Labdane-type diterpenoids from the wood of Cunninghamia konishii

Five new labdane-type diterpenes, 12beta,19-dihydroxymanoyl oxide (1), 8(17),13-labdadien-12,15-olid-19-oic acid (2), 12,15-epoxy-8(17),13-labdadien-18-oic acid (3), 8alpha-hydroxy-11E,13Z-labdadien-15-al (4), and (13R)-13-hydroxy-8(17), 11E,14-labdatrien-18-oic acid (5) were isolated from the wood of Cunninghamia konishii. Their structures were elucidated by two-dimensional NMR spectroscopy.     

New lanostane-type triterpenes from Fomes officinalis

Five new lanostane-type triterpenes, named fomefficinic acid A-E (1-5), were isolated from the dried sclerotium of Fomes officinalis, respectively. Their structures were established as 24-methylene-3-oxo-lanost-8-en-21-oic acid (1), 3alpha,15alpha-dihydroxy-24-methylene-lanosta-7,9(11)-dien-21-oic acid (2), 3alpha,15alpha-dihydroxy-24-methylene-lanost-8-en-21-oic acid (3), 15alpha-hydroxy-3-oxo-24-methylenelanost-8-en-21-oic acid (4), 15alpha-acetoxy-3-oxo-24-methylenelanosta-7,9(11)-dien-21-oic acid (5), by spectral analysis and chemical methods as well as comparison with known compounds.     

Triterpenes from the spores of Ganoderma lucidum and their cytotoxicity against meth-A and LLC tumor cells

Six new highly oxygenated lanostane-type triterpenes, called ganoderic acid gamma (1), ganoderic acid delta (2), ganoderic acid epsilon (3), ganoderic acid zeta (4), ganoderic acid eta (5) and ganoderic acid theta (6), were isolated from the spores of Ganoderma lucidum, together with known ganolucidic acid D (7) and ganoderic acid C2 (8). Their structures of the new triterpenes were determined as (23S)-7beta,15alpha,23-trihydroxy-3,11-dioxolanosta-8, 24(E)-diene-26-oic acid (1), (23S)-7alpha,15alpha23-trihydroxy-3,11-dioxolanosta-8, 24(E)-diene-26-oic acid (2), (23S)-3beta3,7beta, 23-trihydroxy-11,15-dioxolanosta-8,24(E)-diene-26-oic acid (3), (23S)-3beta,23-dihydroxy-7,11,15-trioxolanosta-8, 24(E)-diene-26-oic acid (4), (23S)-3beta,7beta,12beta,23-tetrahydroxy-11,15-dioxolanos ta-8,24(E)-diene-26-oic acid (5) and (23S)-3beta,12beta23-trihydroxy-7,11,15-trioxolanosta-8,24(E )-diene-26-oic acid (6), respectively, by chemical and spectroscopic means, which included the determination of a chiral center in the side chain by a modification of Mosher's method. The cytotoxicity of the compounds isolated from the Ganoderma spores was carried out in vitro against Meth-A and LLC tumor cell lines.     

Components from the steamed leaves of Acanthopanax koreanum and their effects on PPAR activity in HepG2 cells

Three ent-kaurane diterpenes (1-3), four lupane-triterpene glycosides (4-7), and an oleanane-triterpene glycoside (8) were isolated from the ethyl acetate and water extracts of the steamed leaves of Acanthopanax koreanum using a combination of various column chromatographies. The structures of the isolates were determined by 1H-, 13C-NMR spectroscopy and mass spectrometry. To investigate the biological effects of the eight compounds (1-8) on peroxisome proliferator-activated receptor gamma (PPARgamma), luciferase reporter assays were used. Among the tested compounds, ent-kaur-16-en-19-oic acid (1), 16alpha-hydroxy-ent-kauran-19-oic acid (2), and 17-hydroxy-ent-kaur-15-en-19-oic acid (3) showed considerable effects on PPARgamma activity, compared with the positive control, troglitazone. To evaluate specificity and sensitivity of the active compounds (1-3) in the regulation of transactivation of PPARs, Gal4-PPARs-LBD luciferase reporter assays were examined. In this study, the three ent-kaurane diterpenes (1-3) were found to up-regulate PPARbeta/delta and PPARgamma activities, whereas they did not activate PPARalpha activity.     

