Two new 19-oxygenated polyhydroxy steroids from the soft coral nephthea chabroli(1)

Two new 19-oxygenated polyhydroxy steroids, 24-methylene cholest-5-en-1alpha,3beta,19-triol (1) and 24-methylene cholest-5-en-3beta,7beta,9alpha,19-tetrol (2), and three known steroids, ergost-5,24(28)-dien-3beta,19-diol (litosterol), cholest-5-en-3beta,7beta,19-triol, and ergost-5,24 (28)-dien-3beta, 7beta,19-triol, have been isolated from the soft coral Nephthea chabroli and characterized through interpretation of spectral data.     

总合草苔虫的化学成分研究

对采自深圳大亚湾的总合草苔虫Bugula neritinaL.中化学成分进行研究,从石油醚层和正丁醇层分离得到7个化合物。利用波谱分析和文献对照的方法,确定它们的结构分别为胆甾醇(Ⅰ);胆甾-4-烯-3-酮(Ⅱ);胆甾醇肉豆蔻酸酯(Ⅲ);3,β5,α9α-三羟基-(22E,24R)-麦角甾-7,22-二烯-6-酮(Ⅳ);3,β5,α6β-三羟基-(22E,24R)-麦角甾-7,22-二烯(Ⅴ);尿嘧啶(Ⅵ);胸腺嘧啶(Ⅶ)。其中化合物Ⅱ-Ⅶ为首次从总合草苔虫中分离得到。     

蟾衣化学成分及体外抗肿瘤活性研究

目的:对源于蟾蜍的新资源蟾衣进行化学成分研究,并对蟾衣提取物及分离得到的主要化合物进行抗肿瘤活性评价.方法:蟾衣粗粉采用95％乙醇回流提取,提取物采用正相硅胶、反相硅胶和葡聚糖凝胶Sephadex LH-20柱色谱分离,结合结晶法对化合物进行纯化,通过波谱分析鉴定化合物的结构;采用MTT法对95％乙醇提取物及分离得到的主要化合物进行体外抗肿瘤活性评价.结果:从蟾衣95％乙醇提取物中分离鉴定了8个化合物,分别为棕榈酸胆甾烯酯(1),胆甾醇(2),5α,8α-epidioxycholesta-6-en-3β-ol(3),胆甾-5-烯-3β,7β-二醇(4),胆甾-7-烯-3β,5α,6β-三醇(5),3-十八烷氧基-1,2-丙二醇(6),△4,5(E),△9,10(Z)-鞘胺醇-正十五碳酸酰胺(7)和蟾蜍噻咛(8);抗肿瘤活性筛选表明,蟾衣95％乙醇提取物和分离得到的主要化合物对试验的细胞株均无抑制作用.结论:化合物1～8均为首次从蟾衣中分离得到,其中化合物3,5～7为首次从中华大蟾蜍和蟾蜍属中分离得到.     

Oculatol, oculatolide, and A-nor sterols from the sponge Haliclona oculata

Chemical investigation of the marine sponge Haliclona oculata resulted in the isolation of eight new compounds including oculatol (1) and oculatolide (2) and six unusual A-nor steroids, 2-ethoxycarbonyl-2beta-hydroxy-A-nor-ergosta-5,24(28)-dien-4-one (3), 2-ethoxycarbonyl-24-ethyl-2beta-hydroxy-A-nor-cholesta-5-en-4-one (4), 2-ethoxycarbonyl-2beta,7beta-dihydroxy-A-nor-ergosta-5,24(28)-dien-4-one (5), 2-ethoxycarbonyl-2beta,7beta-dihydroxy-A-nor-cholesta-5-en-4-one (6), 2-ethoxycarbonyl-2beta,7beta-dihydroxy-24-methyl-A-nor-cholesta-5,22(E)-dien-4-one (7), and 2-ethoxycarbonyl-2beta,7beta-dihydroxy-A-nor-cholesta-5,22(E)-dien-4-one (8), along with 16 known steroids and indole derivatives. Their structures were unambiguously determined on the basis of extensive spectroscopic analyses.     

