Poriacosones A and B: two new lanostane triterpenoids from Poria cocos

Two new lanostane triterpenoids, poriacosones A (8) and B (9), together with eight known compounds were isolated from the sclerotia of Poria cocos (Schw.) Wolf (Polyporaceae), and identified by spectroscopic analysis, including IR, UV, CD, ESI-TOF-MS, HR-SIMS, 1D-, and 2D-NMR spectra. The structures of the new compounds were established as 3alpha,16alpha-dihydroxy-24-oxolanost-7,9(11)-dien-21-oic acid (8) and 3beta,16alpha-dihydroxy-24-oxolanost-7,9(11)-dien-21-oic acid (9).     

Anti-inflammatory ergostanes from the basidiomata of Antrodia salmonea

Three new anti-oxidative ergostanes, methyl antcinate L (1), antcin M (2), and methyl antcinate K (3), together with nine additional known compounds, 3-ketodehydrosulphurenic acid, sulphurenic acid, dehydrosulphurenic acid, 3beta,15alpha-dihydroxylanosta-7,9(11),24-trien-21-oic acid, zhankuic acid A, zhankuic acid B, zhankuic acid C, antcin C, and antcin K were isolated from the basidiomata of Antrodia salmonea, a newly identified species of Antrodia (Polyporaceae) in Taiwan. These three new compounds were identified as methyl 3alpha,7alpha,12alpha-trihydroxy-4alpha-methylergosta-8,24(29)-dien-11-on-26-oate (1), 3alpha,12alpha-dihydroxy-4alpha-methylergosta-8,24(29)-dien-11-on-26-oic acid (2), and methyl 3alpha,4beta,7beta-trihydroxy-4alpha-methylergosta-8,24(29)-dien-11-on-26-oate (3) by spectroscopic analysis. We studied their antioxidative potential on the production of reactive oxygen species and nitric oxide (NO) in neutrophils and microglial cells, respectively. Compounds 1-3 displayed potent antioxidative activity with IC50 values of around 2.0-8.8 microM that was partially due to inhibition (6-67%) of NADPH oxidase activity but not through direct radical-scavenging properties. Compounds 1-3 also inhibited NO production with IC50 values of around 1.7-16.5 microM and were more potent than a non-specific NOS inhibitor. We conclude that these three new compounds 1, 2, and 3 exhibit anti-inflammatory activities in activated inflammatory cells.     

赤芝子实体中灵芝酸类成分的研究

自赤芝［Ｇａｎｏｄｅｒｍａｌｕｃｉｄｕｍ（Ｆｒ．）Ｋａｒｓｔ．］子实体的二氯甲烷提取物中分离得到一个新的四环三萜化合物，命名为灵芝酸ＤＭ（ｇａｎｏｄｅｒｉｃａｃｉｄＤＭ，Ｉ）。根据光谱（ＵＶ，ＩＲ，１ＨＮＭＲ，１３ＣＮＭＲ，ＭＳ２ＤＮＭＲ）分析，确定其结构为Ｉ式。同时还分离得到二个已知的灵芝酸类化合物，即灵芝酸Ａ（ｇａｎｏｄｅｒｉｃａｃｉｄＡ，Ｉ）和灵芝酸Ｃ（ｇａｎｏｄｅｒｉｃａｃｉｄＣ，ＩＩ）。     

Two new triterpenoids from the resin of Boswellia carterii

Two new triterpenoids, 3-oxotirucalla-7,9(11),24-trien-21-oic acid (1) and 18Hα,3β,20β-ursanediol (2), along with 15 known triterpenes, α-amyrin, α-boswellic acid, β-boswellic acid, acetyl α-boswellic acid, acetyl β-boswellic acid, 9,11-dehydro-β-boswellic acid, 9,11-dehydro-α-boswellic acid, acetyl 11α-methoxy-β-boswellic acid, 11-keto-β-boswellic acid, acetyl 11-keto-β-boswellic acid, acetyl α-elemolic acid, 3β-hydroxytirucalla-8,24-dien-21-oic acid, elemonic acid, 3α-hydroxytirucalla-7,24-dien-21-oic acid, and 3α-hydroxytirucall-24-en-21-oic acid, were isolated from the resin of Boswellia carterii Birdw.     

