Bromophenols coupled with nucleoside bases and brominated tetrahydroisoquinolines from the red alga Rhodomela confervoides

Three new bromophenols C-N coupled with nucleoside base derivatives (1-3) and three new brominated 1,2,3,4-tetrahydroisoquinolines (5-7), together with a new brominated tyrosine derivative (4), have been isolated from polar fractions of an ethanolic extract of the red alga Rhodomela confervoides. By spectroscopic and chemical methods including HRMS and 2D NMR data, their structures were determined as 7-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyl]-3,7-dihydro-1H-purine-2,6-dione (1), 7-(2,3-dibromo-4,5-dihydroxybenzyl)-3,7-dihydro-1H-purine-2,6-dione (2), 9-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyl]adenine (3), (-)-8S-(3-bromo-5-hydroxy-4-methoxy)phenylalanine (4), (-)-3S-8-bromo-6-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid (5), methyl (-)-3S-8-bromo-6-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylate (6), and methyl (-)-3S-6-bromo-8-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylate (7). Compounds 5-7 were semisynthesized by using 4 as the starting material.     

Hyrtioerectines A-C, cytotoxic alkaloids from the red sea sponge hyrtioserectus

A Red Sea specimen of the marine sponge Hyrtios erectus was found to contain three new alkaloids, hyrtioerectines A-C (1-3). Hyrtioerectine A (1) possesses the carbon bond-linked moieties 6-hydroxy beta-carboline and 6-hydroxyindole. The structure elucidation of 1-3 was based on intensive study of their spectral data including 1D (1H and 13C) and 2D (1H-1H COSY, HOHAHA, NOESY, ROESY, HMQC, and HMBC) NMR, together with high-resolution mass spectra. Hyrtioerectines A-C were moderately cytotoxic.     

Hyrtiazepine, an azepino-indole-type alkaloid from the Red Sea marine sponge Hyrtios erectus

Biological and chemical investigations of the methanolic crude extract of the Red Sea marine sponge Hyrtios erectus led to the isolation of a novel azepino-indole-type alkaloid named hyrtiazepine (2) and 5-hydroxy-1H-indole-3-carboxylic acid methyl ester (3), together with the known metabolites hyrtiosulawesine (1), 5-hydroxyindole-3-carbaldehyde (4), hyrtiosin A (5), and hyrtiosin B (6). Their structures were elucidated on the basis of mass spectrometry and detailed 2D NMR spectroscopic data. Hyrtiosulawesine (1) displayed a significant antiphospholipase A2 activity with an IC50 value of 14 microM in a fluorometric assay using Crotalus adamanteus venom phospholipase A2.     

Cacalolides from Senecio madagascariensis

14-Isovaleryloxy-O-methyl-1,2-dehydrocacalol (1) and cycloart-23-ene-3,25-diol, beta-sitosterol, and stigmasterol, along with five new cacalolides, 1-hydroxy-2-methoxy-1,2,3,4-dehydro-6-dehydroxycacalone (2), 1-hydroxy-2-methoxy-1,2,3,4-dehydrocacalone (3), 1,2-dimethoxy-1,2,3,4-dehydro-6-dehydroxycacalone (4), 1,2-dimethoxy-1,2,3,4-dehydrocacalone (5), and 2-methoxy-O-methyl-1-oxo-2,3-dehydrocacalol (6), were isolated from Senecio madagascariensis collected from Colombia. The structures of the new compounds were determined using one- and two-dimensional NMR techniques. In addition, the structure of 2 was corroborated by derivatizations and single-crystal X-ray diffraction studies.     

Antiinflammatory constituents from Heterotheca inuloides

Three new compounds, cadalen-15-oic acid (1), 3,7-dihydroxy-3(4H)-isocadalen-4-one (2), and dicadalenol (3), were isolated from the aerial parts of Heterotheca inuloides (Mexican arnica), together with the known compounds 7-hydroxycadalene (4), 7-hydroxy-4alphaH-3,4-dihydrocadalene (5), 1alpha-hydroxy-1(4H)-isocadalen-4-one (6), 1alpha-hydroxy-4alphaH-1,2,3,4-tetrahydrocadalen-15-oic acid (7), 7-(3,3-dimethylallyloxy)coumarin, caryolan-1,9beta-diol, and quercetin. The structures of the new compounds were elucidated by spectroscopic methods. The antiinflammatory activities of the extracts and the isolated compounds were evaluated by determining the inhibition of TPA-induced mouse ear edema. The natural products 3, caryolan-1,9beta-diol, and quercetin were the most active substances tested and displayed dose-dependent activities.     

