New cyclopropyl-triterpenoids from the aerial roots of Ficus microcarpa

Four new cyclopropyl-triterpenes, 27-nor-3beta-hydroxy-25-oxocycloartane (1), (22E)-25,26,27-trinor-3beta-hydroxycycloart-22-en-24-al (2), 3beta-acetoxy-15alpha-hydroxy-13,27-cyclours-11-ene (3), 3beta-acetoxy-12alpha-formyloxy-13,27-cycloursan-11alpha-ol (4), together with (23E)-27-nor-3beta-hydroxycycloart-23-en-25-one (5) were isolated from the aerial roots of Ficus microcarpa. Compounds 3 and 4 are rare 13,27-cycloursane-type triterpenes. Their structures were elucidated by spectroscopic and chemical methods.     

Studies on the constituents of Cimicifuga species. XXVIII. Cycloart-7-enol glycosides from the underground parts of Cimicifuga simplex Wormsk

Four new cycloart-7-ene triterpenol arabinosides, bugbanosides C-F, were isolated from the underground parts of Cimicifuga simplex Wormsk. (Ranunculaceae). The structures were elucidated as 12beta-acetoxy-3beta,15alpha,-24R,25-tetrahydroxy-16,23-dione-cycloart-7-ene 3-O-alpha-arabinopyranoside, 12beta-acetoxy-24R,25-epoxy-3beta,15alpha-dihydroxy-16,23-dione-cycloart-7-ene 3-O-alpha-L-arabinopyranoside, 12beta-acetoxy-24R,25-epoxy-3beta-hydroxy-16,23-dione-cycloart-7-ene 3-O-alpha-L-arabinopyranoside, and 16,23R:16,24S-diepoxy-3beta,12beta,15alpha,25-tetrahydroxy-cycloart-7-ene 3-O-alpha-L-arabinopyranoside on the basis of spectral and chemical evidence. The circular dichroism (CD) of bugbanosides C-F showed strong negative maxima at 214-217 nm due to a cycloart-7-ene system, as well as other cycloart-7-ene triterpenes. The CD data showed to be useful in determining basic skeletons, including absolute stereostructures of cycloart-7-ene triterpenes.     

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.     

Two new polyporusterones isolated from the sclerotia of Polyporus umbellatus

In the course of searching for marker components, two new polyporusterones were isolated from the sclerotia of Polyporus umbellatus, together with another three known analogs. The structures of the new ones were elucidated as (20S,22R,24R)-16,22-epoxy-3beta,14alpha,23beta,25-tetrahydroxyergost-7-en-6-one (1) and (23R,24R,25R)-23,26-epoxy-3beta,14alpha,21alpha,22alpha-tetrahydroxyergost-7-en-6-one (2) by chemical and spectroscopic means, including HR-FAB-MS, 1D- and 2D-NMR.     

Complete assignments of 1H and 13C NMR spectral data for three polyhydroxylated 12-ursen-type triterpenoids from Dischidia esquirolii

The complete assignments of all the (1)H and (13)C NMR signals of three polyhydroxylated 12-ursen-type triterpenes, 6beta,19alpha,22alpha-trihydroxyurs-12-en-3-oxo-28-oic acid (1), 3beta,6alpha,19alpha,23-tetrahydroxyurs-12-en-28- oic acid (2) and 3beta,6beta,19alpha,23-tetrahydroxyurs-12-en-28-oic acid (3), were carried out by means of homo- and hetero-nuclear two-dimensional NMR experiments. Compounds 1-3 were isolated from the aerial parts of Dischidia esquirolii. Of them, 1 and 2 were identified as new polyhydroxylated ursolic acid derivatives. Compound 2 is the C-6 hydroxyl epimer of 3, which was isolated first from Adina rubella, and its structure is revised in this paper.     

