Antifungal rosane diterpenes and other constituents of Hugonia castaneifolia

The rosane diterpenoids hugorosenone [3beta-hydroxyrosa-1(10),15-dien-2-one], 18-hydroxyhugorosenone and 18-hydroxy-3-deoxyhugorosenone, and 12-hydroxy-13-methylpodocarpa-8,11,13-trien-3-one were isolated as antifungal constituents of H. castaneifolia Engl. root bark, together with the previously reported di-podocarpanoids hugonone A and hugonone B that were weakly active, and 1(10),15-rosadiene-2beta,3beta-diol (hugorosenol), 4alpha-methoxyhimachal-10-en-5beta-ol (hugonianene B) and 2-hydroxyhenpentacont-2-enal, and the known compounds tetracosyl-(E)-ferrulate and caryophyllene oxide, all of which were inactive. Hugorosenone also exhibited activity against Anopheles gambiae mosquito larvae. Structural determination was achieved based on spectroscopic data.     

Anti-tumor promoting diterpenes from the stem bark of Thuja standishii (Cupressaceae).

Three new labdane-type diterpenoids, labda-8(17),13-dien-15,12R-olid-19-oic acid (1), 12S-hydroxylabda-8(17),13(16),14-trien-19-oic acid (2) and 13-ethoxylabda-8(17),11,14-trien-19-oic acid (3), along with known diterpenoids, trans-communic acid (4), totarol (5), 12-methoxyabieta-8,11,13-trien-11-ol (6), and 7 alpha,8 alpha-epoxy-6 alpha-hydroxyabieta-9(11),13-dien-12-one (7) were isolated from the stem bark of Thuja standishii. The structures of 1--3 were established by spectroscopic methods and chemical conversion. These compounds together with standishinal (8), 12-hydroxy-6,7-seco-abieta-8,11,13-trien-6,7-dial (9) and 6 alpha-hydroxysugiol (10) were tested for their inhibitory effects on Epstein--Barr virus early antigen (EBV-EA) activation induced by 12-O-tetradecanoylphorbol-13-acetate (TPA), as a test for potential cancer chemopreventive agents. Compound 10 showed strong inhibitory effect on EBV-EA induction (100% inhibition at 1000 mol ratio/TPA), and compounds 2 and 6 showed moderate inhibitory effects on EBV-EA induction. In addition, 15-oxolabda-8(17),11Z,13E-trien-19-oic acid (11) was found to exhibit the anti-tumor promoting activity in two-stage mouse skin carcinogenesis test using 7,12-dimethylbenz[a]anthracene and TPA.     

Antifungal isopimaranes from Hypoestes serpens

Five isopimarane diterpenes (7beta-hydroxyisopimara-8,15-dien-14-one, 14alpha-hydroxyisopimara-7,15-dien-1-one, 1beta,14alpha-dihydroxyisopimara-7,15-diene, 7beta-hydroxyisopimara-8(14),15-dien-1-one and 7beta-acetoxyisopimara-8(14),15-dien-1-one) have been isolated from the leaves of Hypoestes serpens (Acanthaceae). All compounds exhibited antifungal activity against both the plant pathogenic fungus Cladosporium cucumerinum and the yeast Candida albicans; two of them also displayed an acetylcholinesterase inhibition. The structures of the compounds were determined by means of spectrometric methods, including 1D and 2D NMR experiments and MS analysis.     

18-nor-Podocarpanes and podocarpanes from the Bark of Taiwania cryptomerioides

Seven nor- and podocarpane-type diterpenes were isolated from the bark of Taiwania cryptomerioides Hayata, including three 18-nor-podocarpanes: 18-nor-1beta,4alpha,14-trihydroxy-13-methoxy-8,11,13-podocarpatriene (1), 18-nor-1beta,4alpha,13,14-tetrahydroxy-8,11,13-podocarpatrien-7-one (2), 18-nor-1beta,4alpha,14-trihydroxy-13-methoxy-8,11,13-podocarpatrien-7-one (3), 1beta,14,19-trihydroxy-13-methoxy-8,11,13-podocarpatrien-7-one (4), 1beta,13,14,18-tetrahydroxy-8,11,13-podocarpatrien-7-one (5), 18-acetoxy-1beta,13,14-trihydroxy-8,11,13-podocarpatrien-7-one (6), and 1beta,14,18-trihydroxy-13-methoxy-8,11,13-podocarpatrien-7-one (7). Their structures were determined by application of 1D and 2D NMR spectroscopy and other techniques. Podocarpane-type diterpenes do not occur extensively in nature, and the presumed oxidative enzyme in this plant will be of interest to identify.     

