肋果茶中的萜类化学成分研究

从肋果茶(Sladenia celastrifolia)95％乙醇提取物的乙酸乙酯部位中分离得到15个萜类化合物,经波谱学方法分别鉴定为sladeniafolin A(1),grasshopper ketone (2),(3S,5R,6S,7E,9R) -7-megastigmene-3,6,9-triol (3),hedytriol (4),(3S,5R,6R,7E,9R) -3,5,6,9-tetrahydroxy-7-megastigmene(5),1′S*,4′R*-8-(4′-hydroxy-2′,6′,6′-trimethylcyclohex-2-enyl)-6-methyloct-3E,5E,7E-trien -2-one (6),2α,3α,19α,23-tetrahydroxyurs-12-en-28-oic acid (7),2α,3β,19α,23-tetrahydroxyurs-12-en-28-oic acid(8),pomolic acid(9),3-O-acetyl pomolic acid(10),ursaldehyde (11),camarolide (12),3β-hydroxyurs-11-en-13β(28) -olide (13),3β-hydroxy -11α,12α-epoxy-urs-13β,28-olide (14)和28-0-β-D-glucopyranosyl euscaphic acid (15).以上化合物均首次从该植物中分离得到,其中1为新的C9裂环烯醚萜.     

Antifeedant/insecticidal terpenes from asteraceae and labiatae species native to Argentinean semi-arid lands

To validate the potential as added-value resources of Asteraceae and Labiatae species of Argentinean semi-arid lands, we have selected 13 of their major terpenoids belonging to several chemical classes and tested their insect antifeedant and toxic activity on the herbivorous insects Spodoptera littoralis and Leptinotarsa decemlineata. The antifeedant effects of the test compounds were structure- and species-dependent. The most active antifeedant to L. decemlineata was the eudesmane sesquiterpene gamma-costic acid (13), followed by the labdane diterpene 2alpha,3alpha-dihydroxycativic acid (8), the clerodane diterpenes 6-acetylteucjaponin B (5), bacchotricuneatin A (1), bartemidiolide (7), butanolide (4), and the sesquiterpenes ilicic acid (11) and tessaric acid (10) (eudesmane and eremophilane type, respectively). S. littoralis was only affected by the clerodanes and showed the strongest response to salviarin (3) and 5, followed by hawtriwaic acid (6) and 12-epi-bacchotricuneatin A (2). Orally injected S. littoralis larvae were negatively affected by 5. Most of the diterpenes had selective cytotoxic effects to insect-derived Sf9 cells with the clerodane 1 being the most active, followed by the eudesmane costic acid (12), the only cytotoxic sesquiterpene. None of these compounds was cytotoxic to mammalian CHO cells.     

尼泊尔水东哥的化学成分研究

从尼泊尔水东哥树皮的95%乙醇提取物中首次分离到12个化合物,应用波谱方法或与已知品对照的手段鉴定为auranamide(1)、aurantiamide benzoate(2)、齐墩果酸(3)、β-谷甾醇(4)、β-胡萝卜甙(5)、乌苏酸(6)、2α,3α-二羟基-12-烯-28-乌苏酸(7)、2α,3β,24-三羟基-12-烯-28-乌苏酸(8)、(2S,3S,4R,10E)-2-[(2′R)-2′-hydroxytetracosanoylamino]-10-octadecene-1,3,4-triol(9)、2α,3α,24-三羟基-12-烯-28-齐墩果酸(10)、2α,3β-二羟基-12-烯-28-乌苏酸(11)和2α,3α,24-三羟基-12-烯-28-乌苏酸(12)。     

攀援孔药花化学成分研究

从攀援孔药花全草95%乙醇提取物中首次分离得到19个化合物,通过波谱数据或与已知物对照,它们分别鉴定为:(2S,3S,4R)-2-[(2R)-2-羟基-二十一酰胺基]-二十一烷-1,3,4-三醇(1)、(2S,3S,4R)-2-二十四酰胺基-十八烷-1,3,4-三醇(2)、胡萝卜甙(3)、β-谷甾醇(4)、(20S,22E,24R)-5α,8α-表二氧-麦角甾-6,22-二烯-3β-醇(5)、6β-羟基-豆甾-4-烯-3-酮(6)、十六烷酸-1-甘油酯(7)、桦木酸(8)、大黄素(9)、二十二烷酸-1-甘油酯(10)、对羟基苯甲醛(11)、十七烷酸-1-甘油酯(12)、金色酰胺醇乙酸酯(13)、十九烷酸-1-甘油酯(14)、棕榈酸(15)(、E)-p-香豆酸(16)、(22E,24S)-24-甲基-5α-胆甾-7,22-二烯-3β,5α,6β-三醇(17)、2-去氧-β-蜕皮激素(18)和auranamide(19)。     

