Neuroprotective limonoids of root bark of Dictamnus dasycarpus

A methanolic extract of Dictamnus dasycarpus root bark afforded four new degraded limonoids, 9alpha-hydroxyfraxinellone-9- O-beta- d-glucoside ( 1), dictamnusine ( 2), dictamdiol A ( 3), and dictamdiol B ( 4), together with eight known compounds, dictamdiol ( 5), fraxinellone ( 6), fraxinellonone ( 7), 9beta-hydroxyfraxinellone ( 8), calodendrolide ( 9), obacunone ( 10), limonin ( 11), and rutaevin ( 12). Compounds, 2, 3, 6, 9, 10, and 11 showed significant neuroprotective activity against glutamate-induced neurotoxicity in primary cultures of rat cortical cells at a concentration of 0.1 microM.     

Cytotoxic sesquiterpene lactones from Eupatorium lindleyanum

Ten new guaiane type sesquiterpene lactones, namely, eupalinilides A-J (1-10), as well as nine known compounds, eupachinilide C (11), eupachifolin D (12), eupachinilide E (13), 2alpha-hydroxyeupatolide (14), 3-deacetyleupalinin A (15), heliangine (16), 8beta-tigloyloxy-2,3-seco-6betaH,7alphaH-helianga-4Z,11(13)-diene-3,10beta;6, 12-diolid-2-oic acid (17), 8beta-(4'-hydroxytigloyloxy)-3beta,14-dihydroxy-6betaH,7alphaH-germacra-1(10)Z,4Z,11(13)-trien-6,12-olide (18), and 8beta-tigloyloxy-3beta,14-dihydroxy-6betaH,7alphaH-germacra-1(10)Z,4E,11(13)-trien-6,12-olide (19), were isolated from the whole plant of Eupatorium lindleyanum. Eupalinilides B (2), C (3), E (5), F (6), and I (9) have been tested for cytotoxicity against P-388 and A-549 tumor cell lines. The results showed that eupalinilides B (2) and E (5) demonstrated potent cytotoxicity. The structures of these compounds were determined by spectroscopic methods including 1D and 2D NMR spectra.     

Cytotoxic sesquiterpenoids from Eupatorium chinense

Ten new sesquiterpenoids, namely, eupachinilides A-J (1-10), together with seven known sesquiterpenoids, eupachifolin D (11), budlein B (12), 8 beta-(4'-hydroxytiglyloxy)-2 beta-hydroxy-1 alpha H,5 alpha H,6 beta H,7 alpha H-guai-3,10(14),11(13)-trien-6,12-olide (13), 1,10-hydrobahia (14), 2 alpha-hydroxyeupatolide (15), eupaserrin (16), and mollisorin B (17), were isolated from the whole plant of Eupatorium chinense. Their structures were elucidated mainly by spectral methods, especially 2D NMR techniques. Eupachinilides A (1), E (5), F (6), and I (9) exhibited moderate cytotoxic activities against several tumor cell lines. The structures assigned previously for eupachifolins B (11a), C (13a), and D (11) were revised by spectral analysis and 2D NMR techniques.     

Cassane diterpenoids of Caesalpinia pulcherrima

Five new cassane diterpenoids (1-5) were isolated from the roots of Caesalpinia pulcherrima, along with the known isovouacapenol C (6), pulcherrimin A (11), and 6beta-cinnamoyl-7beta-hydroxyvouacapen-5alpha-ol (12). Compounds 3-5 possess the alpha,beta-butenolide moiety, whereas compounds 1 and 2 contain a more usual 2,3-disubstituted furan unit. Compounds 7 and 8 were derived from hydrolysis of 6, while 9 and 10 were derived from acetylation and oxidation of 6, respectively. The (1)H and (13)C NMR spectra of all compounds were completely assigned using a combination of 2D NMR experiments, including (1)H-(1)H COSY, HSQC, HMBC, and T-ROESY sequences.     

