Spiranoid withanolides from Jaborosa odonelliana

Six new spiranoid withanolides, (20R,22R,23S)-5alpha-chloro-6beta,12beta,17beta,22-tetrahydroxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (2), (20R,22R,23S)-5beta,6beta-epoxy-12beta,17beta,22-trihydroxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (3), (20R,22R,23S)-5beta,6beta-epoxy-4beta,12beta,17beta,22-tetrahydroxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (4), (20R,22R,23S)-5alpha,6beta,12beta,17beta,22-pentahydroxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (5), (20R,22R,23S)-6beta,12beta,17beta,22-tetrahydroxy-5alpha-methoxy-1-oxo-12,23-cycloergosta-2,24-dien-26,23-olide (6), and (20R,22R,23S)-6beta,12beta,17beta,22-tetrahydroxy-2alpha,5alpha-epidioxy-1-oxo-12,23-cycloergosta-3,24-dien-26,23-olide (7), were isolated from the leaves of Jaborosa odonelliana. Compounds 2-7 were characterized by a combination of spectroscopic methods (1D and 2D NMR, MS) and molecular modeling.     

The microbiological transformation of two 15beta-hydroxy-ent-kaurene diterpenes by Gibberella fujikuroi

The incubation of 15beta-hydroxy-3-oxo-ent-kaur-16-ene (1) with the fungus Gibberella fujikuroi afforded 11beta-hydroxy-3,15-dioxo-ent-kaurane (6), 11beta,15beta-dihydroxy-3-oxo-ent-kaur-16-ene (8), 7beta,11beta,15beta-trihydroxy-3-oxo-ent-kaur-16-ene (9), 7alpha,11beta-dihydroxy-3,15-dioxo-ent-kaurane (7), and 7alpha,11beta,15beta-trihydroxy-3-oxo-ent-kaur-16-ene (10). The incubation of 15beta-hydroxy-ent-kaur-2,16-diene (3) with the same fungus yielded 7alpha,11beta-dihydroxy-15-oxo-ent-kaur-2-ene (12), 7alpha,11beta,15beta-trihydroxy-ent-kaur-2,16-diene (13), 7beta,15beta-dihydroxy-ent-kaur-2,16-dien-19,6-olide (14), 1beta,7beta,15beta-trihydroxy-ent-kaur-2,16-dien-19-oic acid (15), 7alpha,11beta,16alpha-trihydroxy-15-oxo-ent-kaur-2-ene (17), and 7alpha,15beta,17-trihydroxy-11beta,16beta-epoxy-ent-kaur-2-ene (19). These results indicated that a 3-oxo group in ent-kaur-16-ene derivatives inhibits the oxidation at C-19, typical of the biosynthetic pathway of gibberellins and kaurenolides, while a 2,3-double bond or a 15beta-OH does not. In both substrates a 15beta-alcohol directs hydroxylations at C-11(beta) and C-7(alpha), while in those with a 2,3-double bond the functionalization of C-1(beta) is favored.     

New lanostane-type triterpenoids from Ganoderma applanatum

Four new lanostane-type triterpenes were isolated from the MeOH extract of the fruiting bodies of Ganoderma applanatum. Their structures were established as 3beta,7beta,20,23xi-tetrahydroxy-11,15-dioxolanosta-8-en-26-oic acid (1), 7beta,20,23xi-trihydroxy-3,11,15-trioxolanosta-8-en-26-oic acid (2), 7beta,23xi-dihydroxy-3,11,15-trioxolanosta-8,20E(22)-dien-26-oic acid (3), and 7beta-hydroxy-3,11,15,23-tetraoxolanosta-8,20E(22)-dien-26-oic acid methyl ester (4), respectively, by extensive spectroscopic analyses.     

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.     

