Mixed lignan-neolignans from Tarenna attenuata

Six new mixed lignan-neolignans and 20 known compounds were isolated from the whole plant of Tarenna attenuata. By analysis of physical and spectroscopic data, the structures of the new compounds were elucidated as (1R,5R,6R)-6-{4-O-[2-(1-(4-hydroxy-3-methoxyphenyl))glycerol]-3,5-dimethoxyphenyl}-3,7-dioxabicyclo[3.3.0]octan-2-one (1), 5' '-methoxyhedyotisol A (2), 4' '-O-(8-guaiacylglycerol)buddlenol A (3), 5' '-methoxy-4' '-O-(8-guaiacylglycerol)buddlenol A (4), 4,6-dimethoxy-5-hydroxy-3-hydroxymethyl-2-(3,4,5-trimethoxyphenyl)-2,3-dihydrobenzofuran (5), and 7-O-ethylguaiacylglycerol (6). Compounds 1, 5, 6, and 8 showed potent antioxidant activities against H2O2-induced impairment in PC12 cells, and compounds 1, 2, 5, and 7 scavenged DPPH radical strongly with IC50 values of 72, 87, 45, and 55 microM, respectively.     

大黄橐吾的化学成分研究Ⅱ

目的:从菊科橐吾属植物大黄橐吾的根及根茎中提取分离活性成分,为其资源开发提供科学依据。方法:以90%乙醇提取,采用硅胶柱色谱、凝胶柱色谱、重结晶等方法分离纯化化合物,根据理化常数及波谱数据进行结构鉴定。结果:共分离鉴定了9个化合物,分别为Δ^12,13-羽扇豆醇(1),异莨菪亭(2),isoline(3),duciformine(4),(2S,3S,4R)-鞘氨醇-(2′R)-Δ^5′,6′(E)-2′-羟基正二十四碳酰胺(5),正二十四碳酸(6),正二十四酸单甘油酯(7),反式-阿魏酸正二十二酯(8),反式-咖啡酸正二十二酯(9)。结论:化合物1,2,5~7为首次自该植物中分离得到,其中化合物2,5~7为首次自橐吾属中分得。     

New cytotoxic clerodane diterpenoids from the leaves and twigs of Casearia membranacea

Bioassay-guided fractionation of an EtOAc-soluble extract of Casearia membranacea has resulted in the isolation of six new clerodane diterpenes, caseamembrins A-F (1-6), and a known compound, rel-(2S,5R,6R,8S,9S,10R,18S,19R)-diacetoxy-18,19-epoxy-6-hydroxy-2-(2-methylbutanoyloxy)cleroda-3,13(16),14-triene (7). The structures of 1-6 were established on the basis of extensive 1D and 2D NMR spectroscopic analysis. In addition, the new derivatives, 8 and 9, were prepared by acylation of 7 and 3, respectively. The isolated diterpenoids and their derivatives were tested against human prostate (PC-3) and hepatoma (Hep3B) cancer cells. Compounds 1, 3-5, and 7 exhibited cytotoxicity against both tumor cells, with IC(50) values below 3 micromicro, while compounds 2, 6, 8, and 9 were less effective.     