Cytotoxic alkaloids from Fusarium incarnatum associated with the mangrove tree Aegiceras corniculatum

Several unusual alkaloids, N-2-methylpropyl-2-methylbutenamide (1), 2-acetyl-1,2,3,4-tetrahydro-β-carboline (2), fusarine (3), fusamine (4), and 3-(1-aminoethylidene)-6-methyl-2H-pyran-2,4(3H)-dione (5), were isolated from the culture broth of Fusarium incarnatum (HKI0504), an endophytic fungus of the mangrove plant Aegiceras corniculatum. Compounds 2, 4, and 5 exhibit weak antiproliferative and cytotoxic activities against HUVEC, K-562, and HeLa human cell lines, respectively.     

臭辣树化学成分

目的:研究臭辣树的化学成分。方法:采用硅胶柱层析的方法分离和纯化化合物,根据理化性质和波谱方法鉴定化合物结构。结果:从臭辣树中分离得到13个化合物,包括6个生物碱:2methyl6hydroxy1,2,3,4tetrahydroβcarboline(1),N,Ndimethyltryptamine(2),Npcoumaroyltyramine(3),dictamnine(4),robustine(5),haplophine(6);3个柠檬苦素类化合物:limonin(7),rutaevine(8),和evodol(9);2个黄酮类化合物:quercetin(10)和( )dihydroquercetin(11);以及βsitosterol(12)和daucosterol(13)。结论:化合物1为新化合物,其它化合物均为首次从本植物中分离得到。     

Alkaloids from Porcelia macrocarpa.

Three new azaanthracene alkaloids, 6,7-dimethoxycleistopholine (3), 5-hydroxy-6-methoxycleistopholine (4), and 5-hydroxy-6,7-dimethoxycleistopholine (5), along with 14 known alkaloids, including the new natural product 6-methoxycleistopholine (2), were isolated from a CH2Cl2 extract of the branches of Porcelia macrocarpa.     

Morphinane alkaloids with cell protective effects from Sinomenium acutum

One new morphinane alkaloid, sinomenine N-oxide (1), and one new natural occurring morphinane alkaloid, N-demethylsinomenine (2), together with six known alkaloids, 7,8-didehydro-4-hydroxy-3,7-dimethoxymorphinan-6-ol (3), sinomenine (4), sinoacutine (5), N-norsinoacutine, acutumine, and acutumidine, were isolated from the stems of Sinomenium acutum. Their structures were elucidated on the basis of spectroscopic analysis and chemical methods. Compounds 2, 3, and 5 have protective effects against hydrogen peroxide-induced cell injury.     

Isolation of gelsedine-type indole alkaloids from Gelsemium elegans and evaluation of the cytotoxic activity of gelsemium alkaloids for A431 epidermoid carcinoma cells

Four new gelsedine-type indole alkaloids (1-4) were isolated from the leaves of Gelsemium elegans, together with 11 known alkaloids. The structures were determined as 14-acetoxygelsenicine (1), 14-acetoxy-15-hydroxygelsenicine (2), 14-hydroxy-19-oxogelsenicine (3), and 14-acetoxygelselegine (4), respectively, by spectroscopic analysis. The cytotoxic effects of 14 Gelsemium alkaloids including two new compounds (1, 2) were evaluated using the A431 human epidermoid carcinoma cell line. Of these, the gelsedine-type alkaloids 14-acetoxy15-hydroxygelsenicine (2) [corrected] 14,15-dihydroxygelsenicine (5), gelsedine (7), and gelsemicine (8) showed potent cytotoxic effects.     

钩枝藤茎枝生物碱类成分的研究

 目的对钩枝藤茎、枝的化学成分进行研究。方法采用氧化铝柱色谱,硅胶柱色谱,Sephadex LH-20凝胶柱色谱进行分离,通过理化和波谱分析鉴定结构。结果分离并鉴定了7生物碱个化合物。分别为ancistrobertsonine B(1),an- cistrotectorine(2),(1S,3S)-5-(4,5-二甲氧基-2-甲基萘-1-基)-6,8-二甲氧基-1,3-二甲基-1,2,3,4-四氢异喹啉(3),(1S,3R)-5-(4,5-二甲氧基-2-甲基萘-1-基)-6,8-二甲氧基-1,3-二甲基-1,2,3,4-四氢异喹啉(4),ancistro- cline(5),ancistrocladinine(6),hamatinine(7)。结论化合物1,3,4,6,7均为首次从该植物中分离得到。     