秦岭冷杉茎叶的化学成分研究

目的研究秦岭冷杉Abies chensiensis茎叶的化学成分。方法利用大孔吸附树脂、葡聚糖凝胶、硅胶柱色谱、半制备高效液相色谱等多种色谱方法分离纯化,根据理化性质及波谱数据对化合物进行结构鉴定。结果从秦岭冷杉95%乙醇提取物中分离得到24个化合物,分别鉴定为7,14,24-mariesatrien-26,23-olide-3α,23-diol(1)、(23R)-3α-hydroxy-9,19-cyclo-9β-lanost-24-en-26,23-olide(2)、7-oxocallitrisicacid(3)、23-hydroxy-3-oxomariesia-8(9),14,24-trien-26,23-olide(4)、紫果冷杉三萜E(5)、3-oxo-9β-lanosta-7,24-dien-26,23R-olide(6)、7,14,22Z,24-mariesatetraen-26,23-olide-3-one(7)、(+)-rel-3α-hydroxy-23-oxocycloart-25 (27)-en-26-oic acid(8)、cycloart-25-en-3β,24-diol(9)、紫果冷杉三萜H(10)、3-oxo-24,25,26,27-tetranolanost-8-en-23-oic acid(11)、abiesadine C(12)、13β-epidioxy-8(14)-abieten-18-oic acid(13)、dehydroabietic acid(14)、15-hydroxydehydroabietic acid(15)、methyl 18-methoxydehydroabietate(16)、7β-hydroxy dehydroabietic acid(17)、dehydroabietan-18-ol(18)、centdaroic acid(19)、abietic acid(20)、6,8,11,13-abi-etatrien-18-oic acid(21)、abiesadine B(22)、abiesadine N(23)、12β-hydroxyabietic acid(24)。结论所有化合物均为首次从该植物中分离得到,其中化合物11为属内首次分离得到。     

Four cycloartane triterpenoids and six related saponins from Passiflora edulis

Four cycloartane triterpenes, cyclopassifloic acids A (1), B (2), C (3), and D (4), and six related saponins, cyclopassiflosides I (5), II (6), III (7), IV (8), V (9), and VI (10), were isolated from the leaves and stems of Passiflora edulis, and their structures were elucidated on the base of extensive NMR experiments and chemical methods. Cyclopassifloic acids A-D were assigned as 22(R), 24(S)-1alpha,3beta,22,24,31-pentahydroxy-24-methylcycloartan -28-oic acid; 24(S)-1alpha,3beta,24, 31-tetrahydroxy-24-methylcycloartan-28-oic acid; 20(S),24(S)-1alpha, 3beta,21,24,31-pentahydroxy-24-methylcycloartan-28-oic acid; and 22(R)-1alpha,3beta,22-trihydroxy-24-oxocycloartan-28-oic acid, respectively. Cyclopassiflosides I-VI, in turn, were established as the 28-O-beta-D-glucopyranosides of cyclopassifloic acids A-D. Finally, cyclopassiflosides III and V were demonstrated as the 28, 31-bis-O-beta-D-glucopyranosides of cyclopassifloic acids B and C, respectively. Also obtained in this investigation were the known compounds passiflorin (11) and passifloric acid (12).     

Antitubercular activity of triterpenoids from Lippia turbinata

Assay-guided fractionation of the antitubercular MeOH-CH(2)Cl(2) extract obtained from Lippia turbinata led to the isolation of four novel triterpenoids-3beta,25-epoxy-3alpha,21alpha-dihydroxy-22beta-(3-methylbut-2-en-1-oyloxy)olean-12-ene-28-oic acid (1); 3beta,25-epoxy-3alpha,21alpha-dihydroxy-22beta-angeloyloxyolean-12-ene-28-oic acid (2); 3beta,25-epoxy-3alpha,21alpha-dihydroxy-22beta-tigloyloxyolean-12-ene-28-oic acid (3); and 3beta,25-epoxy-3alpha-hydroxy-22beta-(2-methylbutan-1-oyloxy)olean-12-ene-28-oic acid (4)-together with the known triterpenoids lantanilic acid (5), camaric acid (6), lantanolic acid (7), and rehmannic acid (8). The MIC values of 1-8 for growth inhibition of Mycobacterium tuberculosis were determined in the radiorespirometric BACTEC system.     

