Chemical constituents of leaves and stem bark of Plumeria obtusa

The continued studies on the constituents of the fresh leaves and stem bark of Plumeria obtusa Linn. have led to the isolation and characterization of four new triterpenoids, dammara-12,20(22)Z-dien-3-one (1), dammara-12,20(22)Z-dien-3beta-ol (2), olean-12-en-3beta,27-diol (3), and 27-hydroxyolean-12-en-3-one (4) and 12 known compounds, which included eight triterpenoids; dammara-3beta,20(S),25-triol (5), urs-12-en-3beta-hydroxy-27-Z-feruloyloxy-28-oic acid (6), 3beta-hydroxyolean-12-en-28-oic acid (7), 3beta,27-dihydroxylupan-29-ene (8), 3beta-hydroxylupan-29-en-28-oic acid (9), 3beta-hydroxyursan-12-en-28-oic acid (11), 3beta-hydroxy-27-p-coumaroyloxy-olea-12-en-28-oic acid (12) and urs-12-en-3-one (15); an iridoid 1alpha-plumieride (10); a cardenolide 3alpha,14beta-dihydroxy-17beta-card-20(22)-enolide (13); a fatty acid ester methyl n-octadecanoate (14) and a steroid 3beta-hydroxy-delta5-stigmastane (16). The new constituents were characterized through spectroscopic studies including 1D (1H and 31C NMR) and 2D (COSY-45, NOESY, J-resolved, HMQC and HMBC) NMR and chemical transformations. This is the first report on the isolation of dammarane triterpenoids from P. obtusa. Compounds 5 and 6 are hitherto unreported from P. obtusa. The known compounds were identified by comparison of their spectral data with those reported in the literature.     

Triterpenoid saponins from Pteleopsis suberosa stem bark

Thirteen oleanane saponins (1-13), four of which were new compounds (1-4), were isolated from Pteleopsis suberosa Engl. et Diels stem bark (Combretaceae). Their structures were determined by 1D and 2D NMR spectroscopy and ESI-MS spectrometry. The compounds were identified as 2alpha,3beta,19alpha,23,24-pentahydroxy-11-oxo-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (1), 2alpha,3beta,19beta,23,24-pentahydroxy-11-oxo-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (2), 2alpha,3beta,19alpha,23-tetrahydroxy-11-oxo-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl ester (3), and 2alpha,3beta,6beta,19alpha,24-pentahydroxy-11-oxo-olean-12- en-28-oic acid 28-O-beta-D-glucopyranosyl ester (4). The presence of alpha,beta-unsaturated carbonyl function was not common in the oleanane class and the aglycons of these compounds were not found previously in the literature. Moreover, the isolated compounds were tested against Helicobacter pylori standard and vacA, and cagA clinical virulence genotypes. Results showed that compound 6 has an anti-H. pylori activity against three metronidazole-resistant strains (Ci 1 cagA, Ci 2 vacA, and Ci 3).     

Triterpenoids from Sanguisorba officinalis

Seven triterpenoids, i.e., 3beta-[(alpha-L-arabinopyranosyl)oxy]-19beta-hydroxyurs-12,20(30)-dien-28-oic acid (1), 3beta-[(alpha-L-arabinopyranosyl)oxy]-urs-11,13(18)-dien-28-oic acid beta-D-glucopyranosyl ester (2), 2alpha,3alpha,23-trihydroxyurs-12-en-24,28-dioic acid 28-beta-D-glucopyranosyl ester (3), 3beta-[(alpha-L-arabinopyranosyl)oxy]-urs-12,19(20)-dien-28-oic acid (4), 3beta-[(alpha-L-arabinopyranosyl)oxy]-urs-12,19(29)-dien-28-oic acid (5), 3beta-[(alpha-L-arabinopyranosyl)oxy]-19alpha-hydroxyolean-12-en-28-oic acid (6), 2alpha,3beta-dihydroxy-28-norurs-12,17,19(20),21-tetraen-23-oic cid (7), together with three known ones (8-10), were isolated from the roots of Sanguisorba officinalis. Their structures were determined by spectroscopic and chemical methods. Compounds 7 and 10 showed marginal inhibition activity against the growth of tumor cell lines.     