椭圆嗜蓝孢孔菌子实体的化学成分

从椭圆嗜蓝孢孔菌Fomitiporia ellipsoidea子实体的石油醚提取物中分离得到6个化合物,分别是麦角甾-7,22,25-三烯-3-酮,21-羟基羊毛甾-7,9(11),24-三烯-3-酮,麦角甾-7,22-二烯-3β-棕榈酸酯,麦角甾-7,22-二烯-3-酮,麦角甾醇和过氧化麦角甾醇;从其脱脂后的氯仿提取中分离得到了3个化合物,分别是：苯并(1,2-b;5,4-b′)二呋喃-3,5-二酮-8-甲酸甲酯,麦角甾-7,22-烯-3b-醇和b-谷甾醇。其中苯并(1,2-b;5,4-b′)二呋喃-3     

非洲隔囊蚁巢伞的化学成分研究(英文)

从肯尼亚安波塞利产的隔囊蚁巢伞(Termitomyces schimperi)子实体中分离得到8个已知化合物,通过波谱方法鉴定它们的结构为(22E,24R)-麦角甾-5,7,22-三烯-3β-醇(1),(3β,5α,9α-三羟基麦角甾-7,22-二烯-6-酮(2),5α,8α-过氧-(22E,24R)-麦角甾-6,22-二烯-3β-醇(3),麦角甾-4,6,8(14),22-四烯-3-酮(4),D-阿拉伯糖醇(5),D-半乳糖醇(6),脑苷脂B(7)和脑苷脂D(8)。所有化合物均首次从该真菌中分离得到。     

Two Antioxidative Diterpenes from Rosemary (Rosmarinus officinalis L.) and a Revised Structure for Rosmanol†

Two new antioxidative compounds, named epirosmanol (4a) and isorosmanol (6a), were isolated from the leaves of rosemary (Rosmarinus officinalis L.). The structures have been determined to be 7β,11,12-trihydroxy-6,10-(epoxymethano)abieta-8,l 1,13-trien-20-one and 6α,ll,12-trihydroxy-7,10-(epoxymethano)abieta-8,ll,13-trien-20-one, respectively, on the basis of chemical and spectroscopic evidence. Both are isomers of rosmanol (1a), whose structure was revised to be 7α,ll,12-trihydroxy-6,10-(epoxymethano)abieta-8,ll,13-trien-20-one by the NOE experiment and X-ray analysis.

These two antioxidants showed high activity in both lard and linoleic acid and, particularly in lard, were about four times more active than such synthetic antioxidants, as BHA and BHT.     

New neutral diterpenes from southern pine tall oil

Five new diterpene natural products isolated from southern pine (Pinus spp.) tall oil were characterized as 8(14),15-pimaradiene-3β,18-diol, 19-hydroxy-15,16-dinorlabd-8(17)-en-13-one, 8,13β-epoxy-14-labden-6α-ol, 8,11, 13-abietatriene-15,18-diol and 9,10-secoabieta-8,11,13-trien-18,10-olide.     

思茅松松香中的一个新二萜

从思茅松（Pinus kesiya var.langbianensis）的松香中分离得到一个新奇的松香烷二萜化合物——思茅松素,经现代波谱分析将其化学结构确定为13（14）-烯-8,12-环氧-1-松香酸（1）,同时分离得到5个已知化合物,分别为abiet-8,11,13-trien-15-hydroxy-18-oic acid（2）;pimarol（3a）;iso-pimarol（3b）;abiet-trien-18．oic acid（4）;15．hydroxy abietic acid（5）。     

Ergosterimide, a new natural Diels-Alder adduct of a steroid and maleimide in the fungus Aspergillus niger

Ergosterimide (1), a natural Diels-Alder adduct of ergosteroid and maleimide, was characterized from the culture extract of Aspergillus niger EN-13, an endophytic fungus isolated from the marine brown alga Colpomenia sinuosa. In addition, four known steroids including (22E,24R)-ergosta-5,7,22-trien-3beta-ol (2), (22E,24R)-ergosta-4,6,8(14),22-tetraen-3-one (3), (22E,24R)-5alpha,8alpha-epidioxyergosta-6,22-dien-3beta-ol (4), and (22E,24R)-ergosta-7,22-dien-3beta,5alpha,6beta-triol (5) were also isolated and identified. The structures of these compounds were elucidated by extensive analysis of 1D and 2D NMR and IR spectra and MS data. The plausible biosynthetic pathway of 1 was also discussed. To the best of our knowledge, 1 is the first natural Diels-Alder adduct of steroid and maleimide reported so far.     

Sterols from a soft coral, Dendronephthya gigantea as farnesoid X-activated receptor antagonists

Three new steroids 3-oxocholest-1,22-dien-12β-ol (1), 3-oxocholest-1,4-dien-20β-ol (2), 3-oxocholest-1,4-dien-12β-ol (3), and three known steroids (20S)-20-Hydroxyergosta-1,4,24(28)-trien-3-one (4) [7a], 5α,8α-Epidioxycholesta-6,22-dien-3β-ol (5) [10] and 5-cholestene-3β,12β-diol (6) [11] were isolated from a soft coral Dendronephthya gigantea. Their chemical structures and relative stereochemistry were elucidated by the analysis of HRMS and 2-D NMR spectroscopic data. The steroids 1 and 2 showed notable inhibitory activity against farnesoid X-activated receptor (FXR) with IC(50)'s 14 and 15μM.     