野桂花化学成分研究

从野桂花（Osmanthus yunnanensis）地上部分95％乙醇提取物中首次分离得到18个化合物,应用波谱方法及与已知品对照的手段鉴定它们为：E-阿魏酸二十烷基酯（1）、β-谷甾醇（2）、羽扇豆醇（3）、齐墩果酸（4）、7-oxo-β—sitosterol（5）、乙酰齐墩果酸（6）、（6＇-O－palmitoyl）－sitosterol-3-O-β—D—glucoside（7）、rotundioic acid（8）、地榆糖甙II（9）、3β-hydroxy－27-p－（E）－eoumaroyloxyolean－12－en-28－oicacid（10）、3β—laydroxy-27-p－（Z）－coumaroyloxy－olean－12－en-28-oicacid（11）、hycandinic acid ester（12）、绿原酸丁酯（13）、4,5-二咖啡酰奎尼酸丁酯（14）、28-O-β-D—glueopyranosyl rottmdioic acid（16）以及三个半萜类化合物：4,5-dihydroxyprenyl caffeate（15）、4-（6-O-caffeoyl -β-D—glucopyranosyloxy）-5-hydroxyprenyl caffeate（17）、4-β-D—glucopyranosyloxy5-hydroxyprenyl caffeate（18）。     

钮子瓜化学成分研究

从民间药物钮子瓜全草95%乙醇提取物中首次分离得到14个化合物,应用波谱方法及与已知品对照的手段鉴定它们为(2S,3S,4R,10E)2[(2R)2-羟基二十四烷酰氨基]10十八烷-1,3,4-三醇(1)、(2S,3S,4R)2-二十四烷酰胺基十八烷-1,3,4-三醇(2)、胡萝卜苷(3)、swertish(4)、苯甲酸(5)、水杨酸(6)、loliolide(7)、胸腺嘧啶(8)、尿嘧啶(9)、(23Z)-9,19-环阿尔廷-23-烯-3β,25-二醇(10)、(20S,22E,24R)5α,8α-表二氧麦角甾6,22二烯3β醇(11)、十六烷酸1甘油酯(12)、大豆脑苷Ⅰ(13)、(22E,24S)24甲基5α胆甾7,22二烯3β,5α,6β三醇(14)。     

Stereoselective synthesis of (6Z,10E,12Z)-octadeca-6,10,12-trienoic acid, (8Z,12E,14Z)-eicosa-8,12,14-trienoic acid,and their [1-14C]-radiolabeled analogs

To study the metabolic fate of conjugated linoleic acid isomers, we synthesized, in seven steps, from 1-heptyne, (6Z,10E,12Z)-octadeca-6,10,12-trienoic acid, (8Z,12E,14Z)-eicosa-8,12,14-trienoic acid, and their [1-(14)C]-analogs. In the case of (6Z,10E,12Z)-octadecatrienoic acid, a series of palladium-catalyzed cross-coupling reactions between 1-heptyne and (E)-1,2-dichloro-ethene, a coupling reaction with a Grignard reagent and cleavage of the dioxolane gave (E)-dodec-4-en-6-ynal 3. Stereoselective Wittig reaction between aldehyde 3 and triphenyl-[5-(tetrahydro-pyran-2-yloxy)-pentyl]-phosphonium provided a dienyne. Stereocontrolled reduction of the triple bond and replacement of the tetrahydropyranyl group by a bromine gave (5Z,9E,11Z)-1-bromo-heptadeca-5,9,11-triene 10. Formation of the alkenyl lithium derivative and carbonation with CO(2) furnished (6Z,10E,12Z)-octadecatrienoic acid. (8Z,12E,14Z)-eicosa-8,12,14-trienoic acid was obtained by the same route but using triphenyl-[5-(tetrahydro-pyran-2-yloxy)-heptyl]-phosphonium iodide for the Wittig reaction. [1-(14)C]-analogs were obtained from the bromides by carbonation with (14)CO2. In all cases, chemical or radiochemical purities were found to be better than 95% after purification by flash chromatography on silica gel (>99% after additional purification by RP-HPLC). Metabolism studies in animals are in progress.     