Antiproliferative constituents from Umbelliferae plants VI. New ursane-type saikosaponin analogs from the fruits of Bupleurum rotundifolium

The MeOH extract of the fruits of Bupleurum rotundifolium showed inhibitory activity against human gastric adenocarcinoma (MK-1) cell growth (GI(50): 6.25 microg/ml). From this extract, 10 new ursane-type triterpene glycosides viz. three 3-O-triosides (called rotundifoliosides A, I, and J) of 13beta,28-epoxy-3beta,16alpha-dihydroxyurs-11-ene, two (G and H) of 13beta,28-epoxy-3beta,16alpha,23-trihydroxyurs-11-ene, two (E and F) of 13beta,28-epoxy-3beta,16alpha,21beta-trihydroxyurs-11-ene, two (B and C) of 3beta,11alpha,16alpha,28-tetrahydroxyurs-12-ene, and one (D) of 3beta,11alpha,28-trihydroxy-15alpha,16alpha-epoxyurs-12-ene were isolated in addition to 16 new oleanane-type triterpene glycosides (rotundiosides J-Y), echinocystic acid 3-O-sulfate and 3 known oleanane-type triterpene glycosides (rotundiosides A, F and G). The isolation, structures and antiproliferative activity of the new ursane-type triterpene glycosides against MK-1, human uterus carcinoma (HeLa), and murine melanoma (B16F10) cell lines are described with some comments on the structural requirements for their activity.     

Three new pentacyclic triterpenes and some flavonoids from the fruits of an Indian Ayurvedic plant Dendrophthoe falcata and their estrogen receptor binding activity

Extensive chromatographic screening of extracts of the fruits of the Indian Ayurvedic plant, Dendrophthoe falcata, resulted in the isolation of three new triterpenes, 3beta-acetoxy-1beta-(2-hydroxy-2-propoxy)-11alpha-hydroxy-olean-12-ene (1), 3beta-acetoxy-11alpha-ethoxy-1beta-hydroxy-olean-12-ene (2) and 3beta-acetoxy-1beta-hydroxy-11alpha-methoxy-olean-12-ene (3) along with nine known compounds, 3beta-acetoxy-1beta,11alpha-dihydroxy-olean-12-ene (4), 3beta-acetoxy-1beta,11alpha-dihydroxy-urs-12-ene (5), 3beta-acetoxy-urs-12-ene-11-one (6), 3beta-acetoxy-lup-20(29)-ene (7), 30-nor-lup-3beta-acetoxy-20-one (8), (20S)-3beta-acetoxy-lupan-29-oic acid (9), kaempferol-3-O-alpha-L-rhamnopyranoside (10), quercetin-3-O-alpha-L-rhamnopyranoside (11), and gallic acid (12). The structures of these compounds were determined using 1D and 2D NMR and high resolution electrospray mass spectrometry. These compounds were assayed for binding to estrogen receptors-alpha and beta and kaempferol-3-O-alpha-L-rhamnopyranoside (10) was found to be a ligand for both receptors with greater affinity for beta. The triterpenes (1-9) are reported for the first time in the genus Dendrophthoe and assumes taxonomic significance.     

New triterpenoids from Corchorus trilocularis

Two new tetracyclic triterpenoid trilocularol A and trilocularol A 3-glucoside and one pentacyclic triterpenoid tirlocularoside A were isolated from Corchorus trilocularis L., their structure were elucidated as 3beta,6alpha,16alpha,20(S),27-pentahydroxydammar-24(Z)-ene (1), 3beta-D-glucopyranosyloxy-6alpha,16alpha,20(S),27-tetrahydroxydammar-24(Z)-ene (2) and 2alpha,3beta,19alpha,30-tetrahydroxyurs-12-en-24,28-dioic acid 28-O-beta-D-glucopyranosyl ester (3). respectively, on the basis of detailed spectroscopic studies.     