广西产美味猕猴桃根正丁醇部位化学成分研究

目的：研究广西产美味猕猴桃根正丁醇部位的化学成分。方法：应用色谱技术分离纯化，根据理化性质和波谱数据鉴定化合物结构。结果：从美味猕猴桃根正丁醇部位中分离并鉴定了6个化合物，分别为毛花猕猴桃酸B(1)，2α，3β，24 -三羟基-12-烯-28-乌苏酸(2)，2α，3α，24 -三羟基-12-烯-28-乌苏酸(3)，2α，3α，23-三羟基-12，20(30)-二烯-28-乌苏酸(4)，2α，3α，24-三羟基-12，20(30)-二烯-28-乌苏酸(5)，正丁基-O-β-D-吡喃果糖苷(6)。结论：化合物1～4，6均为首次从该植物中分离得到，其中化合物6为首次从猕猴桃属植物中分得。     

Labdane-type diterpenes and a nordrimane-type sesquiterpene from the stem bark of Thuja standishii

Two new labdane-type diterpene aldehydes, 15-oxolabda-8(17),11(Z), 13(E)-trien-19-oic acid (1) and 15-oxolabda-8(17),11(Z), 13(Z)-trien-19-oic acid (2), and a new nordrimane-type sesquiterpene, 12-oxo-11-nordrim-8-en-14-oic acid (3), along with a known diterpene, 15-nor-14-oxolabda-8(17),12(E)-dien-19-oic acid (4), were isolated from the stem bark of Thuja standishii. The structures of 1-3 were established by spectroscopic methods.     

Diterpenoids from the roots of Suregada glomerulata

Six new diterpenoids, 7beta,8alpha-dihydroxy-12-oxo- ent-abietan-16,14-olide ( 1), 3,4,18beta-cyclopropa-7beta,17-dihydroxy- ent-abieta-8(14),13(15)-dien-16,12-olide ( 2), 3alpha,7beta-dihydroxy- ent-abieta-8(14),13(15)-dien-16,12-olide ( 3), 3-oxo-8beta,14beta-epoxy- ent-abieta-11,13(15)-dien-16,12-olide ( 4), 17-hydroxy- ent-pimara-8(14),15-dien-3-one ( 5), and 3alpha,6beta-dihydroxy- ent-kaur-16-ene ( 6), and two known compounds, 7beta-hydroxy- ent-abieta-8(14),13(15)-dien-16,12-olide ( 7) and jolkinolide B, were isolated from roots of Suregada glomerulata. The structures of the new compounds were elucidated on the basis of 1D and 2D NMR and other spectroscopic studies. The structure of compound 1 was confirmed by X-ray crystallography. Cytotoxic activities were evaluated against five human tumor cell lines.     

Microbial transformations of isosteviol

Microbial transformations of the tetracyclic diterpenoid isosteviol (ent-16-ketobeyeran-19-oic acid) (2) have revealed that isosteviol is metabolized by Cunninghamella bainieri, Actinoplanes sp., Mucor recurvatus, and Cunninghamella blakesleeana to yield five new metabolites, ent-11alpha,12alpha-dihydroxy-16-ketobeyeran-19-oic acid (5), ent-11alpha,12alpha,17-trihydroxy-16-ketobeyeran-19-oic acid (6), ent-12alpha,15alpha-dihydroxy-16-ketobeyeran-19-oic acid (7), ent-7alpha,15alpha-dihydroxy-16- ketobeyeran-19-oic acid (8), and ent-9alpha-hydroxy-16-ketobeyeran-19-oic acid (9), together with three known metabolites, ent-7alpha-hydroxy-16-ketobeyeran-19-oic acid (3), ent-7beta-hydroxy-16-ketobeyeran-19-oic acid (4), and ent-12alpha-hydroxy-16-ketobeyeran-19-oic acid (10). The structures of these metabolites were established on the basis of HRFABMS and 1D and 2D NMR spectral data. In addition, metabolites 3-10 were tested for antihypertensive activity and were found to be less active than the parent compound 2.     

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.     