Jiquilpane hydrocarbon skeleton generated by two successive Wagner-Meerwein rearrangements of longipinane derivatives

The molecular rearrangement of (1R,3S,4S,5S,7S,8R,9S,10R,11R)-7,8,9-triacetyloxylongipinan-1-ol (4) under acidic conditions afforded (1S,4R,5R,7S,8R,9S,10S)-7,8,9-triacetyloxyuruap-3(12)-ene (5), while 6, the C(3)-stereoisomer of 4, after two consecutive Wagner-Meerwein rearrangements followed by two 1,2-hydride migrations, afforded (4R,5R,7S,8S,9S,10S,11S)-7,8,9-triacetyloxyjiquilp-3(12)-ene (7), which possesses a new hydrocarbon skeleton. The structures of the new substances were elucidated by 1D and 2D NMR data in combination with X-ray diffraction analyses of the uruapane, longipinane, and jiquilpane derivatives 5, 6, and 14, respectively. Molecular modeling at the ab initio level was used to study the reaction mechanisms, while deuterium labeling was employed to confirm the C-C bond migrations and the hydride shifts.     

Biologically active polyketide metabolites from an undetermined fungicolous hyphomycete resembling Cladosporium

Eight new polyketide-derived metabolites [cladoacetals A and B (1 and 2), 3-(2-formyl-3-hydroxyphenyl)propionic acid (3), 3-deoxyisoochracinic acid (4), isoochracinol (5), 7-hydroxy-3-(2,3-dihydroxybutyl)-1(3H)-isobenzofuranone (6), (+)-cyclosordariolone (10), and altersolanol J (11)] and six known metabolites [two isomeric 1-(1,3-dihydro-4-hydroxy-1-isobenzofuranyl)butan-2,3-diols (7a/b), 7-hydroxy-1(3H)-isobenzofuranone (8), isoochracinic acid (9), altersolanol A (12), and macrosporin (13)] have been isolated from solid-substrate fermentation cultures of an undetermined fungicolous isolate (NRRL 29097) that resembles Cladosporium sp. All structures were assigned primarily by analysis of 1D and/or 2D NMR data. Five of the compounds showed antibacterial activity.     

Investigation of brominated tryptophan alkaloids from two thorectidae sponges: Thorectandra and Smenospongia

Chemical investigation of an NCI-DTP collection of Thorectandra sp. and a UCSC collection of Smenospongia sp. yielded six new brominated tryptophan derivatives: 6-bromo-1'-hydroxy-1',8-dihydroaplysinopsin (4), 6-bromo-1'-methoxy-1',8-dihydroaplysinopsin (5), 6-bromo-1'-ethoxy-1',8-dihydroaplysinopsin (6), (-)-5-bromo-N,N-dimethyltryptophan (7), (+)-5-bromohypaphorine (8), and 6-bromo-1H-indole-3-carboxylic acid methyl ester (11). Additionally, the known compounds aplysinopsin (1), 1',8-dihydroaplysinopsin (2), 6-bromo-1',8-dihydroaplysinopsin (3), (1H-indole-3-yl)acetic acid (9), and (6-bromo-1H-indol-3-yl)acetic acid methyl ester (10) were also encountered. The structures of 4-8 and 11 were confirmed on the basis of analysis of (1)H and (13)C (1D and 2D) NMR data as well as comparison to known compounds. Compounds 1, 3-8, 10, and 11 were found to inhibit the growth of Staphylococcus epidermidis with either weak or moderate MICs.     

Eremophilane-type sesquiterpene derivatives from Senecio aegyptius var. discoideus

Investigation of a CH(2)Cl(2) extract of the aerial parts of Senecio aegyptius var. discoideus afforded nine eremophilane compounds, of which six are new (1-6), namely, 1beta-hydroxy-8alphaH-eremophil-7(11),9-dien-8beta,12-olide (1), 1beta,8alpha-dihydroxyeremophil-7(11),9-dien-8beta,12-olide (2), 1beta-hydroxy-8alpha-methoxyeremophil-7(11),9-dien-8beta,12-olide (3), 1-oxo-8alpha-methoxy-10alphaH-eremophil-7(11)-en-8beta,12-lactam (4), 1beta,10beta-epoxy-8alpha-hydroxyeremophil-7(11)-en-8beta,12-olide (5), and 1beta,10beta-epoxy-8alpha-methoxyeremophil-7(11)-en-8beta,12-olide (6). The structures of 1-6 were elucidated by spectroscopic methods and by comparison with literature data. The antibacterial activity of the isolated compounds was tested against Bacillus cereus and a Serratia sp.     