Biotransformation of cycloartane-type triterpenes by the fungus Glomerella fusarioides

Biotransformation of three cycloartane-type triterpenes, cycloartenol (1), 24-methylenecycloartanol (2), and cycloartenone (3), by the fungus Glomerella fusarioides was studied. Compound 1 was converted to 3, cycloart-25-ene-3beta,24-diol (4), and cycloartane-3beta,24,25-triol (5). Compound 2 was metabolized to cycloeucalenol (6) and two new compounds, 24-methylcycloartane-3beta,24,24(1)-triol (7) and 24(1)-methoxy-24-methylcycloartane-3beta,24-diol (8). Compound 3 was converted into two new metabolites, 4alpha,4beta,14alpha-trimethyl-9beta,19-cyclopregnane-3,20-dione (9) and 25-hydroxy-24-methoxycycloartan-3-one (14), and four known compounds, viz., cycloartane-3,24-dione (10), 24-hydroxycycloart-25-en-3-one (11), (23E)-25-hydroxycycloart-23-en-3-one (12), and 24,25-dihydroxycycloartan-3-one (13). The structures of four new metabolites, 7, 8, 9, and 14, were established by spectroscopic methods.     

南海蓖麻海绵Biemna fortis Fopsent化学成分及其生物活性

目的：对采自我国南海的蓖麻海绵Biemna fortis Topsent的化学成分进行研究，从中寻找有生物活性的次生代谢产物。方法：用硅胶柱层析和凝胶柱层析对蓖麻海绵的甲醇提取物进行分离纯化，根据其化学性质，结合现代波谱技术（MS，NMR等），对得到的化合物进行结构鉴定。结果：分离得到9个甾体、2个邻苯二甲酸酯、1个长链脂肪醛类化合物，其结构分别鉴定为melithasterolB（1），（24R）-ergosta-7，22-diene-3，5，6．triol（2），（24R）-er-gosta-4，6，8（14），22-tetraene-3-one（3），（24R）-ergosta-4，7，22-triene-3-one（4），（24R）-ergosta-6，22-diene-5，8-epidioxy-3-ol（5），6-hydroxy-cholest-4-en-3-one（6），cholest-4-ene-3，6-dione（7），cholest-4-en-3-one（8），cholest-5，22-diene-3-one（9），bis-（2-ethylhexyl）phthalate（10），bis-diisobutylphthalate（11）和hexaldehyde（12）。结论：化合物1-4，6．10，12系首次从蓖麻海绵中分离得到；化合物7不但对T和B淋巴细胞的增殖具有显著抑制活性，而且对Ⅱ型糖尿病靶标分子蛋白质酪氨酸磷酸酯酶PTPIB具有显著的抑制活性，其IC50为1．6mol·L^-1。     

翻白叶树根化学成分研究

目的:对翻白叶树根化学成分进行研究。方法:应用溶剂萃取、正相硅胶柱色谱、ODS开放柱色谱、Sephadex LH-20柱色谱以及制备高效液相进行分离和纯化,采用波谱技术进行结构鉴定。结果:分离并鉴定出10个化合物,分别为金色酰胺醇酯(asperglaucide,1),2-甲氧基-4-羟基苯酚-1-O-β-D-呋喃芹菜糖基-(1→6)-O-β-D-葡萄糖苷[2-methoxy-4-hydroxyphenol-1-O-β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranoside,2],5,5’-二甲氧基-9-β-D-木糖基-(-)-异落叶松脂素[5,5’-dimethoxy-9-β-D-xylopyranosyl-(-)-isolariciresinol,3],(-)-表儿茶素[(-)-epicatechin,4],圣草酚(eriodictyol,5),花旗松素(taxifolin,6),3β-羟基-12-烯-28-乌苏酸(3β-hydroxy-12-en-28-ursolic acid,7),2β,3β-二羟基-12-烯-28-齐墩果酸(2β,3β-dihydroxy-12-en-28oleanolic acid,8),槲皮素(quercetin,9),豆甾-4-烯-3-酮(cholest-4-en-3-one,10)。结论:化合物1～10为首次从该植物中分得。     