Terpenoids from Turraeanthus species

Chemical investigation of the root bark of Turraeanthus mannii and the stem of T. longipes resulted in the isolation of two new diterpenes, 13-methyl-labda-8(17)-en-15-oic acid (1) and 13-(hydroxymethyl)-14-hydroxy-ent-labda-8(17)-en-15-oic acid (2), along with two known diterpenes, 19-hydroxy-ent-labda-8(17),13-dien-15,16-olide (3) and 19-acetoxy-ent-labda-8(17),13-dien-15,16-olide (4), and the phytosterol, stigmasterol. The structure elucidation of the new compounds has been achieved using spectroscopic techniques.     

Cytotoxic diterpenoids from Vietnamese medicinal plant Croton tonkinensis GAGNEP

Six new ent-kaurane-type diterpenoids were isolated from the leaves of the endemic Vietnamese medicinal plant Croton tonkinensis GAGNEP. (Euphorbiaceae) together with three known ent-11alpha-acetoxy-7beta,14alpha-dihydroxykaur-16-en-15-one (1), ent-kaur-16-en-15-one 18-oic acid (5) and ent-18-hydroxykaur-16-ene (7). Their structures were determined by spectroscopic analyses to be ent-7beta-acetoxy-11alpha-hydroxykaur-16-en-15-one (2), ent-18-acetoxy-11alpha-hydroxykaur-16-en-15-one (3), ent-11alpha-acetoxykaur-16-en-18-oic acid (4), ent-15alpha,18-dihydroxykaur-16-ene (6), ent-11alpha,18-diacetoxy-7beta-hydroxykaur-16-en-15-one (8), and ent-(16S)-1alpha,14alpha-diacetoxy-7beta-hydroxy-17-methoxykauran-15-one (14). ent-Kaurane-type diterpenoids from Croton tonkinensis 2-4, 6, and 9-13, were tested for toxicity in the brine shrimp lethality assay. Compounds 9, 10, and 12 demonstrated significant activity, compounds 2, 3, 6, and 11 showed weak activity, and compounds 4 and 13 were inactive.     

<Emphasis Type="Italic">seco</Emphasis>-Kaurane skeleton diterpenoids from <Emphasis Type="Italic">Croton oblongifolius</Emphasis>

A new seco-kaurane type diterpenoid, ent-3,4-seco-17-oxo-kaur-4(19),15(16)-dien-3-oic acid, and a known compound, ent-3,4-seco-kaur-4(19),16(17)-dien-3-oic acid, were isolated from the stem bark of Croton oblongifolius. The structures of these compounds were established on the basis of spectroscopic data.     

A new neuroprotective pinusolide derivative from the leaves of Biota orientalis

A new pinusolide derivative, 15-methoxypinusolidic acid (1), and another new isopimarane diterpene, ent-isopimara-15-en-3 alpha,8 alpha-diol (2) with three known diterpenes, lambertianic acid (3), isopimara-8(9),15-dien-18-oic acid (4) and isopimara-7(8),15-dien-3 beta,18-diol (5) were isolated from the 90% MeOH fraction of Biota orientalis (L.) ENDL. (Cupressaceae) leaves. Chemical structures of 1-5 were elucidated by analyses of their spectral data, including the two-dimensional (2D) NMR technique. Compound 1 showed significant protective activity against glutamate-induced neurotoxicity in primary cultures of rat cortical cells.     

Two new compounds from the leaves of Calocedrus microlepic var. formosana

Two new compounds, 15-methoxypinusolidic acid (1) and isonerylgeraniol-18-oic acid (2) together with four knowns taiwaniaflavone (3), nerylgeraniol-18-oic acid (4), 3-(3,4-dihydroxyphenyl)-1-propanol (5), and amentoflavone (6) are isolated from the leaves of Calocedrus microlepic var. formosana. Compounds 1 and 2 were elucidated as labdane diterpene and linear diterpene, respectively, through spectral studies.     

