homo- and heteronuclear NMR experiments (heteronuclear single quantum coherence (HSQC), (1)H-(1)H correlation spectroscopy (COSY), heteronuclear multiple bond connectivity (HMBC), and nuclear Overhauser effect spectroscopy (NOESY)), and by comparison with the literature references, they were identified as 3 triterpenoids, 23 diterpenoids, 1 sesquiterpenoid, 13 flavonoids, 12 lignans, and 20 other components. Among these compounds, three were identified as new including abieta-7,13-diene-12α-methoxy-18-oic acid (1), 7α-methoxy-dehydroabietic acid (2), and 5-hydroxy-6-methyl-7,4'-dimethoxyflavone-8-O-β-D-glucopyranoside (3). These three new compounds (1-3) and all the known terpenoids (4-28) were tested for cytotoxic activities against four tumor cell lines: A549, COLO-25, QGY-25, and THP-1. However, none of them showed a positive effect (IC??>100 μM).     

Steroids and sex hormones. 242. Preparation of 14-beta-hydroxy-2-keto-delta-16-steroids: a new highly productive access to 33-O-methyl-17-alpha, 20-xi-tetrahydrobatrachotoxinin A

A novel method for the reductive epoxide opening in a 14β, 15β-epoxy-20-oxo-Δ¹⁶-pregnene 4 affords an almost quantitative yield of the 14β-hydroxy-20-oxo-Δ¹⁶-pregnene 5. This leads to a considerable improvement of the formerly published synthesis of 3-O-methyl 17 α, 20ξ-tetrahydrobatrachotoxinin A ( 2 ) [3].     

Design, Synthesis and Anticancer Activity of 4-Morpholinothieno[3,2-<i>d</i>]pyrimidine Derivatives Bearing Arylmethylene Hydrazine Moiety

Three series of 4-morpholinothieno[3,2-d]pyrimidine derivatives containing arylmethylene hydrazine moiety (11a-f, 13a-k and 15a-h) were synthesized and their chemical structures as well as the relative stereochemistry were confirmed. The synthesized compounds were evaluated for their cytotoxicity against three cancer cell lines (H460, HT-29, MDA-MB-231). Most of them exhibited moderate to significant cytotoxicity and high-selectivity against one or more cell lines, especially compounds 11c, 13b, 15f and 15g possessing dramatically increased cytotoxicity as compared with the positive controls, which were further evaluated for six other cancer cell lines and one normal cell line. The most promising compound 11c, bearing 3,4-methylenedioxy phenyl group, showed remarkable cytotoxicity against H460, HT-29 and MDA-MB-231 cell lines with IC50 values of 0.003?μM, 0.42?μM and 0.74?μM, which was 1.6- to 290-fold more potent than GDC-0941.     

A new triterpene and protective effect of Periploca somaliensis Browicz fruits against CCl4-induced injury on human hepatoma cell line (Huh7)

The potential hepatoprotective effect of the methanolic extract of Periploca somaliensis Browicz fruits, its different fractions (n-hexane, chloroform and n-butanol) and the major isolated compound ursolic acid was evaluated using the human hepatoma cell line (Huh7) based on the changes in the activity of aspartate aminotransferase, alanine transaminase, glutathione and superoxide dismutase. Each sample was tested at three different concentrations (1000, 100 and 10 μg/mL). All tested samples exhibited a potent concentration-independent cytoprotective effect relative to silymarin as a reference standard. Chromatographic fractionation of the chloroform-soluble fraction of the methanol extract of P. somaliensis Browicz fruits afforded two known triterpenes, namely ursolic acid, and 11α,12α-epoxy-3β-hydroxy-olean-13β,28-olide, and a newly discovered one, namely 3β-hydroxy-urs-11-en-13β,28-olide. The structures of the isolated compounds were elucidated by the analysis of 1D and 2D NMR spectral data.     

In vitro antitumor activity of triterpenes from Ceriops tagal

The embryo of Ceriops tagal was extracted with 95% ethanol at room temperature, and four triterpenes (1-4) were separated from this extract. For the first time these triterpenes were the separated from this plant. Compounds (1-4) were tested in vitro for antitumor activity against three cell lines (human liver cancer cell (H-7402), human B-lymphoblastoid cell (Raji), and human cervical carcinoma cell (Hela)). Compounds 1 and 3 were effective to inhibit cell proliferation and growth of H-7402 and Hela, the IC(50) of them on H-7402 were 14.42 microg mL(-1) and 9.97 microg mL(-1), and the IC(50) of them on Hela were 11.84 microg mL(-1) and 11.32 microg mL(-1). All compounds 1-4 were not effective to inhibit cell proliferation and growth of Raji. The effects of compound 4 on inhibiting proliferation and growth of these three cancer cells was also not obvious.