苍耳子中苯丙素类化学成分的研究

目的 研究菊科植物苍耳(Xanthium sibiricum Patrin ex Widder)的干燥成熟带总苞的果实(苍耳子)中苯丙素类化学成分。方法 采用正相硅胶柱色谱、反相十八烷基硅烷键合硅胶(ODS)柱色谱、Sephadex LH-20凝胶柱色谱和半制备高效液相色谱(HPLC)等色谱方法进行分离纯化,并结合高分辨质谱(HR-ESI-MS)、核磁共振(NMR)对分离得到的化合物进行结构鉴定。采用脂多糖(LPS)诱导的巨噬细胞RAW 264.7为筛选模型评价分离得到化合物的抗炎活性。结果 从苍耳子体积分数95%乙醇提取物的乙酸乙酯萃取物中分离并鉴定了24个苯丙素类化合物,分别为c-藜芦酰乙二醇(1)、3,4'-二羟基-3'-甲氧基苯丙酮(2)、阿魏醛(3)、丁香脂素(4)、蛇菰宁(5)、落叶松脂醇(6)、愈创木基甘油(7)、3-hydroxy-l-(4-hydroxy-3,5-dimethoxyphenyl)-1-propanone(8)、salicifoliol(9)、6-(4-hydroxy-3-methoxyphenyl)-3,7-dioxabicyclo[3.3.0]octan-2-ol(10)、榕醛(11)、jatrointelignan D(12)、icariol A₂(13)、异落叶松脂素(14)、ehletianol C(15)、(7R,7'R,7”S,7‴S,8S,8'S,8”S,8‴S)-4”,4‴-dihydroxy-3,3',3”,3‴,5,5'-hexamethoxy-7,9';7',9-diepoxy-4,8”;4',8‴-bisoxy-8,8'-dineolignan-7”,7‴,9”,9‴-tetraol(16)、(7R,7'R,7”R,7‴S,8S,8'S,8”S,8‴S)-4”,4‴-dihydroxy-3,3',3”,3‴,5,5'-hexamethoxy-7,9';7',9-diepoxy-4,8”;4',8‴-bisoxy-8,8'-dineolignan-7”,7‴,9”,9‴-tetraol(17)、2-(4-hydroxy-3-methoxyphenyl)-1-(4-hydroxyphenyl)-propan-1,3-diol(18)、2,3-bis-(4-hydroxy-3-methoxyphenyl)-3-methoxypropanol(19)、楝叶吴萸素B(20)、threo-guaiacylglycerol-8-vanillin ether(21)、erythro-guaiacylglycerol-8-vanillin ether(22)、黄花菜木脂素B(23)和27-对香豆酰氧基熊果酸(24)。结论 化合物6~24为首次从苍耳中分离得到。对分离得到的24个化合物进行抗炎活性筛选,其中,化合物14、21和23具有抗炎活性,其IC₅₀值分别为(28.14±1.89),(16.78±0.68)和(38.42±2.15)μmol·L^-1。     

Lignan glycosides from Neoalsomitra integrifoliola

Five new lignan glycosides, (8R*,7' S*,8' R*)-5,5'-dimethoxy-7-oxolariciresinol 9'-O-beta-D-xylopyranoside (1), (7S,8R)-dihydrodehydrodiconiferyl alcohol 9-O-beta-D-apiofuranosyl-(1-->6)-O-beta-D-glucopyranoside (2), (7S*,8R*,7' S*,8' R*)-4,4'-dimethoxyhuazhongilexin 9-O-beta-D-xylopyranoside (4), (7S*,8R*,7' S*,8' R*)-4,4'-dimethoxyhuazhongilexin 9-O-alpha-L-arabinopyranoside (5), and (7S*,8R*,7' S*,8' R*)-huazhongilexin 9-O-(2-feruloyl)-beta-D-xylopyranoside (6), together with four known compounds, (7R,8S)-dihydrodehydrodiconiferyl alcohol 9-O-beta-D-glucopyranoside (3), the 9-O-beta-D-xylopyranoside of icariol A(2) (7), huazhongilexin (8), and nudiposide (9), were isolated from the leaves of Neoalsomitra integrifoliola. Their structures were determined by spectroscopic analysis and chemical methods. Compounds 2, 3, 8, and 9 showed weak anti-inflammatory activities.     

轮叶棘豆的化学成分研究

目的：研究轮叶棘豆的化学成分。方法：90%乙醇冷浸提取,所得浸膏经硅胶,聚酰胺,C-18,Sephadex LH-20等多种材料进行柱色谱分离,通过波谱学方法鉴定化合物的结构。结果：分离鉴定了8个化合物,分别鉴定为azukisapogenol(1),(22E,24R)-24-甲基-5α-胆甾-7,22-二烯-3β,5α,6β-三醇(2),芹菜素(3),3′,4′-二甲氧基-槲皮素-3-O-β-D-半乳糖吡喃苷 (4),7,4′- 二甲氧基-槲皮素-3-O-α-L-鼠李糖吡喃基(1→2)-β-D-葡萄糖吡喃苷(5),(2S,3S,4R)-N-［(R)-2′-羟基二十四烷醇基］-1,3,4-三羟基-2-氨基-十八-6-烯(6),β-谷甾醇(7),胡萝卜苷(8)。结论：所有化合物均为首次从该植物中分得。     