藤黄化学成分的研究

传统中药藤黄通过各种色谱方法分离纯化, 得到15个化合物, 根据其理化性质和光谱方法鉴定其结构分别为: 2α-羟基-3β-乙酰氧基白桦酯酸(1), 10α-羟基表藤黄酸(2), 藤黄酸(3), 异藤黄酸(4), gambogin (5), gambogoic acid B (6), desoxymorellin (7), isomorellin (8), gambogenic acid (9), isogambogenin (10), gambogellic acid (11), desoxygambogenin (12), morellic acid (13), isomorellic acid (14), 30-hydroxygambogic acid (15). 其中化合物1和2为新化合物.     

Lignans and Kauranes from the Stems of Annona cherimola

Four lignans and six kauranes, (+)-epi-syringaresinol ( 1 ), annocherin A (16β-hydroxy-17,19-diacetoxy-ent-kaurane) ( 2 ), (+)-syringaresinol ( 3 ), (+)-dia-syringaresinol ( 4 ), liriodendrin[(+)-syringaresinol-di-O-β-D-glucopyranoside] ( 5 ), 16α-hydro-17-acetoxy-ent-kauran-19-oic acid ( 6 ), 16β-hydro-17-hydroxy-ent-kauran-19-al ( 7 ), 16α-hydro-17-hydroxy-ent-kauran-19-al ( 8 ), 16β-hydro-17-hydroxy-ent-kauran-19-oic acid ( 9 ) and 16α-hydro-17-hydroxy-ent-kauran-19-oic acid ( 10 ) were isolated from the stems of Annona cherimola. Among them, 1 is obtained for the first time from natural sources and 2 is a new compound. The structures of these compounds were characterized and identified by spectral analyses.     

Structure elucidation and complete NMR spectral assignments of three new lanostanoid triterpenes with unprecedented Delta(16, 17) double bond from Ganoderma lucidum

Three new lanostanoid triterpenes named 3beta,7beta-di- hydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oic acid (1), 3beta,7beta-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oic acid methyl ester (2), and 12beta-acetoxy-3beta,7beta-dihydroxy-11,15,23-trioxo-lanost-8,16-dien-26-oic acid (3) were isolated from the fruit bodies of Ganoderma lucidum. They all show a Delta(16, 17) double bond unprecedented in such types of lanostanoid triterpenes possessing the side chain at C-17. The complete NMR assignments for these compounds were carried out using (1)H, (13)C, DEPT, COSY, HSQC, HMBC, and ROESY NMR experiments.     

Microbial hydroxylation and glycosidation of oleanolic acid by Circinella muscae and their anti-inflammatory activities

Biotransformation of oleanolic acid (OA) by Circinella muscae AS 3.2695 was investigated. Nine hydroxylated and glycosylated metabolites (1–9) were obtained. Their structures were elucidated as 3β,7β-dihydroxyolean-12-en-28-oic acid (1), 3β,7β,21β-trihydroxyolean-12-en-28-oic acid (2), 3β,7α,21β-trihydroxyolean-12-en- 28-oic acid (3), 3β,7β,15α-trihydroxyolean-12-en-28-oic acid (4), 7β,15α-dihydroxy- 3-oxo-olean-12-en-28-oic acid (5), 7β-hydroxy-3-oxo-olean-12-en-28-oic acid (6), oleanolic acid-28-O-β-D-glucopyranosyl ester (7), 3β,21β-dihydroxyolean-12-en-28- oic acid-28-O-β-D-glucopyranosyl ester (8), and 3β,7β,15α-trihydroxyolean-12-en- 28-oic acid-28-O-β-D-glucopyranosyl ester (9) by spectroscopic analysis. Among them, compounds 4 and 9 were new compounds. In addition, anti-inflammatory activities were assayed and evaluated for the isolated metabolites. Most of the metabolites exhibited significant inhibitory activities on lipopolysaccharides-induced NO production in RAW 264.7 cells.     