Constituents of Eugenia sandwicensis with potential cancer chemopreventive activity

A triterpenoid, 3beta-cis-p-coumaroyloxy-2alpha,23-dihydroxyolean-12-en-28-oic acid (1), and two natural products, 3beta-trans-p-coumaroyloxy-2alpha,23-dihydroxyolean-12-en-28-oic acid (2) and 23-trans-p-coumaroyloxy-2alpha,3beta-dihydroxyolean-12-en-28-oic acid (3), were isolated from a chloroform-soluble extract of the stems of Eugenia sandwicensis, along with 10 known compounds. Of these compounds, 2 showed significant inhibitory activity (79.2% at 4 microg/ml) in a 7,12-dimethylbenz[a]anthracene-induced mouse mammary organ culture assay system of relevance to cancer chemoprevention. Gallic acid was isolated as an antioxidative constituent of an ethyl acetate-soluble extract of E. sandwicensis stems. Isolates 1-3 were characterized on the basis of spectral and chemical evidence.     

Bioactive sucrose esters from Bidens parviflora

An investigation on Bidens parviflora led to the isolation of three sucrose esters and a substituted truxillate. Their structures were elucidated as (6-O-(E)-p-coumaroyl)-beta-D-fructofuranosyl-(2-->1)-alpha-D-glucopyranoside, (6-O-(E)-p-coumaroyl)-beta-D-fructofuranosyl-(2-->1)-(6-O-(E)-p-coumaroyl)-alpha-D-glucopyranoside II, 6,6'-sucrose ester of (1alpha,2alpha,3beta,4beta)-3,4-bis(4-hydroxyphenyl)-1,2-cyclobutanedicarboxylic acid, dimethyl ester of (1alpha,2alpha,3alpha,4alpha)-2,4-bis(3,4-dihydroxyphenyl)-1,3-cyclobutanedicarboxylic acid on the basis of spectral and chemical evidence. These compounds were subjected to the following bioassays: the histamine release inhibition of rat mast cells induced by antigen-antibody reaction and the inhibitory activity of PGE(2) production by macrophages.     

绿槽枝衣的化学成分

从地衣绿槽枝衣( Sulcaria virens) 中分离得到一个新的亚油酸异丙叉衍生物, 通过波谱学方法包括2D-NMR 确定其化学结构为: 9, 10-O-异丙叉基- (12 Z)-十八碳烯酸(1) 。同时还得到其它12 个已知化合物:( 9 Z, 12 Z )-十八碳二烯酸(2), 扁枝衣二酸(3), ( R ) -松萝酸(4), 枕酸甲酯( 5), 黑茶渍素(6) , virensic acid ( 7), abieslactone (8), 3α-羟基羊毛甾-7, 24-二烯-26, 23 R-内酯(9), 蒲公英赛醇(10 ), 蒲公英赛酮 ( 11 ), (22 E , 24 R )-5α, 8α-过氧麦角甾-6, 22-二烯-3β-醇(12) 和2, 2′-四氢角鲨烯(13)。     

Activity of lupane triterpenoids from Maytenus species as inhibitors of nitric oxide and prostaglandin E2

In the present study, we report that three new lupane triterpenes (1-3), in addition to 16 known ones (4-19), were isolated from the root bark of Maytenus cuzcoina and the leaves of Maytenus chiapensis. Their structures were elucidated by spectral analysis, including homonuclear and heteronuclear correlation NMR experiments (COSY, ROESY, HSQC, and HMBC). The natural compounds and derivatives 6a, 6b, 9a, and 9b have been tested for potential anti-inflammatory activity, and several compounds including 3-epicalenduladiol (2), 11alpha-hydroxy-glochidone (3), rigidenol (6), acetoxy-rigidenol (6a), 11alpha-acetoxy-30-chloro-3-oxo-lup-20(29)-ene (6b), betulin (9), 28-acetoxy-betulin (9a), epibetulin (12), epibetulinic acid (13), and betulonic acid (16) exhibited potent inhibitory effects on NO and prostaglandin E(2) production in mouse macrophages (RAW 264.7) stimulated with bacterial endotoxin. The structure-activity relationship is discussed in detail.     