New taxanes from the needles of Taxus canadensis

Ten new taxanes were isolated from the methanol extract of the needles of the Canadian yew, Taxus canadensis. On the basis of their spectral analysis, their structures were established as 9alpha-hydroxy-2alpha,7alpha,10beta-triacetoxy-5alpha-cinnamoyloxy-3,11-cyclotaxa-4(20)-en-13-one (1), 9alpha,10beta-diacetoxy-5alpha-cinnamoyloxy-3,11-cyclotaxa-4(20)-en-13-one (2), 9alpha,20-dihydroxy-2alpha,10beta,13alpha-triacetoxytaxa-4(5),11(12)-diene (3), 2alpha,9alpha,10beta-triacetoxy-20-cinnamoyloxy-11,12-epoxytaxa-4-en-13-one (4), 9alpha-hydroxy-2alpha,10beta,13alpha-triacetoxy-5alpha-(3'-methylamino-3'-phenyl)-propionyloxytaxa-4(20),11-diene (5), 2alpha,10beta-diacetoxy-5alpha,9alpha-dihydroxytaxa-4(20),11-dien-13-one (6), 2alpha,9alpha-diacetoxy-5alpha,10beta-dihydroxytaxa-4(20),11-dien-13-one (7), 5alpha,9alpha-dihydroxy-2alpha,10beta,13alpha-triacetoxytaxa-4(20),11-diene (8), 5alpha,10beta-dihydroxy-2alpha,9alpha,13alpha-triacetoxytaxa-4(20),11-diene (9), and 7beta,11beta-dihydroxy-2alpha,9alpha,10beta,13-tetraacetoxy-5alpha-cinnamoyloxytaxa-4(20),12-diene (10). Taxane 1 is the first example of a 3,11-cyclotaxane with a 7-epi-alpha-oxygenated group. Taxane 4 is the first taxane with a C-11,12-epoxide ring as well as a C-4(5)-endo-double bond. Taxanes with a 12(13) double bond as in 10 instead of the usual 11(12) double bond have been found so far only in the needles, stem, and seeds of the Japanese yew.     

Two new 26,27-cyclosterols from the marine sponge Strongylophora corticata

Two novel steroids with a cyclopropane ring at C-25 and C-26, 7-oxopetrosterol (1) and 7alpha-hydroxypetrosterol (2), along with two known compounds, petrosterol (3) and 23,24-dihydrocalysterol (4), have been isolated from the Japanese marine sponge Strongylophora corticata. The structures of 1 and 2 were determined as 26, 27-cyclo-24,27-dimethyl-3beta-hydroxycholest-5-en-7-one and 26, 27-cyclo-24,27-dimethylcholest-5-en-3beta,7alpha-diol on the basis of spectroscopic investigations.     

ent-Kaurane diterpenoids from Isodon japonicus

Five ent-kaurane diterpenoids, 6beta,7beta,14beta-trihydroxy-1alpha,19-diacetoxy-7alpha,20-epoxy- ent-kaur-16-en-15-one (1), 1alpha,6beta,7beta-trihydroxy-11alpha,19-diacetoxy-7alpha,20-epoxy-ent-kaur-16-en-15-one (2), 6-hydroxy-1alpha,19-diacetoxy-6,7-seco-ent-kaur-16-en-15-one-7,20-olide (3), 19-hydroxy-1alpha,6-diacetoxy-6,7-seco- ent-kaur-16-en-15-one-7,20-olide (4), and 6-aldehyde-1alpha,19-diacetoxy-6,7-seco- ent-kaur-16-en-15-one-7,20-olide (5), along with 10 known ent-kaurane diterpenoids, pseurata C (6), longikaurin C (7), effusanin C (8), longikaurin B (9), longikaurin D (10), effusanin D (11), excisanin B (12), lasiokaurin (13), megathyrin A (14), and loxothyrin A (15), were isolated from the aerial parts of Isodon japonicus. Their structures were determined on the basis of spectroscopic (1D-, 2D-NMR and MS) and chemical evidence. The isolates were evaluated for their inhibitory effects on LPS-induced production of nitric oxide in murine macrophage RAW264.7 cells.     

Bioactive metabolites from the South African marine mollusk Trimusculus costatus

A reinvestigation of extracts of the endemic South African intertidal limpet Trimusculus costatus yielded the known labdane diterpenes 6beta,7alpha-diacetoxylabda-8,13 E-dien-15-ol ( 1) and 2alpha,6beta,7alpha-triacetoxylabda-8,13 E-dien-15-ol ( 2) and three new metabolites, 6beta,7alpha,15-triacetoxylabda-8,13 E-diene ( 3), 3alpha,11-dihydroxy-9,11-seco-cholest-4,7-dien-6,9-dione ( 4), and cholest-7-en-3,5,7-triol ( 5). Chiral derivatization and X-ray analysis were used to confirm the labdane absolute configuration of 2. Compounds 1, 2 and 4 exhibited moderate activity (3-25 microM) against the WHCO1 human esophageal cancer cell line.     