Two new triterpenoids from the resin of Boswellia carterii

Two new triterpenoids, 3-oxotirucalla-7,9(11),24-trien-21-oic acid (1) and 18Hα,3β,20β-ursanediol (2), along with 15 known triterpenes, α-amyrin, α-boswellic acid, β-boswellic acid, acetyl α-boswellic acid, acetyl β-boswellic acid, 9,11-dehydro-β-boswellic acid, 9,11-dehydro-α-boswellic acid, acetyl 11α-methoxy-β-boswellic acid, 11-keto-β-boswellic acid, acetyl 11-keto-β-boswellic acid, acetyl α-elemolic acid, 3β-hydroxytirucalla-8,24-dien-21-oic acid, elemonic acid, 3α-hydroxytirucalla-7,24-dien-21-oic acid, and 3α-hydroxytirucall-24-en-21-oic acid, were isolated from the resin of Boswellia carterii Birdw.     

Eremophilane sesquiterpenes from Cacalia ainsliaeflora

Chemical investigation of Cacalia ainsliaeflora afforded four new eremophilane sesquiterpenes (1 - 3, 5) and a known sesquiterpene (4), which were identified as 3 beta-angeloyloxy-8 alpha-hydroxy-6 beta-methoxyeremophil-7(11),9(10)-dien-8,12-olide (1), 3 beta-angeloyloxy-6 beta,8 alpha-dihydroxyeremophil-7(11),9(10)-dien-8,12-olide (2), 3 beta-angeloyloxy-8 alpha-hydroxy-6 beta-ethoxyeremophil-7(11),9(10)-dien-8,12-olide (3), 3 beta-angeloyloxy-8-oxo-eremphila-6,9-dien-12-oic acid (4), and 3,8-oxo-eremophila-6,9-dien-12-oic acid (5) respectively. These compounds were assayed against Escherichia coli, Staphylococcus aureus and Bacillus subtilis, and compounds 1, 2, 4 and 5 showed weak antibacterial activity. The structures of the compounds were established by 1D and 2D NMR experiments.     

Trypanosomicidal kaurane diterpenes from Wedelia paludosa

The diterpenes ent-kaur-16-en-19-oic acid, ent-kaur-9(11),16(17)-dien-19-oic acid and 3 alpha-angeloiloxy-ent-kaur-16-en-19-oic acid were identified as trypanosomicidal compounds of the ethanolic extract from the aerial parts of Wedelia paludosa D.C. (Asteraceae), showing activity up to the lowest dose of 0.68 mg/mL in the in vitro assay against trypomastigotes of T. cruzi, the causative agent of Chagas' disease (American trypanosomiasis). The other isolates, friedelan-3 beta-ol, ent-kaur-16 alpha-ol-19-oic acid, beta-amyrin acetate and (22-E)-stigmasta-5,22-dien-3 beta-ol, were inactive. This is the first report on the trypanosomicidal activity of ent-kaur-9(11),16(17)-dien-19-oic acid and 3 alpha-angeloiloxy-ent-kaur-16-en-19-oic acids; this effect was already known for ent-kaur-16-en-19-oic acid.     

赤芝孢子粉三萜化学成分研究

自赤芝(Ganoderma lucidum Karst)孢子粉酸性部分分离得到一个新的四环三萜化合物,命名为ganosporeric acid A(1),根据光谱(IR,¹HNMR,¹³CNMR和MS)分析确定其结构为Ⅰ所示。同时还分到四个已知化合物:ganoderic acid B(Ⅱ),ganodefic acid C(Ⅲ),ganoderic acidE(Ⅳ),和ganodermanontriol(Ⅴ)。这些化合物均为首次从赤芝孢子粉中得到。     

Chemical constituents from Trichosanthes cucumeroides

One new triterpenoid, 3β-[(E)-caffeoyloxy]-D:C-friedooleana-7,9(11)-dien-29-oic acid (1) and nine known triterpenoidsidentified as cucurbitacin B (2), 23,24-dihydrocucurbitacin B (3), 23,24-dihydrocu-curbitacin D (4), cucurbitacin D (5), cucurbalsaminol A (6), 3-epi-isocucurbitacin D (7), curbitacin G (8), cucurbitacin J (9) and cucurbitacin I (10)were purified from Trichosanthes cucumeroides. Their structures were confirmed by spectroscopic data analysis and comparison with previous literature. All compounds were obtained from T.cucumeroides for the first time.     

Two new lanostanoids from Ganoderma resinaceum

Two new lanostane triterpenoids, 3-epipachymic acid (3alpha-acetoxy-16alpha-hydroxy-24-methylene-5alpha-lanost-8-en-21-oic acid, 1) and 3alpha-(3-hydroxy-5-methoxy-3-methyl-1,5-dioxopentyloxy)-24-methylene-5alpha-lanost-8-en-21-oic acid (2), together with a known compound, 3-oxo-5alpha-lanosta-8,24-dien-21-oic acid (3), were isolated from the fruiting body of Ganoderma resinaceum. The structure elucidation was accomplished by spectroscopic methods, especially NMR experiments. Compound 2 showed significant cytotoxic activity with IC(50) value of 2.5 microg/ml in Hep-2 cell line.     

