Two new sesquiterpene lactones from Ixeris chinensis

Phytochemical investigation of Ixeris chinensis NAKAI (Asteraceae) has resulted in the isolation of a new guaianolide-type sesquiterpene lactone, ixerochinolide (1) as well as the related glucoside, ixerochinoside (2). In addition, the known guaianolides, 8beta-hydroxy-3-oxo-guaia-4(15),10(14),11(13)-trien-1alpha,5alpha,6beta,7alphaH-12,6-olide (8beta-hydroxydehydrozaluzanin), 8beta,15-dihydroxy-2-oxo-guaia-1(10),3,11(13)-trien-5alpha,6beta,7alphaH-12,6-olide (lactucin), 3beta,8alpha,10alpha-trihydroxy-guaia-4(15),11(13)-dien-1alpha,5alpha,6beta,7alphaH-12,6-olide (10alpha-hydroxy-10,14-dihydro-desacylcynaropicrin) and 3beta-D-glucopyranosyloxy-8beta-(p-hydroxyphenylacetyloxy)-guaia-4(15),10(14),11(13)-trien-1alpha,5alpha,6beta,7alphaH-12,6-olide (8-epicrepioside) were identified. The structures were determined on the basis of spectral analyses, especially 1- and 2D NMR. Compound 1 exhibited significant cytotoxicity against human PC-3 tumor cells.     

Six new ursane- and oleanane-type triterpenes from the aerial roots of Ficus microcarpa

Four new ursane-type triterpenes, 3beta-acetoxy-11alpha-methoxy-12-ursene (1), 3beta-acetoxy-11alpha-ethoxy-12-ursene (2), 3beta-acetoxy-11alpha-hydroperoxy-12-ursene (3), 3beta-hydroxy-11alpha-hydroperoxy-12-ursene (4), and two new oleanane-type triterpenes, 3beta-acetoxy-11alpha-ethoxy-12-oleanene (5), 3beta-acetoxy-111alpha-hydroperoxy-12-oleanene (6), together with 3beta-acetoxy-11alpha-hydroxy-12-ursene (7), 3beta,11alpha-diacetoxy-12-ursene (8), 3beta-acetoxy-11alpha-hydroxy-12-oleanene (9), were isolated from the aerial roots of Ficus microcarpa L. f. Their structures were elucidated by spectroscopic and chemical methods.     

Structural determination of three new eudesmanolides from Inula helenium

Ten sesquiterpenens were isolated from Inula helenium. Among them, three eudesmanolides: 15-hydroxy-11betaH-eudesm-4-en-8beta,12-olide (1), 3alpha-hydroxy-11betaH-eudesm-5-en-8beta,12-olide (2) and 2beta, 11alpha-dihydroxy-eudesm-5-en-8beta,12-olide (3) are new compounds. Their chemical structures were determined by spectral methods including 2D NMR.     

Sesquiterpene lactones from Crepis cameroonica (Asteraceae)

In addition to one known compound, 3beta,8alpha-dihydroxyguaian-4(15),10(14),11(13)-trien-6,12 olide (8-desacylcynaropicrin) (3), two new sesquiterpene lactones have been isolated from the aerial parts of Crepis cameroonica. By means of spectroscopic analysis, the structures and relative configurations of the new compounds were established as 3beta,9beta-dihydroxyguaian-4(15),10(14),11(13)-trien-6,12 olide (1) and 8alpha-hydroxy-4alpha(13),11beta(15)-tetrahydrozaluzanin C (2). The in vitro antimicrobial spectrum of pure compounds and crude extracts are also reported.     