Terpene isocyanides, isocyanates, and isothiocyanates from the Okinawan marine sponge Stylissa sp

Seven new nitrogenous terpenoids, (1R,6R,7S,10S)-10-isothiocyanatocadin-4-ene (1), (1S,2S,5S,6S,7R,8S)-13-isothiocyanatocubebane (2), (1R,3S,4R,7S,8S,12S,13S)-7-isocyanoamphilecta-10,14-diene (3), (1S,3S,4R,7S,8S,12S,13S)-8-isocyanoamphilecta-11(20),14-diene (4), (3S,4R,7S,8S,11S,13S)-8-isocyanoamphilecta-1(12),14-diene (5), 8-isocyanatocycloamphilect-10-ene (6), and 8-isothiocyanatocycloamphilect-10-ene (7), were isolated from the Okinawan sponge Stylissasp., along with 12 known related compounds. Structural determinations of these compounds were made by spectroscopic analysis, and assessment was made of their cytotoxicity toward HeLa cells.     

Brominated sesquiterpenes from the red alga Laurencia obtusa

Four new sesquiterpenes, (8R)-8-bromo-10-epi-beta-snyderol (1), (8S)-8-bromo-beta-snyderol (2), 5-bromo-3-(3'-hydroxy-3'-methylpent-4'-enylidene)-2,4,4-trimethylcyclohexanone (3), and the epoxide 4, have been isolated from the chloroform-methanol extract of Laurencia obtusa, together with the three known compounds alpha-snyderol (5), alpha-snyderol acetate (6), and stigmasterol. The structures of the isolated compounds were elucidated through spectroscopic analyses. Compound 1 showed antimalarial activity, with IC(50) values of 2700 and 4000 ng/mL against the D6 and W2 clones of Plasmodium falciparum, respectively.     

New neolignans that inhibit DNA polymerase beta lyase

Bioassay-directed fractionation of a methyl ethyl ketone extract of the roots of Endlicheria aff. resulted in the isolation of four new neolignans (1-4) and eight known compounds, namely, canellin A (5), canellin C (6), 3'-methoxyguianin (7), (7S,8R,1'S,5'S,6'R)-Delta(2',8')-3',6'-dihydroxy-5'-methoxy-3,4-methylenedioxy-4'-oxo-8.1',7.5'-neolignan (8), armenin-B (9), dillapiole (10), 1-allyl-2,6-dimethoxy-3,4-methylenedioxybenzene (11), and omega-hydroxyisodillapiole (12). The structures of the new compounds (1-4) were established as (7S,8R,1'S,5'S,6'R)-Delta(2',8')-5',6'-dihydroxy-3'-methoxy-3,4-methylenedioxy-4'-oxo-8.1',7.5'-neolignan, (7S,8R,1'S,5'S,6'R)-Delta(2',8')-3',5',6'-trihydroxy-3,4-methylenedioxy-4'-oxo-8.1',7.5'-neolignan, 2,4-dimethoxy-5,6-methylenedioxy-1-(2-propenyl)benzene, and 2,6-dimethoxy-3,4-methylenedioxycinnamyl alcohol, respectively, on the basis of spectroscopic interpretation.     

Phelligridins C-F: cytotoxic pyrano[4,3-c][2]benzopyran-1,6-dione and furo[3,2-c]pyran-4-one derivatives from the fungus Phellinus igniarius

