Four new eremophilendiolides from Ligularia atroviolacea

From Ligularia atroviolacea, four new eremophilendiolides, 81$-hydroxy-eremophil-3,7 （11）-dien-12,8α（14,6α）-diolide （1）, 8β-methoxy-eremophil-3,7（11）-dien-12,8α（14,6α）-diolide （2）, 8α-hydroxy-eremophil-3,7（11）-dien-12,8lβ（14,6α）-diolide （3） and eremophil-3,7（11）,8-trien-12,8 （14,6α）-diolide （4）, as well as a known diolide （5） were isolated. Their structures were elucidated on the basis of 1D and 2D NMR as well as ESI-MS spectral data.     

24-nor-Ursane type triterpenoids from the stems of Rumex japonicus

Fractionation of an EtOAc-soluble extract of the stems of Rumex japonicus led to the isolation of two new 24-norursane type triterpenoids, 2alpha,3alpha,19alpha-trihydroxy-24-norurs-4(23),12-dien-28-oic acid (1) and 4(R),23-epoxy-2alpha,3alpha,19alpha-trihydroxy-24-norurs-12-en-28-oic acid (2), along with the known compounds myrianthic acid (3), tormentic acid, and emodin. The structures of 1 and 2 were elucidated by spectroscopic methods, particularly by extensive 1D and 2D NMR studies.     

A novel bieremophilanolide from Ligularia lapathifolia

A new bieremophilanolide was isolated from the roots and rhizomes of Ligularia lapathifolia. Its structure was established as 8,8'-bi-3beta-angeloyloxy-eremophil-7(11)-en-12,8alpha(14beta,6alpha)-diolide (1) by IR, MS, 1D, and 2D NMR experiments.     

Bioactive eremophilanolides from Senecio poepigii

A new bioactive eremophilanolide, 1alpha-tigloyloxy-8betaH,10betaH-eremophil-7(11)-en-8alpha,12-olide, was isolated from Senecio poepigii and its structure was elucidated by spectral analysis. 1alpha-Angeloyloxy-8beta-methoxy-10betaH-eremophil-7(11)-en-8alpha,12-olide was also isolated. Antifungal and insect antifeedant properties were evaluated.     

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.     

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.     

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.     

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.     

8β-hydroxyeremophil-7(11)-ene-12,8α(4β,6α)-diolide分子的晶体结构

8β-hydroxyeremophil-7(11)-ene-12,8α(4β,6α)-diolide was isolated from the Ligularia intermedia and char- acterized by MS, multi NMR and X-ray single crystal diffraction. Its crystal structure was determined as in a orthorhombic type, with space group P212121 with a=6.8519(5), b=10.7191(8), c=18.5942(14) oA, V =1365.67(18) oA3, Z=4, and the calculated density is 1.354 mg/m3. F(000)=592, μ=0.101 mm-1.     

Chemical constituents from Farfugium japonicum var. formosanum

Two new eremophilenolides, 6beta,8beta,10beta-trihydroxyeremophil-7(11)-en-12,8-olide (1) and 3beta-acetoxy-8alpha-hydroxy-6beta-methoxyeremophila-7(11),9-dien-12,8-olide (2) along with twenty-nine other compounds were obtained from the methanolic extracts of the aerial parts and rhizomes of Farfugium japonicum (L.) Kitam. var. formosanum (Hayata) Kitam. (Compositae = Asteraceae). The structures of the isolated compounds were characterized and identified by spectral techniques. Compounds 5, 6, 10, 12-24, 29, and 30, were reported for the first time from this genus. Cytotoxicity and anti-inflammatory activity of the isolated compounds were evaluated. Compounds 3 and 16 possessed moderate cytotoxicity against human breast cancer cell line (MCF 7). Compounds 3, 16, 25 and 26 exhibited moderate cytotoxicity against hepatoma cells (Hep G2 and Hep 3B). With respect to the anti-inflammatory activity, compounds 15 and 16 (each 10 microg/mL) inhibited superoxide anion generation by human neutrophils in response to fMLP/CB by 92.0% and 87.3%, respectively.     

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).     

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).     

Two new eremophilanolides from Xanthium sibiricum

Two new eremophilanolides, sibiriolides A (1) and B (2), were isolated from the aerial parts of Xanthium sibiricum. The structures of the new compounds were identified as 4S,5R,7R,8R, 11R-2-oxo-1(10)-eremophilen-12,8-olide (1) and 4S,5R,7R,8R,11S-2-oxo-1(10)-eremophilen-12,8-olide (2) by HREIMS and NMR spectroscopic techniques in combination with X-ray crystallographic analysis and CD measurements.     

New Eremophilenolides from Senecio dianthus

From the aerial parts of Senecio dianthus, four new eremophilenolides ( 1 – 4 , resp.) and one new eremophilenolide alkaloid ( 5 ), of the relatively uncommon eremophilenoid‐type sesquiterpenoid lactones, were isolated together with three known sesquiterpenoid lactones, 10β‐hydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 6 ), 8β,10β‐dihydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 7 ), and 10α‐hydroxy‐1‐oxoeremophila‐7(11),8(9)‐dien‐12,8‐olide ( 8 ). On the basis of IR, MS, and NMR data, particularly 2D‐NMR analyses, the structures of the new compounds were established as: 2β‐(angeloyloxy)‐10β‐hydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 1 ), 6β‐(angeloyloxy)‐10β‐hydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 2 ), 2β‐(angeloyloxy)‐8β,10β‐dihydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 3 ), 2β‐(angeloyloxy)‐8α‐hydroxyeremophila‐7(11),9(10)‐dien‐12,8β‐olide ( 4 ), and 8β‐amino‐10β‐hydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 5 ). In addition, the relative configuration of 1 was corroborated by X‐ray diffraction analysis.     