Triterpenoid saponins and phenylethanoid glycosides from stem of Akebia trifoliata var. australis

A detailed phytochemical study on the 70% aqueous ethanol extract of stems of Akebia trifoliata (Thunb.) Koidz. var. australis (Diels) Rehd led to isolation of five compounds, together with 12 known triterpenoid saponins and three known phenylethanoid glycosides. The structures of the five compounds were elucidated on the basis of analysis of spectroscopic data and physicochemical properties as: 2alpha, 3beta, 23-trihydroxy-30-norolean-12-en-28-oic acid beta-D-glucopyranosyl ester (1), 2alpha, 3beta, 23-trihydroxy-30-norolean-12-en-28-oic acid beta-D-xylopyranosyl-(1-->3)-O-alpha-D-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl ester (2), 2alpha, 3beta, 23-trihydroxyurs-12-en-28-oic acid beta-D-xylopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl ester (3), 3-beta-[(beta-D-glucopyranosyl-(1-->3)-O-alpha-L-arabinopyranosyl)oxy]-23-hydroxy-30-norolean-12-en-28-oic acid alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl ester (4) and 3-beta-[(alpha-L-xylopyranosyl-(1-->2)-O-alpha-L-arabinopyranosyl)oxy]-30-norolean-12-en-28-oic acid alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-O-beta-D-glucopyranosyl ester (5), named mutongsaponin A, B, C, D and E, respectively.     

Microbial metabolism of steviol and steviol-16alpha,17-epoxide

Steviol (2) possesses a blood glucose-lowering property. In order to produce potentially more- or less-active, toxic, or inactive metabolites compared to steviol (2), its microbial metabolism was investigated. Incubation of 2 with the microorganisms Bacillus megaterium ATCC 14581, Mucor recurvatus MR 36, and Aspergillus niger BCRC 32720 yielded one new metabolite, ent-7alpha,11beta,13-trihydroxykaur-16-en-19-oic acid (7), together with four known related biotransformation products, ent-7alpha,13-dihydroxykaur-16-en-19-oic acid (3), ent-13-hydroxykaur-16-en-19-alpha-d-glucopyranosyl ester (4), ent-13,16beta,17-trihydroxykauran-19-oic acid (5), and ent-13-hydroxy-7-ketokaur-16-en-19-oic acid (6). The preliminary testing of antihyperglycemic effects showed that 5 was more potent than the parent compound (2). Thus, the microbial metabolism of steviol-16alpha,17-epoxide (8) with M. recurvatus MR 36 was continued to produce higher amounts of 5 for future study of its action mechanism. Preparative-scale fermentation of 8 yielded 5, ent-11alpha,13,16alpha,17-tetrahydroxykauran-19-oic acid (10), ent-1beta,17-dihydroxy-16-ketobeyeran-19-oic acid (11), and ent-7alpha,17-dihydroxy-16-ketobeyeran-19-oic acid (13), together with three new metabolites: ent-13,16beta-dihydroxykauran-17-acetoxy-19-oic acid (9), ent-11beta,13-dihydroxy-16beta,17-epoxykauran-19-oic acid (12), and ent-11beta,13,16beta,17-tetrahydroxykauran-19-oic acid (14). The structures of the compounds were fully elucidated using 1D and 2D NMR spectroscopic techniques, as well as HRFABMS. In addition, a GRE (glucocorticoid responsive element)-mediated luciferase reporter assay was used to initially screen the compounds 3-5, and 7 as glucocorticoid agonists. Compounds 4, 5 and 7 showed significant effects.     

Pentacyclic triterpenoid and saponins from Gambeya boukokoensis

Chemical studies of the EtOAc extract of Gambeya boukokoensis Aubr. et Pellegr. stem bark led to the isolation of eight compounds. Three of them were elucidated as new compounds and designated as: gamboukokoensein A, 1alpha,2alpha,3beta,19alpha,23-pentahydroxyurs-12-en-28-oic acid; gamboukokoenside A, 2beta,3beta,6beta,28-tetrahydroxyolean-12-en-23-oic acid 23-O-alpha-L-arabinopyranosyl ester and gamboukokoenside B, 6beta,28-dihydroxy-3-oxoolean-12-en-23-oic acid 23-O-alpha-L-arabinopyranosyl ester. The other five compounds were known and identified as myrianthic acid, protobassic acid, oleanolic acid, erythrodiol and chondrillasterol. Their structures were elucidated on the basis of one and two dimensional NMR spectroscopic techniques, FABMS, ESMS and chemical evidence.     