鞭打绣球中的一个新单萜苷

从鞭打绣球(Hemiphragma heterophyllum Wall.)全草中分离到1个新单萜苷和7个已知化合物.通过波谱数据分析,新单萜苷的结构鉴定为(4S)-α-萜烯醇-8-O-β-D-比喃木糖-(1→6)-β-D-比喃葡萄糖苷,已知化合物分别鉴定为globularin(2)、(2S 3S,4R,9E)-1,3,4-trihydroxy-2-[(2'R)-hydroxy-tetracosanoylamino]-9-octadecene(3)、β-香树素(4)、齐墩果酸(5)、肉桂酸(6)、β-谷甾醇(7)和胡萝卜甙(8).除化合物2外,其余化合物均为首次从鞭打绣球中分离得到.     

C(15) Acetogenins from the red alga Laurencia obtusa.

Four C(15) acetogenins, 13-epilaurencienyne (3Z) (1), 13-epipinnatifidenyne (3E) (2), (3E, 6S(*), 7R(*), 9S(*), 10S(*), 12R(*))-9-chloro-13-bromo-6:12-epoxy-7, 10-diacetoxypentadec-3-en-1-yne (3), (3Z, 6S(*), 7R(*), 9S(*), 10S(*), 12R(*))-9-chloro-13-bromo-6:12-epoxy-7, 10-diacetoxypentadec-3-en-1-yne (4), along with the known 13-epilaurencienyne (3E) (5), have been isolated from the organic extract of the red alga Laurencia obtusa, collected in the Aegean Sea, Greece. The structures of the new natural products, as well as their relative stereochemistry, were established by means of spectral data analysis, including 2D NMR spectroscopic experiments. Some of the new metabolites exhibited significant insecticidal activity.     

中华青荚叶的一个新果糖酯

从山茱萸科中华青荚叶( Helwingia chinensis )的乙醇提取物中分离得到一个新果糖酯和十个已知化合物.通过现代波谱技术分别鉴定为:2- O -(E)-咖啡酰-3- O -(3, 5-二甲氧基香豆酰)-α-D-呋喃果糖甙(1),2- O -β-D-呋喃果糖基α-D-异吡喃糖酯(2),甘草甜素(3),4′-羟基-7- O -葡萄糖-2, 3-二羟黄酮甙(4),黄豆甙(5),5-葡萄糖芹菜甙(6),7- O -葡萄糖芹菜甙(7),4- O -葡萄糖香豆酸(8), 葡萄糖咖啡酸(9), 3β-赤杨醇(10), 薯蓣皂甙3- O -{α-L-鼠李糖吡喃糖基(1→2)-[α-L-阿拉伯呋喃糖基(1→3)]-β-D-葡萄糖吡喃糖} (11).     

Metabolism of arachidonic acid in polymorphonuclear leukocytes. Structural analysis of novel hydroxylated compounds.

Arachidonic acid was incubated with rabbit peritoneal polymorphonuclear leukocytes (glycogen-induced) and compounds obtained from ether extractions were fractionated by silicic acid column chromatography. A fraction containing several unidentified metabolites of arachidonic acid was analyzed by reversed phase-high pressure liquid chromatography. The metabolites were esterified and further purified by silicic acid high pressure liquid chromatography. The structures of the pure compounds were elucidated by infrared and ultraviolet spectrometry, ozonolysis, and gas chromatography-mass spectrometry. The following novel compounds were identified: Compound 1, 5S, 12R-dihydroxy-(E,E,E,Z)-6,8,10,14-eicosatetraenoic acid; Compound 2, 5S, 12S-dihydroxy-(E,E,E,Z)-6,8,10,14-eicosatetraenoic acid; Compound 3, 5, 6-dihydroxy-7,9,11,14-eicosatetraenoic acid; Compound 4, a diastereoisomer of the latter. Evidence for the occurrence of the delta-lactone forms of the 5,12-dihydroxy acids is also presented.     

蔓生百部的化学成分研究

从蔓生百部(Stemona japonica)根中分离得到13个化合物,通过波谱数据,它们鉴定为β-谷甾醇(1)、豆甾醇(2)、5,11-豆甾二烯-3β-醇(3)、苯甲酸(4)、4-甲氧基苯甲酸(5)、1,8-二羟基-3-甲基蒽醌(6)、1,8-二羟基-6-甲氧基-3-甲基蒽醌(7)、氧代狭叶百部碱(8)、百部定碱(9)、异狭叶百部碱(10)、绿原酸(11)、栀子苷(12)和藏红花素A(13).所有化合物均为首次从该植物中分离得到.     