New antioxidant hydroquinone derivatives from the algicolous marine fungus Acremonium sp

A marine fungal isolate, identified as Acremonium sp., was mass cultivated and found to produce two novel hydroquinone derivatives, 7-isopropenylbicyclo[4.2.0]octa-1,3,5-triene-2,5-diol (1) and 7-isopropenylbicyclo[4.2.0]octa-1,3,5-triene-2,5-diol-5-beta-D-glucopyranoside (2). Compound 1 and its glucoside 2 possess a most unusual ring system. The new natural products (3R,4S)-3,4-dihydroxy-7-methyl-3,4-dihydro-1(2H)naphthalenone (3) and (3S,4S)-3,4-dihydroxy-7-methyl-3,4-dihydro-1(2H)-naphthalenone (4) were obtained as a 1:0.8 mixture. 2-(1-Methylethylidene)pentanedioic acid (5) was isolated for the first time as a natural product and its structure proven by X-ray analysis. In addition to these compounds an inseparable mixture of three new isomeric compounds, pentanedioic acid 2-(1-methylethylidene)-5-methyl ester (6), pentanedioic acid 2-(1-methylethylidene)-1-methyl ester (7), and pentanedioic acid 2-(1-methylethenyl)-5-methyl ester (8), was also obtained. Isolated together with the new compounds were three known hydroquinone derivatives, 9, 10, and 11. The structures of all compounds were determined by interpretation of their spectroscopic data (1D and 2D NMR, MS, UV, and IR). Each isolate was tested for its antioxidant properties, and compounds 1 and 9-11 were found to have significant activity.     

大青叶的化学成分研究

目的：对十字花科植物菘蓝Isatis indigotica Fort.叶的化学成分进行研究。方法：大青叶的干燥叶用80%乙醇提取,依次用石油醚,醋酸乙酯,正丁醇萃取,对醋酸乙酯部分采用硅胶、Sephadex LH-20, Rp-8, Rp-18柱色谱进行分离纯化,通过波谱数据分析(MS,¹H-NMR,¹³C-NMR)进行结构鉴定。结论：从醋酸乙酯部分分离鉴定了11个化合物,其中5个生物碱,2个芳香酸,2个木脂素,2个黄酮。分别鉴定为：10H-indolo［3,2-b］quinoline(1),靛玉红(2),4(3H)-喹唑酮(3),(E)-3-(3′,5′-dimethoxy-4′-hydroxybenzylidene)-2-indolinone(4),deoxyvascinone(5),苯甲酸(6),邻羟基苯甲酸(7),(-)-落叶松脂素(8),(+)-异落叶松树脂醇(9),异牡荆素(10),6-β-D-glucopyranosyldiosmetin(11)。其中化合物1,4,5,8,9,11为首次从大青叶中分离得到。     

黄花中华苦荬菜化学成分研究

目的 研究干燥黄花中华苦荬菜全草的化学成分。方法 采用硅胶柱色谱、HPLC、重结晶等方法进行分离纯化,依据理化性质和波谱数据鉴定结构。结果 从黄花中华苦荬菜全草中分离得到15 个化合物,分别鉴定为chinensioide F(1),chinensioide C(2),胡萝卜苷(3),6′-对羟基苯乙酰基-ixerin D(4),对羟基苯乙酸甲酯(5),对羟基苯乙醇(6),3,5-二甲氧基-4-羟基苯丙醇(7),10α-羟基-愈创木烷-12,6-内酯-3-酮(8),β-谷甾醇(9),chinensioide E(10),chinensioide D(11),ixerochinoside(12),3β,10α-二羟基-4(15),11(13)-愈创木二烯-12,6-内酯(13),10α-羟基-11βH-4(15)-愈创木烯-12,6-内酯(14),木犀草素-7-O-β-D-葡萄糖苷(15)。结论 化合物1为新化合物,命名为chinensiode F,4~7、12~14首次从该植物中分离得到。     