Three unique pyrano[4,3-c][2]benzopyran-1,6-dione derivatives and a new furo[3,2-c]pyran-4-one, named phelligridins C-F (2-5), together with hispolon (8), (E)-4-(3,4-dihydroxyphenyl)but-3-en-2-one (9), 4-hydroxybenzaldehyde, protocatechualdehyde, syringic acid, protocatechuic acid, caffeic acid, isoergosterone, and octadecyl ferulate were isolated and identified from the ethanolic extract of Phellinus igniarius. Their structures were determined by spectroscopic methods including IR, MS, and 1D and 2D NMR experiments. The structures of the new compounds were characterized as 3-(4-hydroxystyryl)-8,9-dihydroxypyrano[4,3-c]isochromene-4-one (2), 3-(3,4-hydroxystyryl)-8,9-dihydroxypyrano[4,3-c]isochromene-4-one (3), 8,9-dihydroxy-3-[5',6'-dihydroxy-5' '-methyl-3' '-oxo-spiro[fural-2' '(3' 'H),1'-indene]-2'-yl]-1H,6H-pyrano[4,3-c][2]benzopyran-1,6-dione (4), and (3Z)-3-(3,4-dihydroxybenzylidene)-6-(3,4-dihydroxystyryl)-2,3-dihydro-2-methoxy-2-(2-oxo-propyl)furo[3,2-c]pyran-4-one (5), respectively. Some compounds including 2 and 3 showed in vitro selective cytotoxicity against a human lung cancer cell line (A549) and a liver cancer cell line (Bel7402). Possible biogenetic sequences to the formation of 1-9 are postulated.     

Three new sesquiterpenes from roots of Curcuma longa

Objective: To study the chemical constituents from the roots of Curcuma longa. Methods: The structures of the new compounds were elucidated based on extensive spectral analysis, including 1D and 2D NMR, MS, UV, and CD analysis. Results: Two new sesquiterpene compounds (1S,2R,5R,7S,8R)-2,8-epoxy-5-hydroxybisabola-3,10-dioen-9-one (1), (1R,2R,5R,7S,8R)-2,8-epoxy-5-hydroxybisabola-3,10-dioen-9-one (2), and a new natural product 6-(4-Hydroxymethylphenyl)-2-methyl-hept-2-ene-4-one (3) together with three known compounds ar-turmerone (4), 2-methyl-6-(4-hydroxyphenyl-3-methyl)-2-hepten-4-one (5) and 2-methyl-6-(4-hydroxyphenyl)-2-hepten-4-one (6) were isolated from C. longa root extract with 95% ethanol. Conclusion: In the study, three new compounds were isolated from C. longa, and their absolute configurations were determined.     

Structure and stereochemistry of new cytotoxic clerodane diterpenoids from the bark of Casearia lucida from the Madagascar rainforest

Bioassay-guided fractionation of a CH(2)Cl(2)/MeOH extract of the bark of Casearia lucida resulted in the isolation of 11 new clerodane diterpenes, namely, casearlucins A-K (1-11), and three known clerodane diterpenoids, rel-(2S,5R,6R,8S,9S,10R,18S,19R)-diacetoxy-18,19-epoxy-6-hydroxy-2-(2xi-methylbutanoyloxy)cleroda-3,13(16),14-triene (12), rel-(2S,5R,6R,8S,9S,10R,18S,19R)-18,19-diacetoxy-18,19-epoxy-6-methoxy-2-(2xi-methylbutanoyloxy)cleroda-3,13(16),14-triene (13), and rel-(2S,5R,8S,9S,10R,18S,19R)-18,19-diacetoxy-18,19-epoxy-2-(2xi-methylbutanoyloxy)cleroda-3,13(16),14-triene (14). The structures of compounds 1-11 were established on the basis of extensive 1D and 2D NMR spectroscopic data interpretation. All compounds exhibited cytotoxicity activity against the A2780 ovarian cancer cell line, but none of the six compounds selected for testing in multiple cell lines showed significant selectivity.     

Prenylated flavanones with anti-tyrosinase activity from Dalea boliviana

Three new prenylated flavanones, (2S)-5,7,2'-trihydroxy-5'-(1',1'-dimethylallyl)-8-prenylflavanone (1), (2S)-5,7,2'-trihydroxy-8,3'-diprenylflavanone (2), and (2S)-5,2'-dihydroxy-6',6'-dimethylchromeno-(7,8:2',3')-3'-prenylflavanone (3), and a known chromeno (dimethylpyrano) flavanone, obovatin (4), were isolated from the n-hexane extract of Dalea boliviana roots. The compounds were evaluated in vitro in relation to their inhibitory effect on the tyrosinase activity by using a spectrophotometric method.     