Alpha-glucosidase inhibitory constituents from Duranta repens

Three C-alkylated flavonoids 7-O-alpha-D-glucopyranosyl-3,5-dihydroxy-3'-(4"-acetoxyl-3"-methylbutyl)-6,4'-dimethoxyflavone (1), 7-O-alpha-D-glucopyranosyl-3,4'-dihydroxy-3'-(4"-acetoxyl-3"-methylbutyl)-5,6-dimethoxyflavone (2), 3,7,4'-trihydroxy-3'-(8"-acetoxy-7"-methyloctyl)-5,6-dimethoxyflavone (3) and a trans-clerodane type diterpenoid (-)-6beta-hydroxy-5beta,8beta,9beta,10alpha-cleroda-3,13-dien-16,15-olid-18-oic acid (4) are reported from Duranta repens along with (+)-hardwickiic acid (5) and (+)-3,13-clerodadien-16,15-olid-18-oic acid (6), isolated for the first time from this species. Their structures were established on the basis of the spectral methods, especially two dimensional (2D) NMR spectroscopy.     

The Constituents from the Stems of Annona cherimola

Thirty-five compounds including twenty-one alkaloids, lysicamine ( 1 ), liriodenine ( 2 ), atherospermidine ( 3 ), oxoxylopine ( 4 ), oxoanolobine ( 5 ), oxoglaucine ( 6 ), (-)-anonaine ( 7 ), (-)-asimilobine ( 8 ), (-)-xylopine ( 9 ), (-)-anolobine ( 10 ), (-)-norisocorydine ( 11 ), (+)-laurotetanine ( 12 ), (+)-isocorydine ( 13 ), (-)-N-methylasimilobine ( 14 ), (+)-N-methyllaurotetanine ( 15 ), (-)-norushinsunine ( 16 ), (-)-ushinsunine ( 17 ), (-)-N-formylanonaine ( 18 ), (+)-stepharine ( 19 ), (+)-orentaline ( 20 ), and (-)-kikemanine ( 21 ); four kauranes, ent-kaur-16-en-19-oic acid ( 22 ), 16β-hydroxy-17-acetoxy-ent-kauran-19-al ( 23 ), 17-acetoxy-16β-ent-kauran-19-oic acid ( 24 ), and 16β-hydroxy-17-acetoxy-ent-kauran-19-oic acid ( 25 ); two amides, N-trans-femloyltyramine ( 26 ), and N-trans-caffeoyltyramine ( 27 ); one purine, adenosine ( 28 ); one lactam amide, squamolone ( 29 ); and six steroids, β-sitosterol ( 30 ), stigmasterol ( 31 ), β-sitostenone ( 32 ), stigmasta-4,22-dien-3-one ( 33 ), 6β-hydroxy-β-sitosterone ( 34 ), and 6β-hydroxystigmasterone ( 35 ) are isolated from the stems of Annona cherimola. These compounds were characterized and identified by physical and spectral evidence. Among them, (-)-norisocorydine (11) was elucidated as a new enantiomer with a levorotary configuration, which is isolated for the first time.     

The Terpenoids of Maytenus boaria MOL. (Celastraceae)

The known triterpenoids β-amyrin (= olean-12-en-3β-ol; 22 ), lupeol (= lup-20(29)-en-3β-ol; 17 ), betulin (= lup-20(29)-ene-3β,28-diol; 18 ), lup-20(29)-ene-3β,30-diol ( 20 ), oleanolic acid (= 3β-hydroxyolean-12-en-28-oic acid; 21 ), and betulonic acid (= 3-oxolup-20(29)-en-28-oic acid; 19 ), together with epicatechol (= cis-2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H-1-benzopyran-3,5,7-triol; 23 ), 5′-O-methylgallocatechol (= trans-2-(3,4-dihydroxy-5-methoxyphenyl)-3,4-dihydro-2H-1-benzopyran-3,5,7-triol; 24 ), and 4-hydroxybenzaldehyde were isolated from the aerial parts of Maytenus boaria (MOL. ). Additonally, the eight 4,C⁴-dihydro-β-agarofuran sesquiterpenoids 1–8 , one of them a diol with a (4R)-configuration, and compound 9 were present in the extract. The structures of these compounds were established by spectroscopic and chemical means.     