Alkaloids from Eschscholzia californica and their capacity to inhibit binding of [3H]8-Hydroxy-2-(di-N-propylamino)tetralin to 5-HT1A receptors in Vitro

A 70% ethanol extract of California poppy (Eschscholzia californica) was able to bind to 5-HT(1A) and 5-HT(7) receptors at 100 mug/mL. The subsequent isolation procedure yielded the known alkaloids californidine (1), escholtzine (2), N-methyllaurotetanine (3), caryachine (4), and O-methylcaryachine (5), along with a new pavine alkaloid, 6S,12S-neocaryachine-7-O-methyl ether N-metho salt (7). The structure of 7 was determined by spectroscopic data interpretation, while the absolute stereochemistry was determined by means of circular dichroism. From the results obtained from the radioligand-binding assay of the pure compounds, including the commercially available protopine (6), it was evident that the activity on the 5-HT(1A) receptor was at least partly due to the presence of the aporphine alkaloid 3, which showed the highest inhibition of [(3)H]8-hydroxy-2-(di-N-propylamino)tetralin ([(3)H]8-OH-DPAT) binding with an EC(50) value of 155 nM and a K(i) of 85 nM.     

Thymol, benzofuranoid, and phenylpropanoid derivatives: anti-inflammatory constituents from Eupatorium cannabinum

Five new compounds, 9-O-angeloyl-8,10-dehydrothymol (1), 9-(3-methylbutanoyl)-8,10-dehydrothymol (2), eupatobenzofuran (3), 2-hydroxy-2,6-dimethylbenzofuran-3(2H)-one (4), and 1-(2-hydroxy-4-methylphenyl)propan-1,2-dione (5), have been isolated from the aerial part of Eupatorium cannabinum subsp. asiaticum, together with 16 known compounds (6-21). Compounds 6-8, 11, 13, and 15 exhibited inhibition (IC50 values≤18.4 μM) of superoxide anion generation by human neutrophils in response to formyl-L-methionyl-L-leucyl-L-phenylalanine/cytochalasin B (fMLP/CB). Compounds 2, 3, 10, 13, and 15 inhibited fMLP/CB-induced elastase release with IC50 values≤18.3 μM.     

山海绵Mycale parishi化学成分研究

对采自南中国海的山海绵Mycale parishi化学成分进行研究，从中分离鉴定了3个生物碱：5-甲基-1-(2-脱氧-β-D-呋喃核糖)-2，4(1H)-嘧啶二酮(Ⅰ)、尿嘧啶(Ⅱ)、N-2-羟基-1-羟甲基-3-十七烯基-二十五脂肪酸酰胺(Ⅲ)，其中化合物Ⅲ未见文献报道。     

New indole alkaloids from the bark of Nauclea orientalis

Four new alkaloids, nauclealines A (1) and B (2) and naucleosides A (3) and B (4), together with six known compounds, strictosamide (5), vincosamide (6), pumiloside (7), kelampayoside A, sitosterol, and sitosteryl beta-D-glucoside, were isolated from the bark of Nauclea orientalis. The structures of 1-4 were elucidated using 1D and 2D NMR spectral methods, including COSY, DEPT, HMQC, (13)C-(1)H HMBC, and (15)N-(1)H HMBC.     

皮孔葱臭木化学成分的研究

目的对皮孔葱臭木Dysoxylum lenticellatum茎干的化学成分及其细胞毒活性进行研究。方法利用正相硅胶、RP-18柱色谱、葡聚糖凝胶Sephadex LH-20等手段进行分离纯化,根据波谱数据鉴定化合物的结构,采用MTT法进行细胞毒活性测定。结果分离鉴定了12个化合物,分别为β-谷甾醇(1)、豆甾醇(2)、3-oxo-24,25,26,27-tetranortirucall-7-ene-23(21)-lactone(3)、3α-hydroxy-24,25,26,27-tetranortirucall-7-ene-23(21)-lactone(4)、laxiracemosin H(5)、laxiracemosin B(6)、24,25-epoxy-tirucall-7-ene-3,23-dione(7)、丁酰鲸鱼醇(8)、齐墩果酸(9)、蒲公英赛酮(10)、蒲公英赛醇(11)和8-hydroxy-6-methoxy-3-pentylisocoumarin(12)。结论 12个化合物均为首次从该种植物中分离得到,化合物8、10～12为首次从该属植物中分离得到,化合物5、6是甘遂烷型生物碱,化合物3具有明显体外肿瘤细胞生长抑制活性。     