New phenolic constituents from Smilax bracteata

From the methanol extract of Smilax bracteata rhizomes, six new phenolic compounds, (2S,3S)-5-O-beta-D-glucopyranosyloxy-6-methyl-3'-methoxy-3,7,3'-trihydroxyflavan (1), (2S,3S)-5-O-beta-D-glucopyranosyloxy-6-methyl-4'-methoxy-3,7,4'-trihydroxyflavan (2), 3beta-(3',5'-dihydroxyphenyl)-2alpha-(4' '-hydroxyphenyl)dihydrobenzofuran-5-carbaldehyde (3), (1-p-O-coumaroyl-6-O-feruroyl)-beta-D-fructofuranosyl-alpha-D-glucopyranoside (4), (1-p-O-coumaroyl-3,6-di-O-feruroyl)-beta-D-fructofuranosyl-alpha-D-glucopyranoside (5), and (6-O-feruroyl)-beta-D-fructofuranosyl-(6-O-acetyl)-alpha-D-glucopyranoside (6) were isolated together with five known compounds. Their structures were established by spectral data interpretation.     

Cytotoxic dolabellane diterpenes from the Formosan soft coral Clavularia inflata

Six new cytotoxic dolabellane diterpenes, (1R,12R)-dolabella-4(16),7,10-triene-3,13-dione (1), (1R*,7R*,8S*,12R*)-dolabella-4(16),10-diene-7,8-epoxy- 3,13-dione (2), (1R*,10R*,11S*,12R*)-dolabella-4(16),7-diene-10,11-epoxy-3,13-dione (3), (1R)-dolabella-4(16),7,11(12)-triene-3,13-dione (4), (1R*,3R*)-3-hydroxydolabella-4(16),7,11(12)-triene-3,13-dione (5), and (1R*,7R*)-7-hydroperoxydolabella-4(16),8(17),11(12)-triene-3,13-dione (6), have been isolated from the Formosan soft coral Clavularia inflata. The structures of compounds 1-6 were determined by 1D and 2D spectral analysis, and their cytotoxicity against selected cancer cells was measured in vitro.     

Bisindole alkaloids of the topsentin and hamacanthin classes from a marine sponge Spongosorites sp

Seven new (1 and 3-8) and seven known (2 and 9-14) bisindole alkaloids of the topsentin and hamacanthin classes were isolated from the MeOH extract of a marine sponge Spongosorites sp. by bioactivity-guided fractionation. The structure of compound 7 is a revision from our previous report. The planar structures were established on the basis of NMR and MS spectroscopic analyses. Configurations of these compounds were defined by NMR spectroscopy and optical rotation. It is noteworthy that both R and S isomers were isolated for the hamacanthins (1-4, 9, 10, 15, and 16), while a single stereoisomer was isolated for dihydrohamacanthins (5, 11-14, 17, and 18). Compounds 1-4, 6, and 8-14 showed marginal cytotoxicity against five human solid tumor cell lines, and compound 2 showed weak antibacterial activity against clinically isolated methicillin-resistant strains.     

Mono-, Bi-, and triphenanthrenes from the tubers of Cremastra appendiculata

Six newphenanthrene derivatives, including three monophenanthrenes (1-3), two biphenanthrenes (4 and 5), and a triphenanthrene (6), have been isolated from an ethanolic extract of the tubers of Cremastra appendiculata. Using spectroscopic methods, the structures of compounds 1-6 were determined as 1-hydroxy-4,7-dimethoxy-1-(2-oxopropyl)-1H-phenanthren-2-one (1), 1,7-dihydroxy-4-methoxy-1-(2-oxopropyl)-1H-phenanthren-2-one (2), 2-hydroxy-4,7-dimethoxyphenanthrene (3), 2,7,2'-trihydroxy-4,4',7'-trimethoxy-1,1'-biphenanthrene (4), 2,2'-dihydroxy-4,7,4',7'-tetramethoxy-1,1'-biphenanthrene (5), and 2,7,2',7',2' '-pentahydroxy-4,4',4' ',7' '-tetramethoxy-1,8,1',1' '-triphenanthrene (6), respectively. Compounds 1-6 and two known compounds, cirrhopetalanthin (7) and flavanthrinin (8), obtained previously from this plant, were evaluated against six human cancer cells and a normal cell line.     