Inhibitory Constituents against Cyclooxygenases fromAralia cordata Thunb

Seven diterpenes, four polyacetylenes, a lipid glycerol, and two sterols were isolated from the methylene chloride fraction of the root of Aralia cordata. Their chemical structures were determined as (-)-pimara-8(14),15-dien-19-oic acid (2), pimaric acid (3), (-)-kaur-16-en-19-oic acid (4), 17-hydroxy-ent-kaur-15-en-19-oic acid (9), 7alpha-hydroxy-(-)-pimara-8(14),15-dien-19-oic acid (10), 16alpha,17-dihydroxy-(-)-kauran-19-oic acid (11), 16-hydroxy-17-isovaleroyloxy-ent-kauran-19-oic acid (12), falcarindiol (5), dehydrofalcarindiol (6), dehydrofalcarindiol-8-acetate (7), falcarindiol-8-acetate (8), alpha-mono palmitin (13), stigmasterol (1), and daucosterol (14) by the spectral evidences. These compounds were tested with COX-1 and COX-2 inhibition assays. This study found that compounds 2, 4, 5, 6, 7, 8, and 10 inhibited COX-1 dependent conversion of the exogenous arachidonic acid to PGE2 in a dose-dependent manner with IC50 values of 134.2 microM, 121.6 microM, 170 microM, 50.4 microM, 11.7 microM, 99.6 microM, and 69.6 microM, respectively. But, most of these compounds weakly inhibited COX-2 dependent PGE2 generation. Among them, only compound 4 showed relatively significant inhibitory activity (IC50: 127.6 microM).     

Bioactive terpenes from the roots of Chloranthus henryi

12,15-Epoxy-5alpha H,9beta H-labda-8(17),13-dien-19-oic acid (1) and 14-methoxy-15,16-dinor-5alpha H,9alpha H-labda-13(E),8(17)-dien-12-one (2), two new labdane-type diterpenes, and 1alpha-hydroxy-8,12-epoxyeudesma-4,7,11-triene-6,9-dione (3), one new eudesmane-type sesquiterpene, were isolated from Chloranthus henryi Hemsl, along with two known compounds, 8beta H-eudesma-4(14),7(11)-dien-12,8-olide (4) and 8beta-hydroxyeudesma-4(14),7(11)-dien-12,8-olide (5). Their structures were established by a combination of 1D- and 2D-NMR spectroscopic techniques. The new compounds 2, 3 and the known compound 4 exhibited antitumor activities against Hela and K562 human tumor cell lines.     

Terpenoids and steroids from several euphorbiaceae and pinaceae plants]

During the course of a search for biologically active constituents from unexamined plant sources, several biogenetically interesting new di- and tri-terpenes and steroids were isolated from several weeds and shrubs of Euphorbiaceae and the bark, leaves and cones of several Pinaceae trees which had been treated as wastes in the forestry industry. Euphorbia supina contained 3,4-seco-5 alpha- and 5 beta-adian-4(23)-ene-3,5-diols and related oxides, oxygenated fern-8-en-3 beta-ols named supinenolones A-E and unusually migrated oxyfernanes having (9S)- and (9R)-7(8-->9)abeo-9-D:C-friedo-B':A'-neogammacerane skeletons named spirosupinane and neospirosupinane, while E. chamaesyce contained 3,4-seco-oleana-4(23), 18-dien-3-oic acid, 3,4-seco-8 beta H-ferna-4(23),9(11)-dien-3-oic acid and two oxygenated obtusifoliols. The bark of Phyllanthus flexuosus (Euphorbiaceae) contained 11 beta-hydroxy-D:A-friedo-olean-1-en-3-one, lup-20(29)-ene-3 beta, 15 alpha-diol, olean-12-ene-3 beta,15 alpha-diol and olean-12-ene-3 beta,15 alpha,24-triol together with trichadenic acid B for which we revised the structure to 3 beta-hydroxy-D:A-friedo-oleanan-27-oic acid. Two 26-nor-D:A-friedo-olean-14-enes were isolated from P. watsonii. Regarding Pinaceae trees, an unusually migrated abieslactone [(3R, 7S, 9R, 23R)-7-hydroxy-3-methoxy-8-oxo-7(8-->9)abeo-lanost-24-eno-26,23-lactone], named spiroveitchionolide, was isolated from the bark of Abies species, besides nine abieslactone analogues. Two pairs of unusually migrated serratanes, piceanonols A and B and jezananals A and B having novel skeletal systems of 14(13-->12) abeo- and 16(15-->14) abeo-serratanes named piceanane and jezanane, respectively, were also isolated from the stem bark of Picea species, besides three 14 beta,15 beta-epoxyserratanes and two 13 alpha,14 alpha-epoxyserratanes. The leaves of Larix kaempferi contained two deformed abietanes named karamatsuic acid (9,10-seco-9,10 alpha-epoxyabieta-8,11,13-trien-18-oic acid) and larikaempferic acid [9 alpha,13 alpha-epoxy-8-oxo-9(8-->7)abeo-7 beta-abietan-18-oic acid], as well as the cones to contain 8 alpha,12 alpha-epidioxy-15-hydroxyabiet-13-en-18-oic acid, three diepoxy-abietan-18-oic acids and two new dehydroabietic acid analogues. Several of the above compounds exhibited inhibitory effects against tumor-promoting and DNA topoisomerase II activities.     