Dammarane triterpenes of Commiphora confusa resin

Fractionation of a steam distilled residue of Commiphora confusa resin has yielded four novel dammarane triterpenes characterised as (20S)-3beta-acetoxy-12beta,16beta-trihydroxydammar-24-ene, (20S)-12beta,16beta-trihydroxydammar-24-ene-3beta-O-beta-glucopyranoside, (20S)-3beta-acetoxy-12beta,16beta,25-tetrahydroxydammar-23-ene, and (20S)-3beta,12beta,16beta,25-pentahydroxydammar-23-ene. The known compounds beta-amyrin, 3beta-amyrinacetate, 2-methoxyfuranodienone, 2-acetoxyfuranodienone, (20R)-3beta-acetoxy-16beta-dihydroxydammar-24-ene, (20R)-3beta,16beta-trihydroxydammar-24-ene, 3beta-acetoxy-16beta-hydroxydammar-24-ene, 3beta-hydroxydammar-24-ene, 3beta-acetoxydammar-24-ene, and beta-sistosterol were also isolated from the same extract. The structures of the compounds were determined using spectroscopic, physical, and chemical methods.     

New triterpenoid saponins from Stelmatocrypton khasianum

Four new triterpenoid saponins, designated as stelmatotriterpenosides E-H (1-4), together with three known compounds, asterbatanoside B (5), 2alpha,3beta,19alpha,23-tetrahydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (6) and 2alpha,3beta,19alpha,23-tetrahydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (7), were isolated from the stems of Stelmatocrypton khasianum. On the basis of chemical and spectral evidence, the structures of 1-4 were established as 2alpha,3beta,23-trihydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (1), 2alpha,3beta,23-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (2), 2alpha,3beta,19alpha-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl ester (3), and 2beta,3beta,19alpha-trihydroxy-urs-12-en-24,28-dioic acid-24-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl diester (4).     

Further bisabolenes and dammarane triterpenes of Commiphora kua resin

From the resins of Commiphora kua a novel bisabolene; 6-hydroxy-2-methyl-5-(5'-hydroxy-1'(R),5'-dimethylhex-3'-enyl)-phenol together with two new dammarane triterpenes, 3beta,16beta,20(S),25-tetrahydroxydammar-23-ene and 3beta-acetoxy-16beta,20(S),25-trihydroxydammar-23-ene, have been isolated. In addition, being reported are known compounds identified as 2-methyl-5-(4'(S)-hydroxy-1'(R),5'-dimethylhex-5'-enyl)-phenol, 2-acetoxyfuranodienone, 2-methoxyfuranodienone, 3beta,16beta,20(R)-trihydroxydammar-24-ene and its acetate derivative, 3beta-acetoxy-16beta,20(R)-dihydroxydammar-24-ene, and beta-amyrin and its acetate derivative. 2-Methyl-5-(4'(S)-hydroxy-1'(R),5'-dimethylhex-5'-enyl)-phenol displayed fungicidal activity against Cladosporium cucumernum on TLC assay.     

Six new withanolide-type steroids from the leaves of Solanum cilistum

Six new withanolide-type steroids, designated cilistols v, t, i, j, y and w (1-6, respectively), were obtained from the leaves of Solanum cilistum. Their respective structures were characterized by spectroscopic means as follows: Cilistol v (1) was (22R,24Z)-1alpha,3beta,22,26-tetrahydroxyergost-5,24-diene 26-O-beta-D-glucopyranoside, which is regarded as the precursor of other withanolide-type steroids included in this title plant. Cilistol t (2) was (22R,24S,25R,26S)-24,25;22,26-diepoxy-1alpha,3beta,26-trihydroxyergost-5-ene 26-O-beta-D-glucopyranoside, and cilistols j (3) and i (4) corresponded to the substances probably formed by the cleavage of the epoxy ring at C-24 and 25 of 2. Cilistol y (5) was 3-O-sulphonyl (22R,24S,25R,26R)-1-oxo-24,25; 22,26-diepoxy-3beta,17alpha,26-trihydroxyergost-5-ene 26-O-beta-D-glucopyranoside, and cilistol w (6) corresponded to the substance obtained by the fission of the epoxy ring at C-24 and 25 of 5. The occurrence of these withanolide type steroids from Solanum genera is rare and worthy of note.     