Sesquiterpenes and flavonol glycosides from Zingiber aromaticum and their CYP3A4 and CYP2D6 inhibitory activities

Three new sesquiterpenes, (2R,3S,5R)-2,3-epoxy-6,9-humuladien-5-ol-8-one (1), (2R,3R,5R)-2,3-epoxy-6,9-humuladien-5-ol-8-one (2), and (5R)-2,6,9-humulatrien-5-ol-8-one (3), and two new flavonol glycosides, kaempferol-3-O-(2,3-di-O-acetyl-alpha-l-rhamnopyranoside) (4) and kaempferol-3-O-(2,3,4-tri-O-acetyl-alpha-l-rhamnopyranoside) (5), were isolated from the EtOAc-soluble fraction of the water extract of Zingiber aromaticum, along with 13 known compounds (6-18). The structures of the isolated compounds were elucidated on the basis of spectroscopic and chemical analyses. The isolated compounds were tested for their inhibitory activity on the metabolism mediated by CYP3A4 or CYP2D6 using [N-methyl-(14)C]erythromycin or [O-methyl-(14)C]dextromethorphan as a substrate, respectively. Kaempferol-3-O-(2,3,4-tri-O-acetyl-alpha-l-rhamnopyranoside) (5) showed the most potent inhibitory activity (IC(50), 14.4 microM) on the metabolism mediated by CYP3A4, and kaempferol-3-O-methyl ether (14) inhibited CYP2D6 most potently (IC(50), 4.63 microM).     

桫椤化学成分研究

目的:研究桫椤Cyathea spinulosa Wall.的化学成分。方法:采用各种柱色谱进行分离纯化,根据理化性质和光谱数据进行结构鉴定。结果:从桫椤的乙醇提取物中共分离鉴定了8个化合物,分别为:豆甾-4-烯-3,6-二酮(1)、豆甾-3,6-二酮(2)、麦角甾醇(3)、原儿茶醛(4)、1-O-β-D-glucopyranosyl-(2S,3R,4E,8Z)-2-[(2-hydroxyoctade-canoyl)amido]-4,8-octadecadiene-1,3-diol(5)、(2S,3S,4R)-2-[(2'R)-2'-hydroxytetracosanoylamino]-1,3,4-octade-canetriol(6)、β-谷甾醇(7)、胡萝卜苷(8)。结论:其中,化合物1～6为首次从该植物中分离得到。     

桑椹醇提物的化学成分研究

目的研究桑椹Mori Fructus醇提物的化学成分。方法采用硅胶、Sephadex LH-20和ODS柱色谱法及半制备型高效液相色谱进行分离纯化,通过其理化性质和波谱数据对化合物结构进行鉴定。结果从桑椹醇提物中分离得到12个化合物,分别鉴定为桑脂素苷(1)、(7R,8S)-4,7,9,9′-tetrahydroxy-3,3′-dimethoxy-8-O-4′-neolignan-9′-O-β-D-glucopyranoside(2)、2-苯乙基-β-D-吡喃葡萄糖苷(3)、1′-O-苯乙基-β-D-呋喃芹菜糖基-(1→2)-β-D-吡喃葡萄糖苷(4)、苯甲醇-O-β-D-吡喃葡萄糖苷(5)、过氧麦角甾醇(6)、(24R)-6β-hydroxy-24-ethyl-cholest-4-en-3-one(7)、(22E)-5α,8α-epidioxy-24-methyl-cholesta-6,9(11),22-trien-3β-ol(8)、trans-(S)-(+)-脱落酸(9)、cis-(S)-(+)-脱落酸(10)、(S)-(+)-1-甲基-脱落-6-酸(11)、菜豆酸(12)。结论化合物1为未见文献报道的新化合物,化合物2、7~12为首次从该植物中分离得到。