Melampolides from the leaves of Smallanthus sonchifolius and their inhibitory activity of lps-induced nitric oxide production

Two new melampolide-type sesquiterpene lactones, 8beta-epoxyangeloyloxy-9alpha-ethoxy-14-oxo-acanthospermolide (1) and 8beta-angeloyloxy-9alpha-ethoxy-14-oxo-acanthospermolide (2), were isolated from the leaves of yacon [Smallanthus sonchifolia (POEPP. et ENDL.) H. Robinson] along with eleven known melampolides, allo-schkuhriolide (3), enhydrin (4), polymatin A (5), fluctuanin (6), 8beta-angeloyloxy-9alpha-acetoxy-14-oxo-acanthospermolide (7), 8beta-angeloyloxy-14-oxo-acanthospermolide (8), 8beta-methacryloyloxymelampolid-14-oic acid methyl ester (9), uvedalin (10), polymatin B (11), 8beta-tigloyloxymelampolid-14-oic acid methyl ester (12), and sonchifolin (13). Their structures were established on the basis of spectroscopic evidence including 1D- and 2D-NMR experiments. All isolates were evaluated for inhibition of LPS-induced nitric oxide production in murine macrophage RAW 264.7 cells.     

Fargosides A-E, triterpenoid saponins from Holboellia fargesii

Five new triterpenoid saponins, fargosides A, B, C, D, and E, were isolated from the roots of Holboellia fargesii. The structures of fargosides A-E were elucidated on the basis of chemical and physicochemical evidence and found to be 3beta,20alpha-dihydroxy-29-norolean-12-en-28-oic acid 3-O-beta-D-xylopyranosyl-(1-->2)-beta-D-glucopyranoside (1), 3beta,20alpha,24-trihydroxy-29-norolean-12-en-28-oic acid 23-O-beta-D-fucopyranosyl-(1-->2)-[alpha-L-arabinopyranosyl-(1-->3)]-beta-D-glucopyranoside (2), 3beta,23-dihydroxy-30-norolean-2,20(29)-dien-28-oic acid 3-O-alpha-L-arabinopyranosyl-(1-->2)-[beta-D-glucopyranosyluronic acid-(1-->3)]-alpha-L-arabinopyranoside (3), 3beta,23-dihydroxy-30-norolean-12,20(29)-dien-28-oic acid 3-O-methyl beta-D-glucopyranosyluronate-(1-->3)-alpha-L-arabinopyranoside (4), and 3beta,23-dihydroxy-olean-12-en-28-oic acid 3-O-methyl beta-D-glucopyranosyluronate-(1-->3)-alpha-L-arabinopyranoside (5), respectively.     

A new pentacyclic triterpenoid glucoside from Prunus serrulata var. spontanea

A new triterpenoid, 2alpha,3alpha,24-trihydroxyurs-12-en-28-oic acid-28-O-beta-D-glucopyranosyl ester (4) along with four known triterpenoids, ursolic acid (1), 2alpha-hydroxyursolic acid (2), 2alpha,3alpha,24-trihydroxyurs-12-en-28-oic acid (3), and 2alpha,3alpha,19alpha,24-tetrahydroxyurs-12-en-28-oic acid-28-O-beta-D-glucopyranosyl ester (5), were isolated from the leaves of Prunus serrulata var. spontanea (Rosaceae). Compounds 3-5 showed ONOO(-) scavenging activity, whereas compounds 1 and 2 were virtually inactive.     

New triterpene glucosides from the roots of Rosa laevigata Michx

Two new ursane-type triterpene glucosides, 2alpha,3alpha,24-trihydroxyurs-12,18-dien-28-oic acid beta-D-glucopyranosyl ester (1) and 2alpha,3alpha,23-trihydroxyurs-12,19(29)-dien-28-oic acid beta-D-glucopyranosyl ester (2), were isolated from the roots of Rosa laevigata, together with three known compounds: 2alpha,3beta,19alpha-trihydroxyurs-12-en-28-oic acid beta-Dglucopyranosyl ester (3), 2alpha,3alpha,19alpha-trihydroxyurs-12-en-28-oic acid beta-D-glucopyranosyl ester (4) and 2alpha,3beta,19alpha,23-tetrahydroxyurs-12-en-28-oic acid beta-D-glucopyranosyl ester (5). The structures of new compounds were established on the basis of detailed 1D and 2D NMR spectroscopic analyses. Compounds 2 and 5 exhibited modest in vitro antifungal activities against Candida albicans and C. krusei.