Six new dammarane-type triterpene saponins from the leaves of Panax ginseng

Six new minor saponins, together with known ginsenosides, were isolated from the leaves of Panax ginseng. The new saponins were named as ginsenoside-Rh5, -Rh6, -Rh7 -Rh8, -Rh9 and -Rg7, and their structures were elucidated on the basis of chemical and physicochemical evidence to be as follows: ginsenoside-Rh5: 3beta,6alpha,12beta,24zeta-tetrahydroxy-dammar-20(22),25-diene 6-O-beta-D-glucopyranoside (1), -Rh6: 3beta,6alpha12beta,20(S)-tetrahydroxy-25-hydroperoxy-dammar-23-ene 20-O-beta-D-glucopyranoside (2), -Rh7: 3beta,7beta,12beta,20(S)-tetrahydroxy-dammar-5,24-diene 20-O-beta-D-glucopyranoside (3), -Rh8: 3beta,6alpha,20(S)-trihydroxy-dammar-24-ene-12-one 20-O-beta-D-glucopyranoside (4), -Rh9: 3beta,6alpha,20(S)-trihydroxy-12beta,23-epoxy-dammar-24-ene 20-O-beta-D-glucopyranoside (5) and -Rg7: 3-O-beta-D-glucopyranosyl 3beta,12beta,20(S),24(R)-tetrahydroxy-dammar-25-ene 20-O-beta-D-glucopyranoside (6).     

Five new triterpenoid saponins from the roots of Platycodon grandiflorum

Five new triterpenoid saponins, platycoside H [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23-tetrahydroxyolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], platycoside I [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23-tetrahydroxyolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], platycoside J [3-O-beta-D-glucopyranosyl-2beta,3beta,16alpha,23-tetrahydroxyolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], platycoside K [3-O-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23,24-pentahydroxyolean-12-en-28-oic acid], and platycoside L [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23,24-pentahydroxyolean-12-en-28 oic acid], and three known triterpenoid saponins, platycoside F, platycoside B, and platycoside C, were isolated from the roots of Platycodon grandiflorum A. DC. Their chemical structures were elucidated on the basis of their spectral data and chemical evidence.     

Four new cycloartane glycosides from Thalictrum fortunei

Four new cycloartane glycosides were isolated from the aerial parts of Thalictrum fortunei (Ranunculaceae). The chemical structures of these new glycosides were elucidated as 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-beta-D-glucopyranoside, 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-beta-D-quinovopyranosyl-(1-->6)-beta-D-glucopyranoside, 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-beta-D-xylopyranosyl-(1-->6)-beta-D-glucopyranoside, and 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-fucopyranosyl (22S,24Z)-cycloart-24-en-3beta,22,26-triol 26-O-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranoside by extensive NMR methods, HR-ESI-MS, and hydrolysis. This is the first report of (22S,24Z)-3beta,22,26-trihydroxycycloartan-24-ene (thelictogenin A, 5) being glycosylated at C-26.     

New polyhydroxylated furostanol saponins with inhibitory action against NO production from Tupistra chinensis rhizomes

Two furostanol saponins were obtained from the rhizomes of Tupistra chinensis Bak. Their structures were determined as 5beta-furost-delta(25(27))-en-1beta,2beta,3beta,4beta,5beta,7alpha,22xi,26-octaol-6-one-26-O-beta-D-glucopyranoside (1) and 5beta-furost-delta(25(27))-en-1beta,2beta,3beta,4beta,5beta,6beta,7alpha,22xi,26-nonaol-26-O-beta-D-glucopyranoside (2), on the basis of chemical and spectroscopic evidence. Both compounds displayed marked inhibitory action against NO production in rat abdomen macrophages induced by lipopolysaccharide (LPS) at 40 microg/mL.     