蓝柄丽齿菌的化学成分

从担子菌亚门蓝柄丽齿菌(Calodon suaveolens)中首次分离得到8个化合物,通过波谱学技术并借助必要的化学方法最终确定结构,它们是：(22E,24R)-麦角甾-7,22-二烯-3β-醇(1),(22E,24R)-5α,8α-过氧麦角甾-6,22-二烯．3β-醇(2),(22E,24R)-麦角甾．5,7,22-三烯-3β-醇(3),(22E,24R)-3β-羟基麦角甾-5,22-二烯-7-酮(4),对羟基苯甲酸(5),尿嘧啶(6),polyozellin(7),(4E,BE）-2-N-(2’-羟基棕榈酰)-1-O-β-D-吡喃葡萄糖基-9-甲基-4,8-sphingadienine(8)。     

Volatile constituents in the liverwort Tritomaria polita

The essential oil of the liverwort Tritomaria polita, collected in Otztal/Tyrol (Austria), was investigated by chromatographic and spectroscopic methods. Several new compounds were isolated by preparative gas chromatography (GC) and their structures investigated by mass spectrometry (MS) and NMR techniques. In addition to known constituents, the sesquiterpenoids (+)-eudesma-3,11-dien-8-one, (+)-eudesma-3,7(11)-dien-8-one, (+)-6,11-epoxy-eudesmane, (-)-6,7-seco-eudesm-7(11)-en-6-al, (+)-6beta-hydroxy-eudesm-11-ene, (-)-6alpha-hydroxy-eudesm-11-ene, (+)-6,11-epoxy-isodaucane could be identified as natural compounds for the first time.     

虎皮小牛肝菌的化学成分研究

采用硅胶、RP-18、Sephadex LH-20等多种材料进行分离纯化,通过理化方法和波谱分析进行结构鉴定,从虎皮小牛肝菌(Boletinus pictus)子实体的氯仿/甲醇(1:1,v/v)提取部位中分离并鉴定了9个化合物,它们分别为:亚油酸甲酯(1)、9(Z)-十八烷烯酸(2)、麦角甾-5,7,22-三烯-3β-醇(3)、麦角甾-4,6,8(14),22-四烯-3-酮(4)、麦角甾-7,22-二烯-3β,5α,6β,9α-四醇(5)、邻苯二甲酸二丁酯(6)、邻苯二甲酸二异丁酯(7)、烟酰胺(8)和尿嘧啶核苷(9).所有化合物均是首次从虎皮小牛肝菌中得到.     

Six new ergosterols from the marine-derived fungus Rhizopus sp

Six new ergosterols, including 3beta-hydroxyl-(22E, 24R)-ergosta-5,8,22-trien-7,15-dione (1), 3beta-hydroxyl-(22E, 24R)-ergosta-5,8,14,22-tetraen-7-one (2), 3beta,15beta-dihydroxyl-(22E, 24R)-ergosta-5,8(14),22-trien-7-one (3), 3beta,15alpha-dihydroxyl-(22E, 24R)-ergosta-5,8(14),22-trien-7-one (4), 3beta-hydroxyl-(22E, 24R)-ergosta-5,8(14),22-trien-7,15-dione (5), and 5alpha,8alpha-epidioxy-23,24(R)-dimethylcholesta-6,9(11),22-trien-3beta-ol (6), have been isolated from the marine-derived fungus Rhizopus sp., along with four known ones (7-10). The structures of the new compounds were determined on the basis of extensive spectroscopic data. All compounds were evaluated for their cytotoxic activities on P388, A549, HL-60, and BEL-7420 cell lines by the MTT and SRB methods.     

石菖蒲的化学成分研究

运用色谱法从石菖蒲根茎提取物中分离得到18个化合物,经波谱学分析鉴定为:(7S,8R)-4,9’-di-hydroxyl-3,3’-dimethoxyl-7,8-dihydrobenzofuran-1’-propylneolignan(1),(7S,8R)-4,9’-dihydroxyl-3,3’-dimethoxyl-7,8-dihydrobenzofuran-1’-propylneoligan-9-O-β-D-glucopyranoside(2),7’-hydroxylariciresinol-9-acetate(3),5-羟基-3,7,4’-三甲氧基黄酮(4),野漆树苷(5),紫云英苷(6),松属素-3-O-芸香糖苷(7),山奈酚-3-O-芸香糖苷(8),德钦红景天苷(9),isoschaftoside(10),5-羟甲基糠醛(11),反式桂皮酸(12),3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oicacid(13),3,7-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oic acid methyl ester(14),环阿屯醇(15),胡萝卜苷(16),羽扇豆醇(17),(22E,24R)-ergosta-5,7,22-trien-3β-ol(18)。除化合物4、11和16外,其余15个化合物均为首次从该植物中分离得到。     

Structure of a New Antioxidative Phenolic Diterpene Isolated from Rosemary (Rosmarinus officinalis L.)