Daphnane- and tigliane-type diterpenoid esters and orthoesters from Pimelea elongata

Investigation of Pimelea elongata ("Lakebed Pimelea") afforded 18 tigliane- and daphnane-type diterpenes (1-18). Eight of these were new compounds: four (1-3, 5) tigliane esters and four (7, 8, 10, 11) daphnane orthoesters. The 10 known compounds were 12-O-decanoylphorbol-13-acetate (4), P. simplex subtoxin B (6), wikstroelide E (9), pimelotides A and B (12, 13), gnidiglaucin (14), simplexin (15), huratoxin (16), kirkinine D (17), and 12-β-acetoxyhuratoxin (18). The structures and relative configurations of the new compounds were determined by 1D and 2D NMR spectroscopic studies in combination with MS analyses.     

Hydroxylated gedunin derivatives from Cedrela sinensis

Four new limonoids, 11alpha-hydroxygedunin (1), 11beta-hydroxygedunin (2), 7-deacetoxy-7alpha,11alpha-dihydroxygedunin (3), and 7-deacetoxy-7alpha,11beta-dihydroxygedunin (4), were isolated from the cortex of Cedrela sinensis, together with three known compounds, gedunin (5), 7-deacetoxy-7alpha-hydroxygedunin (6), and 11-oxogedunin (7). The structures of 1-4 were determined by a combination of 2D NMR experiments and chemical methods and by X-ray crystallography of 1 and 2.     

Antineoplastic agents. 522. Hernandia peltata (Malaysia) and Hernandia nymphaeifolia (Republic of Maldives)

Bioassay (P388 lymphocytic leukemia cell line and human tumor cell lines)-guided separation of the extracts prepared from the tropical and coastal trees Hernandia peltata (Malaysia) and Hernandianymphaeifolia (Republic of Maldives) led to the isolation of a new lignan designated as hernanol (1) and 12 previously known lignans: (-)-deoxypodophyllotoxin (2), deoxypicropodophyllin (3), (+)-epiaschantin (4), (+)-epieudesmin (5), praderin (6), 5'-methoxyyatein (7), podorhizol (8), deoxypodorhizone (9), bursehernin (10), kusunokinol (11), clusin (12), and (-)-maculatin (13). The oxidative cyclization (with VOF(3)) of lignans 8, 9, and 10 resulted in a new and unusual benzopyran (14), isostegane (15), and a new dibenzocyclooctadiene lactone (16), respectively. The structure and relative stereochemistry of hernanol (1) and lignans 3, 7, 8, 9, 10, 11, and 12 were determined by 1D and 2DNMR and HRMS analyses. The structures and absolute stereochemistry of structures 2, 4, 5, 6, 13, 14, 15, and 16 were unequivocally determined by single-crystal X-ray diffraction analyses. Evaluation against the murine P388 lymphocytic leukemia cell line and human tumor cell lines showed podophyllotoxin derivatives 2 and 3 to be strong cancer cell line growth inhibitors and substances 4, 5, 8, and 15 to have marginal cancer cell line inhibitory activities. Seven of the lignans and one of the synthetic modifications (14) inhibited growth of the pathogenic bacterium Neisseria gonorrhoeae.     

Eleven novel diarylheptanoids and two unusual diarylheptanoid derivatives from the seeds of Alpinia blepharocalyx.

An EtOH extract of the seeds of Alpinia blepharocalyx afforded 11 novel diarylheptanoids, named deoxycalyxin A (1), epicalyxin F (2), calyxin K (3), epicalyxin K (4), calyxin I (5), epicalyxin I (6), calyxin J (7), epicalyxin J (8), and calyxin L (9), an epimeric mixture of calyxin M (10) and epicalyxin M (11), and two unusual diarylheptanoid derivatives, named neocalyxins A (12) and B (13), together with four known calyxins, calyxins A (14), F (15), E (16), and G (17). Structures were elucidated by spectroscopic techniques including 2D NMR spectroscopy. All compounds were examined for cytotoxicity toward murine colon 26-L5 carcinoma and human HT-1080 fibrosarcoma cells. Diarylheptanoids 2, 3, and 5 were cytotoxic against both cell lines, while 4 and 6-8 were cytotoxic against human fibrosarcoma cells.     