Activity of macrocyclic jatrophane diterpenes from Euphorbia kansui in a TrkA fibroblast survival assay

Three new macrocyclic diterpenes, kansuinins F (1), G (2), and H (3), together with four known jatrophane diterpenes, kansuinins D (4), E (5), and A (6) and 3beta,5alpha,7beta,15beta-tetraacetoxy-9alpha-nicotinoyloxyjatropha-6(17)-11E-dien-14-one, were isolated from the roots of Euphorbia kansui. Compounds 1 and 2 were assigned as 6(17)-en-11,12-epoxy-14-one-type jatrophane diterpenes, and compound 3 as a 6(17)-en-11,14-epoxy-12-one jatrophane diterpene. The structures of compounds 1-3 and the relative configurations of compounds 4 and 5 were determined by spectral data analysis. Kansuinin E (5) exhibited a specific survival effect on fibroblasts that expressed TrkA, a high-affinity receptor for nerve growth factor.     

Novel cytotoxic oxygenated C29 sterols from the Colombian marine sponge Polymastia tenax

Three new sterols, 5alpha,6alpha-epoxy-24R-ethylcholest-8(14)-en-3beta,7alpha-diol (1), 5alpha,6alpha-epoxy-24R-ethylcholest-8-en-3beta,7alpha-diol (2), and 3beta-hydroxy-24R-ethylcholesta-5,8-dien-7-one (3), have been isolated from the marine sponge Polymastia tenax, collected in the Colombian Caribbean, and their structures established on the basis of extensive NMR and MS studies. Compounds 1 and 2 showed antiproliferative activity toward A-549, HT-29, H-116, MS-1, and PC-3 tumor cells in the range 0.5-10 microg/mL.     

Three new lanostanoids from Ganoderma lucidum

Three new lanostanoids--ganodermenonol (1), ganodermadiol (2), and ganodermatriol (3) [isolated as its triacetate derivative (3a)]--were isolated from the MeOH extract of Ganoderma lucidum, together with ergosterol and its peroxide. The new compounds were identified as 26-hydroxy-5 alpha-lanosta-7,9(11),24-trien-3-one (1), 5 alpha-lanosta-7,9(11),24-triene-3 beta, 26-diol (2), and 5 alpha-lanosta-7,9(11),24-triene-3 beta, 26,27-triol (3) by their respective spectral data.     

黄秋葵石油醚部位化学成分的研究Ⅱ

目的:对黄秋葵石油醚部位的化学成分进行分离和鉴定.方法:采用硅胶柱色谱、重结晶等方法分离纯化,并根据理化性质和波谱分析鉴定化合物的结构.结果:从黄秋葵石油醚部位分离得到14个化合物,分别为6-羟基豆甾-4-烯-3-酮(1),6β-羟基豆甾-4,22-二烯-3-酮(2),3β-羟基豆甾-烯-7-酮(3),3β-羟基豆甾-5,22-二烯-7-酮(4),豆甾-5-烯-3β,7β-二醇(5),豆甾-5,22-二烯-3β,7β-二醇(6),豆甾-4,22-二烯-3,6-二酮(7),豆甾-4,22-二烯-3-酮(8),麦角甾-7,22-二烯-3β-醇(9),环阿尔廷-25-烯-3,24-二醇(10),羽扇豆醇(11),橙酰胺乙酸酯(12),豆甾醇(13),棕搁酸(14).结论:化合物1～12均为首次从该植物中得到,也为首次从本属植物中分离得到.     

Novel epoxy steroids from the indian ocean soft coral Sarcophyton crassocaule

A detailed further examination of the Indian Ocean soft coral Sarcophyton crassocaule resulted in the isolation of altogether 17 compounds of which two (1 and 2) are novel 17beta,20beta-epoxy steroids and one is a new dihydroxygorgost-5-en (3). The other compounds include the four hippurin steroids (4-7) reported earlier, and some known derivatives such as methyl arachidonate, batyl alcohol, a mixture of monohydroxy sterols, 3beta-hydroxypregn-5-en-20-one, two prostaglandin derivatives (PGB(2) acid and its methyl ester), and 9-oxo-9, 11-secogorgost-5-ene-3beta,11-diol (8). The structure of new dihydroxygorgostene derivative was established as gorgost-5-ene-3beta,11alpha-diol (3), while the structures of the novel epoxy steroids were established as 17beta,20beta-epoxy-23, 24-dimethylcholest-5-ene-3beta,22-diol (2) and its 3beta, 22-diacetate (1), respectively.     