A new antioxidant, phenolic diterpene, named rosmanol, was isolated from the leaves of rosemary (Rosmarinus officinalis L.). Its structure has been determined as 7β,11,12-trihydroxy-6,10-(epoxymethano)abieta-8,11,13-trien-20-one on the basis of chemical and spectroscopic evidence. In addition, all the protons of rosmanol (II) as well as carnosol (I), including the methylene protons of the A ring, were analyzed by 400 MHz ¹-NMR.     

ent-Beyerane diterpenoids from the heartwood of Excoecaria parvifolia

Chromatographic fractionations of the toluene extract of the heartwood of Excoecaria parvifolia collected in Australia resulted in the isolation of 12 beyerane diterpenes (1-12), and the triterpene, lupeol. Four of the isolated diterpenoids (5-7 and 12) have unusual structures: ent-3-oxa-beyer-15-en-2-one, (5); ent-15,16-epoxy-2-hydroxy-19-norbeyer-1,4-dien-3-one (6); methyl ent-2,4-seco-15,16-epoxy-4-oxo-3,19-dinorbeyer-15-en-2-oate (7); and ent-2,17-dihydroxy-19-norbeyer-1,4,15-trien-3-one (12). The structures were established by spectroscopic analyses, NMR data comparisons with similar diterpenes, and chemical correlations. All the diterpenes are assumed to have the same absolute configuration as the co-occurring (+)-stachenol (4). Diosphenol 2 and nor-lactone 5 exhibited significant potency in bioassays for cytotoxic activity against leukemia cells (L1210). Plausible biosynthetic pathways are proposed to explain the origin of the diterpene metabolites.     

Differential metabolism of diastereoisomeric diterpenes by Preussia minima,found as endophytic fungus in Cupressus lusitanica

The plant diastereoisomeric diterpenes ent-pimara-8(14)-15-dien-19-oic acid, obtained from Viguiera arenaria, and isopimara-8(14)-15-dien-18-oic acid, isolated from Cupressus lusitanica, were distinctly functionalized by the enzymes produced in whole cell cultures of the fungus Preussia minima, isolated from surface sterilized stems of C. lusitanica. The ent-pimaradienoic acid was transformed into the known 7β-hydroxy-ent-pimara-8(14)-15-dien-19-oic acid, and into the novel diterpenes 7-oxo-8 β-hydroxy-ent-pimara-8(14)-15-dien-19-oic and 7-oxo-9β-hydroxy-ent-pimara-8(14)-15-dien-19-oic acids. Isopimara-8(14)-15-dien-18-oic acid was converted into novel diterpenes 11α-hydroxyisopimara-8(14)-15-dien-18-oic acid, 7β,11α-dihydroxyisopimara-8(14)-15-dien-18-oic acid, and 1β,11α-dihydroxyisopimara-8(14)-15-dien-18-oic acid, along with the known 7β-hydroxyisopimara-8(14)-15-dien-18-oic acid. All compounds were isolated and fully characterized by 1D and 2D NMR, especially ¹³C NMR. The diterpene bioproduct 7-oxo-9β-hydroxy-ent-pimara-8(14)-15-dien-19-oic acid is an isomer of sphaeropsidin C, a phytotoxin that affects cypress trees produced by Shaeropsis sapinea, one of the main phytopathogen of Cupressus. The differential metabolism of the diterpene isomers used as substrates for biotransformation was interpreted with the help of computational molecular docking calculations, considering as target enzymes those of cytochrome P450 group.     

Concerning the chemical synthesis of 3 beta-hydroxy-5 alpha-cholest-8(14)-en-15-one, a novel regulator of cholesterol metabolism

A four-step synthesis of 3 beta-hydroxy-5 alpha-cholest-8(14)-en-15-one (I) from 7-dehydrocholesterol is described. This synthesis, which is efficient and suitable for kilogram scale work, was carried out in a 33% overall average yield (39% overall best yield). A major byproduct of the hydrolysis of 3 beta-benzoyloxy-14 alpha,15 alpha-epoxy-5 alpha-cholest-7-ene to I was found to be the ring C aromatic sterol 12-methyl-18-nor-5 alpha-cholesta-8,11,13-trien-3 beta-ol. Several other intermediates and byproducts of these reactions were also identified. All new sterols were characterized by 1H- and 13C-NMR.