Cytotoxic and pro-apoptotic effects of novel ganoderic acid derivatives on human cervical cancer cells in vitro

Ganoderic acid T, a triterpenic acid produced by Ganoderma lucidum, has demonstrated therapeutic potential for tumor disease. In the current work, ganoderic acid T was modified to produce more effective small-molecule inhibitors of cancer cell proliferation. Moreover, the anticancer effects of three new ganoderic acid T derivatives, i.e., (22S,24E)-3α,15α,22-triacetoxy-5α-lanosta-7,9(11),24-trien-26-oic acid ethyl ester (TLTO-Ee), (22S,24E)-3α,15α,22-triacetoxy-5α-lanosta-7,9(11),24-trien-26-oic acid propyl ester (TLTO-Pe), and (22S,24E)-3α,15α,22-triacetoxy-5α-lanosta-7,9(11),24-trien-26-oic acid amide (TLTO-A), and one known derivative, (22S,24E)-3α,15α,22-triacetoxy-5α-lanosta-7,9(11),24-trien-26-oic acid methyl ester (TLTO-Me), on the cervical cell line HeLa were investigated and compared. MTT assay indicated that, among the tested compounds, TLTO-A displayed the highest inhibitory effect on the growth of HeLa cells, whereas it showed less cytotoxicity to the non-tumorous cell line MCF-10A than ganoderic acid T. Flow cytometry analysis revealed that all the compounds caused cell cycle arrest at the G1 phase and induced apoptosis. Furthermore, they decreased the mitochondrial membrane potential and enhanced the activities of pro-apoptotic factors caspase-3 and caspase-9 in a dose-dependent manner. Accordingly, the apoptosis induction was presumed to occur through the endogenous pathway. The following order ranks both cytotoxic and pro-apoptotic effects of the compounds against HeLa cells: TLTO-A>ganoderic acid T≈TLTO-Me≈TLTO-Ee≈TLTO-Pe. This study suggests that the carboxyl group of ganoderic acid T is not the main active group and is suitable for its further structural modification. The current work presents valuable information on the design of ganoderic acid T derivatives to develop potential chemotherapy agents.     

Cytotoxic triterpenoids and steroids from the bark of Melia azedarach

Two new triterpenoids (1, 2) and two new steroids (3, 4) along with twelve related known compounds (5-16) were isolated from the bark of Melia azedarach. The new structures were elucidated by means of spectroscopic methods and molecular modeling studies and found to be 21,24-cycloeupha-7-ene-3 β,16 β,21 α,25-tetrol (1), 3 β-acetoxy-12 β-hydroxy-eupha-7,24-dien-21,16 β-olide (2), 29-hydroperoxy-stigmasta-7,24(28) E-dien-3 β-ol (3), and 24 ξ-hydroperoxy-24-vinyl-lathosterol (4). All isolated compounds were tested for their cytotoxic activity against three human cancer cell lines (A549, H460, HGC27) using the CellTiter Glo? luminescent cell viability assay. Among them, compounds 2- 4, 24 ξ-hydroperoxy-24-vinyl-cholesterol (6), kulinone (7), meliastatin 3 ( 8), 3-oxo-olean-12-en-28-oic acid (10), and (22 E,24 S)-5 α,8 α-epidioxy-24-methyl-cholesta-6,22-dien-3 β-ol (12) were found to have cytotoxic effects, with IC?? values of 5.6-21.2?μg/mL.     