委陵菜三萜成分研究

目的：研究委陵菜的化学成分及其抗癌活性。方法：用硅胶柱色谱、凝胶柱色谱等多种柱色谱分离,制备高效液相色谱纯化,得到单体化合物,用各种有机波谱鉴定化合物结构；并对化合物的抗癌活性进行研究。结果：分离得到15个三萜类化合物,鉴定为α-香树素(α-amyrin,1),β-香树素(β-amyrin,2),乌苏酸(ursolic acid,3),2α-羟基乌苏酸(corosolic acid,4),蔷薇酸(euscaphic acid,5),坡模酸(pomolic acid,6),委陵菜酸(tormentic acid,7),2α,3α-二羟基-12-烯-28-乌苏酸(2α,3α-dihydroxyurs-12-en-28-oic acid,8),2β,3β,19α-三羟基-12-烯-28-乌苏酸(2β,3β,19α-trihydroxyurs-12-en-28-oic acid,9),积雪草酸(asiatic acid,10),24-羟基委陵菜酸(24-hydroxy tormentic acid,11),2α,3α,19α,23-四羟基-12-烯-28-乌苏酸(myrianthic acid,12),齐墩果酸(oleanolic acid,13),2α-羟基齐墩果酸(maslinic acid,14),2α,3α-二羟基-12-烯-28-齐墩果酸(2α,3α-dihydroxyolean-12-en-28-oic acid,15)。结论：化合物1,2,4～15为首次从委陵菜中分离得到；化合物4,8～10,12,14和15对人宫颈癌细胞(Hela)和小鼠成纤维细胞(L929)具有一定的细胞毒作用,其中化合物4和9抗癌活性较强。     

Triterpenoids from the resin of Styrax tonkinensis and their antiproliferative and differentiation effects in human leukemia HL-60 cells

Four new triterpenoids, 6beta-hydroxy-3-oxo-11alpha,12alpha-epoxyolean-28,13beta-olide (1), 3beta,6beta-dihydroxy-11alpha,12alpha-epoxyolean-28,13beta-olide (2), 3beta,6beta-dihydroxy-11-oxo-olean-12-en-28-oic acid (3), and 3beta-hydroxy-12-oxo-13Halpha-olean-28,19beta-olide (4), and five known triterpenes, 19alpha-hydroxy-3-oxo-olean-12-en-28-oic acid (5), 6beta-hydroxy-3-oxo-olean-12-en-28-oic acid (6), sumaresinolic acid (7), siaresinolic acid (8), and oleanolic acid (9), were isolated from the resin of Styrax tonkinensis. The structures of these triterpenoids were determined by physicochemical and spectroscopic methods. The configuration of compound 4 was confirmed by X-ray crystallographic analysis. All these triterpenoids inhibited HL-60 cell growth with IG(50) values ranging from 8.9 to 99.4 microM. Oleanolic acid (9) was the most effective antiproliferative agent, with an IG(50) value of 8.9 microM. While 3beta,6beta-dihydroxy-11-oxo-olean-12-en-28-oic acid (3) exhibited the least effective growth inhibition among these triterpenoids, it induced HL-60 cells to undergo differentiation as measured by an NBT reduction assay.     

Plant anticancer agents XLIV. Cytotoxic constituents from Stizophyllum riparium

Bioactivity-guided fractionation of a CHCl3 extract of Stizophyllum riparium has afforded six new compounds, namely, the triterpene esters, 3 beta-hydroxy-24-transferulyloxyurs-12-en-28-oic acid, 3 beta-hydroxy-24-cis-ferulyloxyurs-12-en-28-oic acid, 3 beta, 19-dihydroxy-24-trans-ferulyloxyurs-12-en-28-oic acid, and the pregnane derivatives, 2 alpha, 3 beta, 12 beta-trihydroxypregna-4,7,16-trien-20-one, 2 alpha, 3 beta, 12 beta-trihydroxypregna-4,7-dien-20-one, and 16 alpha-methoxy-2 alpha, 3 beta, 12 beta-trihydroxypregna-4,7-dien-20-one. The structures of these isolates were established by spectroscopic and chemical methods. Compounds 1, 2, and 4 exhibited cytotoxic activity against the P-388 lymphocytic leukemia test system in cell culture.     

Acinospesigenin-A, -B,and -C: three new triterpenoids from Phytolacca acinosa

Three new triterpenoids, designated as acinospesigenin-A (1), -B (2), and -C (3), isolated from the berries of Phytolacca acinosa, have been characterized as 3 beta-acetoxy-11 alpha,23-dihydroxytaraxer-14-en-28-oic acid, olean-12-en-23-al-2 beta,3 beta-dihydroxy-30-methoxycarbonyl-28-oic acid and olean-12-en-23-al-2 beta,3 beta,11 alpha-trihydroxy-30-methoxycarbonyl-28-oic acid, respectively. The compounds have shown antiedemic activity (LD(50) 10-15 mg/kg mass) in albino rats.     