小槐花的化学成分研究

目的:系统研究中药小槐花中的化学成分。方法:利用大孔树脂,Sephadex LH-20,ODS及正相硅胶柱等色谱手段进行分离,通过多种波谱学数据分析进行化合物的结构鉴定。结果:从小槐花60%乙醇提取物中分离得到15个化合物,经结构鉴定分别为豆甾醇(1),β-谷甾醇(2),柠檬酚(3),黄槿酮A(4),异柠檬酚(5),kenusanone I(6),neophellamuretin(7),清酒缸酚(8),古柯三醇(9),黄槿酮D(10),山柰酚(11),8-prenylquercetin(12),leachianone G(13),5,7,4’-三羟基-二氢黄酮醇(14),4H-1-benzopyran-4-one,2-(3,4-dihydroxyphenyl)-2,3-dihydro-3,5,7-trihydroxy-8-(3-methyl-2-butenyl)-,(2R-trans)-(9CI)(15)。结论:除化合物8外,所有化合物均为从该种植物中首次分离得到。     

Antitubercular chromones and flavonoids from Pisonia aculeata

Three new chromones, pisonins A (1), B (2), and D (4), two new flavonoids, pisonivanone [(2S)-5,7,2'-trihydroxy-8-methylflavanone] (7) and pisonivanol [(2R,3R)-3,7-dihydroxy-5,6-dimethoxyflavanone] (8), one new isoflavonoid, pisonianone (5,7,2'-trihydroxy-6-methoxy-8-methylisoflavone) (9), and five compounds first isolated from nature, namely, pisonins C (3), E (5), and F (6), pisoniamide (10), and pisonolic acid (11), together with 18 known compounds have been isolated from the methanol extract of the combined stem and root of Pisonia aculeata. Among these isolates, 2, 7, 14, 16, and 19 exhibited antitubercular activities (MICs≤50.0 μg/mL) against Mycobacterium tuberculosis H37Rv in vitro.     

New cytotoxic indole alkaloids from Tabernaemontana calcarea from the Madagascar rainforest

Bioassay-directed fractionation of the alkaloid portion of a CH(2)Cl(2)-MeOH extract of Tabernaemontana calcarea resulted in the isolation of the three new cytotoxic indole alkaloids, 1-3, and the 12 known alkaloids voacangine (4), isovoacangine (5), coronaridine (6), 11-hydroxycoronaridine (7), voacristine (8), 19-epi-voacristine (9), isovoacristine (10), ibogamine (11), 10-methoxyibogamine (12), 11-methoxyibogamine (13), heyneanine (14), and 19-epi-heyneanine (15). The structures of the new compounds 1-3 were elucidated on the basis of extensive 1D and 2D NMR spectroscopic interpretation. All the compounds exhibited cytotoxic activity against the A2780 ovarian cancer cell line.     

Triterpenoid saponins from Ilex kudincha.

Ten new triterpene saponins, ilekudinosides A-J (2, 6-8, 10, 13-17), together with seven known triterpene saponins, ilexoside XLVIII (1); cynarasaponin C (5); latifolosides A (9), C (3), G (12), and H (4); and kudinoside G (11), were isolated from an aqueous extract of the leaves of Ilex kudincha. They possessed oleanane- and ursane-type triterpenoids as the aglycons. The structures were elucidated by 1D and 2D NMR experiments, including ROE difference, HOHAHA difference, 1H-1H COSY, and 1H-13C COSY (HMQC, HMBC) methods and sugar analysis. Compounds 1 and 5 exhibited acyl CoA cholesteryl acyl transferase (ACAT) inhibitory activity.     

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.