19-nor-11-Oxooleanan-12-ene and 18,19-seco-19-oxours-11,13(18)-diene triterpenes from Diospyros decandra bark

Four new triterpenes, 2α,3β-dihydroxy-19-nor-11-oxo-20-dimethylurs-12-en-24,28-dioic acid (equivalent to 2α,3β-dihydroxy-19-nor-11-oxoolean-12-en-24,28-dioic acid), 2α,3β-dihydroxy-18,19-seco-19-oxours-11,13(18)-dien-24,28-dioic acid, 2α,3β,19α-trihydroxy-11-oxours-12-en-24,28-dioic acid and 2α,3β,19α-trihydroxy-28-1′-β-d-[glucopyranosyl-(1″→6′)-glucopyranosyl]-urs-12-en-24,28-dioic acid were isolated from the methanol extract of the bark of Diospyros decandra as their acetate-methyl ester derivatives. The first two compounds represent the biosynthetic transformation products of 2α,3β,19-trihydroxyurs-24,28-dioic acid via oxidative rearrangement of ring E.     

Two new bioactive oleanane triterpene glycosides from Terminalia arjuna

Two new oleanane-type triterpene glycosides designated as Termiarjunoside I and Termiarjunoside II were isolated from stem bark of Terminalia arjuna (Combretaceae) and characterized as olean-1alpha,3beta,9alpha,22alpha-tetraol-12-en-28-oic acid-3beta-D-glucopyranoside (1) and olean-3alpha,5alpha,25-triol-12-en-23,28-dioic acid-3alpha-D-glucopyranoside (2) based on chemical and spectral data evidences. Both compounds 1 and 2 potently suppressed the release of nitric oxide and superoxide from macrophages and also inhibited aggregation of platelets.     

Ginsenoside Rg8, a new dammarane-type triterpenoid saponin from roots of Panax quinquefolium

A new dammarane-type triterpenoid saponin, ginsenoside Rg(8) (1), was isolated from the roots of Panax quinquefolium, along with five known saponins, (20E)-ginsenoside F(4) (2), ginsenosides Rh(1) (3), Rg(2) (4), F(1) (5), and (20R)-ginsenoside Rh(1) (6). The structure of ginsenoside Rg(8) (1) was determined to be (3beta,6alpha,12beta,20E)-24,25-epoxy-3,12,23-trihydroxydammar-20(22)-en-6-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranoside by various spectroscopic analyses. Among the known saponins, (20E)-ginsenoside F(4) (2) and ginsenoside F(1) (5) were first reported from the title plant.     

Synthesis of deuterium-labeled 16 alpha,19-dihydroxy C19 steroids as internal standards for gas chromatography-mass spectrometry.

[2 beta,7,7,16 beta-2H4]16 alpha,19-Dihydroxyandrost-4-ene-3,17-dione (14) and [7,7,16 beta-2H3]3 beta,16 alpha,19-trihydroxyandrost-5-en-17-one (16), with high isotopic purity, respectively, were synthesized from unlabeled 3 beta-(tert-butyldimethylsiloxy)-androst-5-ene-17 beta-yl acetate (1). The deuterium introduction at C-7 was carried out by reductive deoxygenation of the 7-keto compound 3 with dichloroaluminum deuteride and that at C-2 beta and/or C-16 beta by controlled alkaline hydrolysis of 16-bromo-17-ketone 11 or 12 with NaOD in D2O and pyridine. [7,7-2H2]3 beta-Hydroxyandrost-5-en-17-one (6), obtained from compound 1 by a five-step sequence, was converted to compound 14 or 16 by an eight-step or seven-step sequence, respectively. The labeled steroids 14 and 16 are useful as internal standards for gas chromatography-mass spectrometry analysis of the endogenous levels.