Epoxidation and reduction of DHEA, 1,4,6-androstatrien-3-one and 4,6-androstadien-3beta,17beta-diol

Dehydroepiandrosterone (DHEA) reacted with m-chloroperoxybenzoic acid(m-CPBA) to form 3beta-hydroxy-5alpha,6alpha-epoxyandrostan-17-one (1), but it did not react with 30% H2O2. 1,4,6-Androstatrien-3,17-dione (2) was obtained from DHEA and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone in dioxane. Compound 2 was reacted with 30%H2O2 and 5% NaOH in methanol to give 1alpha,2alpha-epoxy-4,6-androstadien-3,17-dione (3),which was stereoselectively reduced with NaBH4 to form 1alpha,2alpha-epoxy-4,6-androstadien-3beta,17beta-diol (7) and reacted with Li metal in absolute ethanol-tetrahydrofuran mixture to give 2-ethoxy-1,4,6-androstatrien-3,17-dione (8). Compound 2 was also epoxidized with m-CPBA in dichloromethane to afford 6alpha,7alpha-epoxy-1,4-androstadien-3,17-dione (4),which was reacted with NaBH4 to synthesize 6alpha,7alpha-epoxy-4-androsten-3beta,17beta-diol (9).Compound 4 was reduced with Li metal in absolute ethanol-tetrahydrofuran mixture to form 7beta-ethoxy-6alpha-hydroxy-1,4-androstadien-3,17-dione (10). Compound 2 was reduced with NaBH4 in absolute ethanol to form 4,6-androstadien-3beta,17beta-diol (5), which was reacted with 30% H2O2 to give the original compound, but which reacted with m-CPBAto give 4beta,5beta-epoxy-6-androsten-3beta,17beta-diol (6).     

New triterpenoids isolated from the root bark of Ulmus pumila L

Three new triterpenoids, 1-3, were isolated from the dried root bark of Ulmus pumila. Along with the three new compounds, six known triterpenoids, epifriedelanol (4), friedelin (5), oleanolic acid (6), maslinic acid (7), camaldulenic acid (8), and arjunolic acid (9) were also isolated. The structures of new compounds were established as ulmudiol (bauer-7-ene-1alpha,3beta-diol, 1), dehydroulmudiol [bauer-7,9(11)-diene-1alpha,3beta-diol, 2], and ulmuestone [3alpha-hydroxy-11alpha-(4'-hydroxy-3'-methoxy)benzoyloxybauer-1-one, 3], on the basis of extensive 1D and 2D NMR spectroscopic data interpretation. In addition, the cytotoxic activities of these compounds are also reported.     

Structural determination of a new 2(3 --> 20)abeotaxane with an unusual 13beta-substitution pattern and a new 6/8/6-ring taxane from Taxus cuspidata

A new 2(3 --> 20)abeotaxane with an unusual 13beta-substitution pattern and a new 6/8/6-ring taxane were isolated from the methanol extract of the needles of Taxus cuspidata. The structures were established as 2alpha,7beta-diacetoxy-5alpha,10beta,13beta-trihydroxy-2(3 --> 20)abeotaxa-4(20), 11-dien-9-one (1) and 2alpha,5alpha,7beta,9alpha,13alpha-pentahydroxy-10beta-acetoxytaxa-4(20),11-diene (2) on the basis of 1D and 2D NMR spectral data and high-resolution FAB-MS analyses.     

Cytotoxic sterols from marine-derived fungus Pennicillium sp

A new sterol, ergosta-8(14), 22-diene-3,5,6,7-tetraol(3beta, 5alpha, 6beta, 7alpha, 22E) (1), together with four known sterols ergosta-8(9), 22-diene-3,5,6,7-tetraol (3beta, 5alpha, 6beta, 7alpha, 22E) (2), 5alpha,8alpha-epidioxy-24(S)-methylcholesta-6,22-diene-3beta-ol (3), 5alpha,8alpha-epidioxy-24(S)-methylcholesta-6,9(11), 22-triene-3beta-ol (4), 3beta,5alpha,9alpha-trihydroxyergosta-7,22-diene-6-one (5) was isolated from marine fungus Pennicillium sp. Their structures were determined based on chemical analysis and spectral methods (IR, 1D and 2D NMR, HR-FAB-MS). Compounds 1-5 were evaluated for cytotoxicity against human liver cancer cell (Hep G), and most of them exhibited potent activity. Compound 1 display the highest potency with IC50 values 10.4 microg mL-1.     