Chemical Constituents of Siegesbeckia orientalis L.

The aerial parts of Siegesbeckia have been used as the traditional Chinese medicine in the treatment of rheumatic arthritis, hypertension, malaria, neurasthenia, and snakebite. In order to find new and bioactive compounds, the chemical constituents of the aerial parts of S. orientalis L. were investigated and two new compounds, namely β-D-glucopyranosyl-ent-2-oxo-15,16-dihydroxy-pimar-8（14）-en-19-oic-late （compound 1 ） and [1 （10） E,4Z]-8β-angeloyloxy-9α-methoxy-6α, 15-dihydroxy-14-oxogermacra-1 （10）,4,11 （13）-trien-12-oic acid 12,6-1actone （compound 2）, as well as five known ent-pimarane diterpenes （compounds 3-7） were isolated. The structures of the two new compounds were identified by their physicochemical properties and spectral analysis, particularly oneand two-dimensional nuclear magnetic resonance spectral methods.     

Triterpene saponins and iridoid glucosides from galium rivale

Three new glycosides of the oleanene-type triterpenes, rivalosides C-E (1-3), along with three known triterpene saponins, momordin IIb (4) and rivalosides A-B (5-6), and five known iridoid glucosides: monotropein, scandoside, deacetylasperulosidic acid, geniposidic acid and asperulosidic acid, were isolated from aerial parts of Galium rivale. The structures of the new compounds were elucidated by spectral methods and chemical means as 2alpha-acetoxy-3alpha, 19alpha-dihydroxy-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl-(1--> 6)-beta-D-glucopyranoside, 2alpha,3alpha, 19alpha-trihydroxy-olean- 12-en-28-oic acid 28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranoside and 3-O-beta-D-glucuronopyranosyl-24-hydroxy-olean-12-en-28-oic acid 28-O-beta-D-glucopyranoside, for rivalosides C-E, respectively. The taxonomic significance of the rivalosides in G. rivale was discussed.     

Synthesis and structural identification of four dihydroxy acids and 11,12-leukotriene C4 derived from 11,12-leukotriene A4

Using a partially purified 12-lipoxygenase from porcine leukocytes, (5Z,8Z,10E,14Z)-12-hydroperoxy-5,8,10,14-icosate traenoic acid was synthesized from arachidonic acid with a yield of over 35%. The absolute configuration of C-12 was determined as S by chiral-phase column chromatography. It was chemically converted to at least three epoxides with the conjugated triene structure. Two were identified by proton NMR and mass spectrometry to be (5Z,7E,9E,14Z)-(11S,12S)-11,12-oxido-5,7,9,14-ic osatetraenoic acid (11,12-leukotriene A4) and (5Z,7Z,9E,14Z)-(11S,12S)-11,12-oxido-5,7,9,14-ic osatetraenoic acid (7-cis-11,12-leukotriene A4). 11,12-Leukotriene A4 underwent acid hydrolysis to yield two diastereomers of (6E,8E,10E,14Z)-(12S)-5,12-dihydroxy-6,8,10,14-i cosatetraenoic acid and two isomers of (14Z)-(12S)-11,12-dihydroxy-5,7,9,14-icosatetraenoic acid. Upon incubation with rat liver glutathione S-transferase, 11,12-leukotriene A4 was converted to 11,12-leukotriene C4, a spasmogenic compound.     

Hyrtioreticulins A-E, indole alkaloids inhibiting the ubiquitin-activating enzyme, from the marine sponge Hyrtios reticulatus

Hyrtioreticulins A-E (1-5) were isolated from the marine sponge Hyrtios reticulatus, along with a known alkaloid, hyrtioerectine B (6). Structural elucidation on the basis of spectral data showed that 1, 2, and 5 are new tetrahydro-β-carboline alkaloids, while 3 and 4 are new azepinoindole-type alkaloids. Hyrtioreticulins A and B (1 and 2) inhibited ubiquitin-activating enzyme (E1) with IC(50) values of 0.75 and 11μg/mL, respectively, measured by their inhibitory abilities against the formation of an E1-ubiquitin intermediate. So far, only five E1 inhibitors, panapophenanthrine, himeic acid A, largazole, and hyrtioreticulins A and B (1 and 2), have been isolated from natural sources and, among them, 1 is the most potent E1 inhibitor.