Indole alkaloids from three species of the Ervatamia genus: E. officinalis, E. divaricata, and E. divaricata Gouyahua

Six new indole alkaloids, 14,15-didehydro-10,11-dimethoxy-16-epivincamine (1), 14,15-didehydro-10-hydroxy-11-methoxy-16-epivincamine (2), 14,15-didehydro-10,11-dimethoxyvincamine (3), 14,15-didehydro-10-hydroxy-11-methoxyvincamine (4), 19,20-didehydro-6alpha-hydroxyervatamine (5), and dehydroxyervataminol (6), along with 36 known indole alkaloids, were isolated from three species, E. officinalis, E. divaricata, and E. divaricata Gouyahua, of the Ervatamia genus. The structures of these alkaloids were characterized on the basis of spectroscopic methods and chemical correlation. The in vitro cytotoxic activities of all the alkaloids except 7, 18, 27, 38, 40, and 44 against the tumor cell lines P-388 murine leukemia and A-549 human lung carcinoma were evaluated. Only the dimeric indole alkaloids showed cytotoxic activities.     

零余子中环肽类化学成分及其生物活性研究

目的 探究零余子(bulbils of Dioscorea opposita Thunb.)中含氮类化学成分及其生物活性。方法 采用硅胶、Sephadex LH-20、MCI gel CHP-20、ODS等柱色谱及制备型高效液相分离纯化,结合理化性质及其波谱数据鉴定化合物结构。采用多柔比星诱导的NRK-52E细胞损伤模型及皮质酮诱导的PC-12细胞损伤模型分别检测所得化合物的肾细胞保护作用及神经细胞保护作用。结果 从零余子中分离得到15个含氮类化合物,分别鉴定为环(L-苯丙-L-酪)二肽(1)、环(L-缬-L-脯)二肽(2)、环(D-色-D-酪)二肽(3)、环(L-脯-L-酪)二肽(4)、环(L-苯丙-L-丙)二肽(5)、环(L-亮-L-脯)二肽(6)、环(L-异亮-L-脯)二肽(7)、环(D-脯-L-酪)二肽(8)、环(L-苯丙-L-脯)四肽(9)、3-羟基-3-(2-丙酰)-2,4(1H, 3H)-喹啉二酮(10)、3-吲哚甲醛(11)、木瓜新碱A(12)、1-核糖醇基-2,3-二酮-1,2,3,4-四氢-6,7-二甲基-喹喔啉(13)、白曼陀罗酰胺(14)、苯丙氨酸(15)。化合物2、5、9、14能显著提高NRK-52E细胞活力。化合物对PC-12细胞活力均无明显影响。结论 化合物2~5、7~9、11~14均为首次从薯蓣属植物中分离得到。首次报道化合物2、5、9、14在体外中表现出较好的肾细胞保护作用。     

New indole alkaloids from the roots of Ochrosia acuminata

Two new indole alkaloids, polyneuridine-N-oxide (1) and 17-hydroxy-10-methoxy-yohimbane (2), together with seven known alkaloids were isolated from the roots of Ochrosia acuminata collected in Savu, Indonesia. 9-Methoxyellipticine (3) and ellipticine (4) were responsible for the antitumor activities of the extract. The structures of all compounds were elucidated using MS and NMR methods.     

荷叶中的一个新阿朴啡型生物碱

目的荷叶为睡莲科植物莲Nelumbo nucifera的叶,本实验对其化学成分进行研究。方法应用多种色谱技术进行分离纯化,通过理化方法和波谱数据进行结构鉴定。结果分离鉴定出9个生物碱类成分,分别为2-羟基-1-甲氧基-6-甲基-6a,7-去氢阿朴啡(2-hydroxy-1-methoxy-6-methyl-6a,7-dehydroaporphine,1)、杏黄罂粟碱(armepavine,2)、去氢莲碱(dehydroroemerine,3)、去氢荷叶碱(dehydronuciferine,4)、2-羟基-1-甲氧基阿朴啡(2-hydroxy-1-methoxyaporphine,5)、鹅掌楸碱(liriodenine,6)、原荷叶碱(pronuciferine,7)、莲碱(roemerine,8)和荷叶碱(nuciferine,9)。结论化合物1为一新的阿朴啡型生物碱,命名为睡莲碱(nelumnucine)。