A new pyrrolidine derivative and steroids from an algicolous Gibberella zeae strain

A new pyrrolidine derivative, 3-hydroxy-5-(hydroxymethyl)-4-(4'-hydroxyphenoxy)pyrrolidin-2-one (1), and eight known steroids, (22E,24R)-7beta,8beta-epoxy-3beta,5alpha,9alpha-trihydroxyergosta-22-en-6-one (2, a reassigned structure of (22E,24R)-5alpha,6alpha-epoxy-3beta,8beta,14alpha-trihydroxyergosta-22-en-7-one), (22E,24R)-3beta,5alpha,9alpha-trihydroxyergosta-7,22-dien-6-one (3), (22E,24R)-3beta,5alpha-dihydroxyergosta-7,22-dien-6-one (4), (22E,24R)-ergosta-7,22-dien-3beta/,5alpha,6beta-triol (5), (22E,24R)-ergosta-5,22-dien-3beta-ol (6), (22E,24R)-5alpha,8alpha-epidioxyergosta-6,22-dien-3beta-ol (7), (22E,24R)-5alpha,8alpha-epidioxyergosta-6,9(11),22-trien-3beta-ol (8), and (22E,24R)-1(10 --> 6)-abeo-ergosta-5,7,9,22-tetraen-3alpha-ol (9), were isolated from the cultures of Gibberella zeae, an endophytic fungus isolated from the marine green alga Codium fragile. Their structures and relative stereochemistry were elucidated by 1D, 2D NMR and mass spectroscopic techniques. Compound 1 showed cytotoxicity against A-549 and BEL-7402 cell lines.     

Three new taxoids from the leaves of the Japanese yew, Taxus cuspidata

Three new taxane diterpenoids were isolated from the leaves of the Japanese yew, Taxus cuspidta. Their structures were established as 5 alpha,13 alpha-diacetoxy-taxa-4(20),11-diene-9 alpha,10 beta-diol (1), 7 beta,13 alpha-diacetoxy-5 alpha-cinnamyloxy-2(3-->20)-abeo-taxa-4(20),11-diene-2 alpha,10 beta-diol (2), and 2 alpha,10 beta,13 alpha-triacetoxy-taxa-4(20),11-diene-5 alpha,7 beta,9 alpha-triol (3) respectively on the basis of 1D and 2D NMR data.     

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.     

Microbial transformation of dehydroepiandrosterone

Transformation of dehydroepiandrosterone (DHEA) (1) was carried out by a plant pathogen Rhizopus stolonifer, which resulted in the production of seven metabolites. These metabolites were identified as 3beta,17beta-dihydroxyanandrost-5-ene (2), 3beta,17beta-dihydroxyandrost-4ene (3), 17beta-hydroxyandrost-4-ene-3-one (4), 3beta,11-dihydroxyandrost-4-ene-17-one (5), 3beta,7alpha-dihydroandrost-5-ene-17-one (6), 3A,7alpha,17beta-trihydroxyandrost-5-ene (7) and 11beta-hydroxyandrost-4,6-diene-3,17-dione (8). The structures of the transformed products were determined by the spectroscopic techniques.     

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.     

Diterpenes from Sideritis trojana

Six known ent-kaurene, a new ent-kaurane and a new pimarane diterpenes were isolated from Sideritis trojana. The structures of new compounds were determined as ent-7alpha-15beta,16beta-epoxykaurane (1), and ent-2alpha-hydroxy-8(14),15-pimaradiene (2) along with the known compounds siderol (3), sideridiol (4), 7-epicandicandiol (5), isocandol B (6), candol A acetate (7) ent-7alpha-acetoxykaur-15-ene (8) by IR, 1D and 2D NMR techniques and HRMS.     