Chemical investigation and anti-inflammatory activity of Vitex negundo seeds.

The CHCl3 extract of the defatted seeds of Vitex negundo exhibited anti-inflammatory activity and yielded four triterpenoids: 3 beta-acetoxyolean-12-en-27-oic acid [1], 2 alpha, 3 alpha-dihydroxyoleana-5,12-dien-28-oic acid [2], 2 beta,3 alpha-diacetoxyoleana-5,12-dien-28-oic acid [3], and 2 alpha,3 beta-diacetoxy-18-hydroxyoleana-5,12-dien-28-oic acid [5]. This is the first report of the isolation of compounds 2, 3, and 5 from a natural source.     

长柄异木患的化学成分(英文)

目的:研究长柄异木患(Allophylulogipess)茎中的化学成分。方法:对长柄异木患茎甲醇提取物的乙酸乙酯部分进行色谱分离,根据光谱数据和理化性质确定各化合物的结构。结果:分离得到25个化合物,分别鉴定为:ycloart-24-ene-3β,26-diol(1),3-oxotrirucalla-7,24-dien-21-oicacid(2),zizyberenalicacid(3),蛇藤酸(4),ent-4(15)-eudesmene-1β,6a-diol(5),4(15)-eudesmene-1β,8a-diol(6),4(15)-eudesmene-1β,5a-diol(7),甲基埃斯特瑞(8),白桦脂醇(9),白桦脂醛(10),白桦脂酸(11),3β-hydroxy-5a,8a-epidioxyergosta-6,22-dien(12),3-oxo-19a-hydroxyurs-12-en-28-oicacid(13),熊果酸(14),东莨菪内酯(15),梣皮啶(16),黄花菜木脂素A(17),香草醛(18),松柏醛(19),2’,6’-dihydroxy-4’-methoxyacetophenone(20),p-(aminoalkyl)-benzoicacid(21),香草酸(22),1-O-p-coumaroylglucose(23),β-谷甾醇(24),poriferast-5-ene-3β,4β-diol(25)。结论:所有化合物均为首次从长柄异木患(Allophylulogipess)中分离得到。     

Bioactive steroids from the whole herb of Euphorbia chamaesyce

Three new ergostane-type steroids, 3beta-hydroxy-4alpha, 14alpha-dimethyl-5alpha-ergosta-8,24(28)-dien-11 -one (1); 3beta, 11alpha-dihydroxy-4alpha,14alpha-dimethyl-5alpha -ergosta-8, 24(28)-dien-7-one (2); and 3beta,7alpha-dihydroxy-4alpha, 14alpha-dimethyl-5alpha-ergosta-8,24(28)-dien-11 -one (3), were isolated, together with two known triterpenoids, wrightial and lup-20(30)-ene-3beta,29-diol from the whole herb of Euphorbia chamaesyce. Compound 3 showed a potent inhibitory effect on Epstein-Barr virus early antigen activation induced by the tumor promoter 12-O-tetradecanoylphorbol 13-acetate (TPA).     

Chemical constituents of the aerial parts of Schnabelia tetradonta

A phytochemical study on the ethanol extract of the aerial parts of Schnabelia tetradonta led to the isolation of five new compounds, 1-5, together with seven known compounds. The structures of the new compounds were elucidated on the basis of spectral data interpretation as 2alpha,3alpha,23,29-tetrahydroxyolean-12-en-28-oic acid (1), 3-O-beta-d-glucuronopyranosyl-2beta,3beta,16beta-trihydroxy-28-norolean-12-en-15-on-23-oic acid (2), 21-O-beta-d-glucopyranosyl-3beta,21alpha,30-trihydroxyolean-13(18)-en-24-oic acid (3), 6-C-beta-l-arabinopyranosyl-8-C-alpha-l-arabinopyranosylapigenin (4), and 4-acetylaminoethylphenyl 1-O-[6-O-(Z)-p-methoxycinnamoyl-beta-d-glucopyranosyl(1-->2)]-[beta-d-glucopyranosyl(1-->3)]-alpha-l-rhamnopyranoside (5), respectively.