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.     

Two new sesquiterpenes from Sarcandra glabra

Phytochemical study of the ethanol extract of Sarcandra glabra resulted in the isolation of two new sesquiterpenes, glabranols A (1) and B (2). Their structures were elucidated as 8alpha,9alpha,15-trihydroxylinden-4,7(11)-dien-12,8beta-olide (1) and 1beta,4alpha,7beta,11-tetrahydroxyeudesmane (2), by spectroscopic methods including 1D- and 2D-NMR and FTICR-MS.     

Eremophilane‐Type Sesquiterpenes from the Roots of Ligularia virgaurea

From the roots of Ligularia virgaurea, five new eremophilane‐type sesquiterpenes were isolated, including three new eremophilenolides, 6β‐(angeloyloxy)‐1α,8β,10β‐trihydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 1 ), 6β‐(angeloyloxy)‐1β,10β‐epoxy‐8β‐ethoxyeremophil‐7(11)‐en‐12,8α‐olide ( 2 ), and 1β,10β‐epoxy‐8β‐ethoxy‐6β‐[(2‐methylacryloyl)oxy]eremophil‐7(11)‐en‐12,8α‐olide ( 3 ), two new noreremophilanes, 3β‐[(2‐methylacryloyl)oxy]‐8‐oxo‐12‐noreremophil‐6‐en‐11‐one ( 9 ), and 9β‐hydroxy‐8‐oxo‐12‐noreremophil‐6‐en‐11‐one ( 10 ), and six known eremophilanes, namely 4 – 8 , and 11 . Their structures were elucidated by means of spectral methods, such as IR, HR‐ESI‐MS, and 1D‐ and 2D‐NMR, and by comparison of the spectral data with those reported for structurally related compounds.     

Acylated-oxypregnane glycosides from the roots of Araujia sericifera

Twenty-three new acylated-oxypregnane glycosides were obtained from the roots of Araujia sericifera. (Asclepiadaceae). These glycosides were confirmed to be tetraglycosides possessing twelve known compounds, 12-O-benzoyllineolon, 12-O-benzoyldeacylmetaplexigenin, ikemagenin, kidjolanin, cynanchogenin, caudatin, rostratamine, penupogenin, 12-O-benzoylisolineolon, 12-O-tigloyldecylmetaplexigenin (incisagenin), 12-O-benzoyl-20-O-acetylsarcostin, 20-O-benzoyl-12-O-(E)-cinnamoyl-3 beta,5 alpha,8 beta,12 beta,14 beta,17 beta,20-heptahydroxy-(20S)-pregn-6-ene and ten new acylated-oxypregnanes, 12-O-benzoyl-20S-hydroxyisolineolon, 12-O-tigloyllineolon, 12-O-salicyloyllineolon, 12-O-salicyloyldeacylmetplexigenin, 12-O-benzoyl-3 beta,5 alpha,8 beta,12 beta,14 beta,17 beta-hexahydroxypregn-6-en-20-one, 12-O-benzoyl-19-benzoyloxydeacylmetapleligenin, 12-O-benzoyl-19-benzoyloxy-20-O-acetylsarcostin, 12-O-benzoyl-19-salicyloyloxy-20-O-acetylsarcostin, 12-O-benzoyl-5 alpha,6 alpha-epoxydeacylmetaplexigenin, and 12-O-benzoyl-5 alpha,6 alpha-epoxylineolon as their aglycones, using both spectroscopic and chemical methods.     

New Sesquiterpenoids from Ligularia duciformis

From the whole plants of Ligularia duciformis, four new sesquiterpenoids, 3β‐acetoxy‐6β‐methoxyeremophila‐7(11),9(10)‐dien‐12,8β‐olide ( 1 ), 3β‐acetoxy‐8α‐hydroxy‐6β‐methoxyeremophila‐7(11),9(10)‐dien‐12,8β‐olide ( 2 ), 3β‐acetoxy‐10β‐hydroxy‐6β,8β‐dimethoxyeremophil‐7(11)‐en‐12,8α‐olide ( 3 ), and 3β‐acetoxy‐6β,8β,10β‐trihydroxyeremophil‐7(11)‐en‐12,8α‐olide ( 4 ) were isolated. Their structures were established by high‐field NMR techniques (¹H,¹H‐COSY, ¹³C‐APT, HMQC, HMBC, and NOESY) and HR‐ESI‐MS analysis, together with comparison of the spectroscopic data with those of structurally related compounds. In addition, the cytotoxicity of the new compounds against human hepatic cancer cells Bel‐7402, human pneumonic cancer cells A‐549, and human colonic cancer cells HCT‐8 were evaluated, the new compounds showed no cytotoxicity against the three tumor cells (all IC₅₀ values >200 μM ).     

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.