Triterpenoid Acids from Kadsura longipedunculata. Neokadsuranic Acids B and C: Two Novel Triterpenoids with 14 (13 --> 12)abeo-Lanostane Skeletons

Six triterpenoid acids were isolated from the stems of KADSURA LONGIPEDUNCULATA, collected in Kuangxi province. Four of them were new compounds and assigned as (24 Z)-3-oxo-12alpha-acetoxylanosta-8,24-dien-26-oic acid ( 1), (24 Z)-3-oxo-12alpha-hydroxylanosta-8,24-dien-26-oic acid ( 2), (24 Z)-3-oxo-14(13-->12) ABEO-lanosta-8,13(18),24-trien-26-oic acid ( 3), and (24 Z)-3-oxo-13beta-hydroxy-14(13-->12) ABEO-lanosta-8,24-dien-26-oic acid ( 4). Compounds 3 and 4 were named neokadsuranic acids B and C, respectively.     

Diterpenoids from Turraeanthus mannii

Three new compounds, 15-acetoxy-12-hydroxy-16-methyl-labda-8(17),13E-diene (1), ent-labda-8(17),13-dien-15,16-olid-19-oic acid methyl ester (2), and 12-hydroxy-labda-8(17),13-dien-15,16-olide (3), together with two known compounds, 19-acetoxy-ent-labda-8(17),13-dien-15,16-olide (4), and 16-acetoxy-12,15-epoxy-15beta-hydroxy-labda-8(17),13(16)-diene (5) were isolated from the stem bark of Turraeanthus mannii (Meliaceae). The structures of compounds 1 - 3 were elucidated by analysis of the spectroscopic data. The crude methanol extract and compound 5 exhibited weak antibacterial and antifungal activity.     

Glyyunnansapogenins G and H: Two New Pentacyclic Triterpenoids of the 18alphaH-Oleana-9(11),12-diene Type from Glycyrrhiza yunnanensis Roots

Two new pentacyclic triterpenoid sapogenins of the 18alpha H-oleana-9(11),12-diene type named glyyunnansapogenins G and H were isolated from the roots of GLYCYRRHIZA YUNNANENSIS Cheng f. et L. K. Tai. Their structures were elucidated as 18alpha H-oleana-9(11),12-diene-3beta,21alpha,29-triol and 18alpha H-3beta,21alpha-dihydroxyoleana-9(11),12-dien-29-oic acid, respectively, by spectroscopic methods. This is the first report of the occurrence of the 18alpha H series of oleana-9(11),12-diene compounds in nature.     

番荔枝化学成分研究

从番荔枝(Annona squamosa)中分离得到12个化合物,分别鉴定为liriodenine(AS—1),穆坪马兜铃酰胺(moupinamide,AS-2),-(-)-kauran-16α-01-19-oic acid(AS-3),16β,17-dihydroxy-(-)-kauran-19-oic acid(AS-4),anonaine(AS-5),16α,17-dihydroxy-(-)-kauran-19-oic acid(AS-6),(-)-isokaur-15(16)-en-17,19-dioic acid(AS-7),番荔枝酰胺squamosamide(AS-8),16α-methoxy-(-)kauran-19-oicacid(AS-9),sachanoic acid(AS-10),(-)-kauran-19-al-17-oic acid(AS-11),daucosterol(AS-12)。其中,番荔枝酰胺(AS-8)是新化合物,AS-9是第一次从植物中得到的天然产物。     

Cytotoxic and DNA topoisomerases I and II inhibitory constituents from the roots of<Emphasis Type="Italic">Aralia cordata</Emphasis>

Bioactivity-guided fractionation, based on the DNA topoisomerase inhibitory activity, lead to the isolation of five compounds (1-5) from the methylene chloride extract of the roots of Aralia cordata Thunb. (Araliaceae). These compounds were identified as ent-pimara-8(14), 15-dien-19-oic acid (1), ent-pimara-8(14), 15-dien-18-oic acid (2), 16alpha-hydrogen-17-isovaleryloxy-ent-kauran-19-oic acid (3), 16alpha-hydroxy-17-isovaleryloxy-ent-kauran-19-oic acid (4) and dehydrofalcarindiol-8-acetate (5) from their spectral data. Compound 3 was isolated for the first time from this plant, and also showed the strongest inhibition of both DNA topoisomerase I and II activities, with 53 and 96% inhibitions, respectively, at a concentration of 20 microM. However, all the compounds exhibited either weak or no cytotoxicities against the human colon carcinoma cell line (HT-29), the human breast carcinoma cell line (MCF-7) and human hepato blastoma cell line (HepG-2).