Taxanes from rooted cuttings of Taxus canadensis

A 3,11-cyclotaxane (1), a new epoxytaxane (2), an abeo-taxane (3), and 26 known taxanes were isolated in rooted cuttings of the Canadian yew (Taxus canadensis) for the first time. Their chemical structures were characterized as 1 beta,2 alpha,9 alpha-trihydroxy-10 beta-acetoxy-5 alpha-cinnamoyloxy-3,11-cyclotaxa-4(20)-en-13-one (1), 2 alpha,9 alpha,10 beta-triacetoxy-11,12-epoxy-20-hydroxytaxa-4-en-13-one (2), and 7 beta,9 alpha,10 beta,13 alpha-tetraacetoxy-11(15-->1)abeo-taxa-4(20),11-diene-5 alpha,15-diol (3). Metabolite 2 is a new taxane, metabolite 1 has been reported previously in the needles of Taxus baccata, and metabolite 3 was previously discovered as a biotransformation product but is now reported as a natural product for the first time.     

26,27-cyclosterols and other polyoxygenated sterols from a marine sponge Topsentia sp

Thirty sterols (1-30) were isolated from bioactive fractions of a marine sponge Topsentia sp., of which 16 were new (1, 2, 8, 10-14, 16, 17, 19, 21, 24, 25, 27, and 30). They were characterized as sterols with 10 different side chains and as having various functionalities including 5alpha,8alpha-epidioxy (1-9), 5alpha,6alpha-epoxy-7-ol (10-15), 5,8-dien-7-one (24-28), 5-en-3beta-ol (29), and 1(10-->6)abeo-5,7,9-triene-3alpha,11alpha-diol (30) units and included polyoxygenated sterols (16-23). One of the key features of these new sterols is the presence of the (24R,25R,27R)-26,27-cyclo-24,27-dimethylcholestane side chain, whose absolute stereochemistry was defined by an acid-catalyzed ring-opening method and by comparison with the four synthetic isomers of known absolute stereochemistry. The occurrence of several known fungal sterols and relevant new sterols in this sponge suggested their possible origin from symbiotic fungi. Selected compounds were tested against a panel of five human solid tumor cell lines and displayed moderate to marginal cytotoxicity.     

Structure and stereochemistry of epoxyserratanes from the cuticle of Piceajezoensis var. jezoensis

Three new epoxytriterpenes, 14 beta,15 beta-epoxy-21 beta-hydroxyserratan-3-one (1), 13 alpha,14 alpha-epoxy-21 alpha-methoxyserratan-3-one (2), and 13 alpha,14 alpha-epoxy-3 beta-methoxyserratan-21 beta-ol (3), were isolated together with two known triterpenoids, 21 alpha-methoxyserrat-13-en-3-one (4) and 21 beta-hydroxyserrat-14-en-3-one (5), from the cuticle of Picea jezoensis var. jezoensis. The structures of these new compounds were established on the basis of spectral data (NMR, MS) and single-crystal X-ray analyses (1 and 2) and partial synthesis (2 and 3).     

Natural products inhibiting Candida albicans secreted aspartic proteases from Lycopodium cernuum

Activity-guided fractionation of an ethanol extract of Lycopodium cernuum for Candida albicans secreted aspartic proteases (SAP) inhibition resulted in the identification of six new (1-6) and four known (7-10) serratene triterpenes, along with the known apigenin-4'-O-(2' ',6' '-di-O-p-coumaroyl)-beta-D-glucopyranoside (11). On the basis of spectroscopic analysis, the structures of 1-10 were established as 3beta,14alpha,15alpha,21beta,29-pentahydroxyserratane-24-oic acid (lycernuic acid C, 1), 3beta,14alpha,15alpha,21beta-tetrahydroxyserratane-24-oic acid (lycernuic acid D, 2), 3beta,14beta,21beta-trihydroxyserratane-24-oic acid (lycernuic acid E, 3), 3beta,21beta,29-trihydroxy-16-oxoserrat-14-en-24-methyl ester (lycernuic ketone A, 4), 3alpha,21beta,29-trihydroxy-16-oxoserrat-14-en-24-methyl ester (lycernuic ketone B, 5), 3alpha,21beta,24-trihydroxyserrat-14-en-16-one (lycernuic ketone C, 6), 3beta,21beta-dihydroxyserrat-14-en-24-oic acid (lycernuic acid A, 7), 3beta,21beta,29-trihydroxyserrat-14-en-24-oic acid (lycernuic acid B, 8), serrat-14-en-3beta,21beta-diol (9), and serrat-14-en-3beta,21alpha-diol (10). The 13C NMR data for the known compounds 7 and 8 are reported for the first time. Compounds 1 and 11 showed inhibitory effects against C. albicans secreted aspartic proteases (SAP) with IC50 of 20 and 8.5 microg/mL, respectively, while the other compounds were inactive.