A cytotoxic and apoptosis-inducing sesquiterpenoid isolated from the aerial parts of Artemisia princeps PAMPANINI (Sajabalssuk)

Repeated silica gel and octadecyl silica gel (ODS) column chromatography of the aerial parts of Artemisia princeps PAMPANINI (Sajabalssuk) led to the isolation of a new sesquiterpenoid, 3-((S)-2-methylbutyryloxy)-costu-1(10),4(5)-dien-12,6 alpha-olide (2), along with two previously reported sesquiterpenoids: 8 alpha-angeloyloxy-3beta,4 beta-epoxy-6 beta H,7 alpha H,8 beta H-guaia-1(10),11(13)-dien-12,6 alpha-olide (1, carlaolide B) and 3beta,4 beta-epoxy-8 alpha-isobutyryloxy-6 beta H,7 alpha H,8 beta H-guaia-1(10),11(13)-dien-12,6 alpha-olide (3, carlaolide A). The structure of compound 2 was elucidated by spectroscopic data analysis, including one dimensional (1D) and two dimensional (2D) nuclear magnetic resonance (NMR) experiments. Of the isolates, compound 2 exhibited potent cytotoxicity against human cervix adenocarcinoma cells and induced apoptosis.     

Four novel metabolites from microbial transformation of curcumol by Cunninghamella blakesleana

Further study on the microbial transformation of curcumol (1) by Cunninghamella blakesleana (AS3.970) led to the isolation of four novel metabolites. Their structures were elucidated as 3beta-hydroxy curcumol (2), 12-hydroxy curcumol (3), 1alpha-hydroxy-10beta,14-epoxy curcumol (4) and (2S,4S,5S,7S)-10-hydroxymethyl-7-isopropyl-2-methoxy-4-methyl-1-oxaspiro[4,6]undec-10-en-8-one (5) on the basis of spectral methods. All of them were characterized as new compounds.     

A new geranylated aromatic compound from the mushroom Hericium erinaceum

A new geranylated aromatic compound, 5-[(2'E)-3',7'-dimethyl-2',6'-octadienyl]-4-hydroxy-6-methoxy-1-isoindolinone (1), was isolated from the fruiting bodies of the mushroom Hericium erinaceum (Bull.: Fr.) Pers. (Hericiaceae) together with three known sterols, 5alpha,6alpha-epoxy-(22E)-ergosta-8(14),22-diene-3beta,7alpha-diol (2), (22E)-ergosta-7,9(11),22-triene-3beta,5alpha,6beta-triol (3) and (22E)-ergosta-7,22-diene-3beta,5alpha,6alpha,9alpha-tetrol (4). The structure of the new compound was elucidated on the basis of spectral data.     

Two novel steroids from Euphorbia officinarum latex

Two novel steroids, 3beta,7alpha-dihydroxy-4alpha,14alpha-dimethyl-5alpha-cholest-8-en-11-one (2) and 3beta,7beta-dihydroxy-4alpha,14alpha-dimethyl-5alpha-cholest-8-en-11-one (3) were isolated from the latex of Euphorbia officinarum. Their structures were established on the basis of NMR and MS studies.     

A New Jatrophane Diterpenoid Ester from Euphorbia turczaninowii

A new jatrophane diterpenoid ester （2S, 3S, 4R, 5R, 7S, 8R, 13R, 15R） - 3, 5, 7, 8, 15- pentaacetoxy-9, 14-dioxojatropha-6（17）, 11E-diene was isolated from the whole plant of Euphorbia turczaninowii Kar. ＆ Kit.. Its structure was characterized by spectral analysis and confurmed by X-ray crystallographic analysis.     

Five new nortropane alkaloids and six new amino acids from the fruit of Morus alba LINNE growing in Turkey

Investigation of the constituents of the fruits of Morus alba LINNE (Moraceae) afforded five new nortropane alkaloids (1-5) along with nor-psi-tropine (6) and six new amino acids, morusimic acids A-F (7-12). The structures of the new compounds were determined to be 2alpha,3beta-dihydroxynortropane (1), 2beta,3beta-dihydroxynortropane (2), 2alpha,3beta,6exo-trihydroxynortropane (3), 2alpha,3beta,4alpha-rihydroxynortropane (4), 3beta,6exo-dihydroxynortropane (5), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (7), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid (8), (3R)-3-hydroxy-12-1(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (9), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid (10), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-hydroxymethyl-piperidin-1-yl]-dodecanoic acid-3-O-beta-D-glucopyranoside (11), and (3R)-3-hydroxy-12-[(1R,4S,5S)-4-hydroxy-5-methyl-piperidin-1-yl]-dodecanoic acid (12) on the basis of spectral and chemical data.