Cyclooxygenase-2 enzyme inhibitory triterpenoids from Picrorhiza kurroa seeds

A bioassay guided phytochemical study of the ethyl acetate extract of the seeds of Picrorhiza kurroa afforded a new triterpenoid, 2alpha, 3beta, 19beta, 23-tetrahydroxyolean-12-en-28-O-beta-D-glucoside (1), along with five known triterpenoids, 2alpha, 3beta, 19beta, 23-tetrahydroxyolean-12-en-28-oic acid (2), 2alpha, 3beta, 23-trihydroxyolean-12-en-28-O-beta-d-glucoside (3), 2alpha, 3beta, 23-trihydroxyolean-12-en-28-oic acid (4), 2alpha, 3beta, 19beta, trihydroxyolean-12-en-28-oic acid (5), and 2alpha, 3beta, 6beta, 23-tetrahydroxyolean-12-en-28-oic acid (6). Their structures were established by extensive NMR spectral studies. The acetyl derivatives, compounds 7 and 8, were prepared from compounds 1 and 2, respectively, to aid in their structure elucidation. The inhibition of cyclooxygenase-2 (COX-2) enzyme by compounds 1--6 at 100 microg/mL was 38.3%, 39%, 37%, 49.6%, 25%, and 45.0%, respectively. However, compounds 1--6, at 100 microg/mL, did not inhibit cyclooxygenase-1 (COX-1) enzyme. Compound 1 is a novel triterpenoid and compounds 1--6 are isolated for the first time from the seeds of P. kurroa.     

Triterpenoids, essential oil and photo-oxidative 28 --> 13-lactonization of oleanolic acid from Lantana camara

Two novel triterpenoids have been isolated from the roots of Lantana camara L.: 3beta,19alpha dihydroxy ursan-28-oic acid and 21,22beta-epoxy-3beta-hydroxy olean-12-en-28-oic acid in its methyl ester form. Its leaves have yielded an essential oil which is rich in sesquiterpenes. Oleanolic acid, which is thought to be a hepatoprotective compound, was isolated from L. camara roots and converted into its 28 --> 13beta lactone by a facile photo-oxidation reaction.     

Sterols and triterpenes in cell culture of Hyssopus officinalis L

Cell suspension cultures from hypocotyl-derived callus of Hyssopus officinalis were found to produce two sterols i. e. beta-sitosterol (1) and stigmasterol (2), as well as several known pentacyclic triterpenes with an oleanene and ursene skeleton. The triterpenes were identified as oleanolic acid (3), ursolic acid (4), 2alpha,3beta-dihydroxyolean-12-en-28-oic acid (5), 2alpha,3beta-dihydroxyurs-12-en-28-oic acid (6), 2alpha,3beta,24-trihydroxyolean-12-en-28-oic acid (7), and 2alpha,3beta,24-trihydroxyurs-12-en-28-oic acid (8). Compounds 5-8 were isolated as their acetates (6, 8) or bromolactone acetates (5, 7).     

Lanostanes and friedolanostanes from the bark of Garcinia speciosa

The CHCl(3) extract of the bark of Garcinia speciosa contained four 17,14-friedolanostanes and five lanostanes as well as friedelin and common plant constituents. The friedolanostanes were the previously known methyl ester of (24E)-3 alpha,23 alpha-dihydroxy-17,14-friedolanostan-8,14,24-trien-26-oic acid and the methyl esters of three hitherto unknown acids, 3 alpha-hydroxy-16 alpha,23 alpha-epoxy-17,14-friedolanostan-8,14,24-trien-26-oic acid, 3 alpha,23 alpha-dihydroxy-8 alpha,9 alpha-epoxy-17,14-friedolanostan-15-oxo-24-en-26-oic acid and 3 alpha,23 alpha-dihydroxy-17,14-friedolanostan-15-oxo-8(14),24-dien-26-oic acid. New lanostanes were 3 beta,9 alpha-dihydroxylanost-24-en-26-al and the methyl ester of 3 beta-hydroxy-23-oxo-9,16-lanostadien-26-oic acid. Structures were established by analysis of spectroscopic data. In the case of the lanostanes the previously unassigned C-25 stereochemistry was shown to be 25R by X-ray analysis of 3 beta-hydroxy-23-oxo-9,16-lanostadien-26-oic acid. In the case of the friedolanostanes the configuration at C-23 was established as 23R, identical with the absolute configuration at C-23 of mariesiic acids A and B.     

Tirucallane triterpenes from the roots of Ozoroa insignis

Eight tirucallane triterpenes, methyl 3alpha,24S-dihydroxytirucalla-8,25-dien-21-oate (2), methyl 3alpha-hydroxy-24-oxotirucalla-8,25-dien-21-oate (3), methyl 3alpha-hydroxy-25,26,27-trinor-24-oxotirucall-8-en-21-oate (4), 3alpha,25-dihydroxy-24-(2-hydroxyethyl)-tirucall-8-en-21-oic acid (5), 3alpha,24S,25-trihydroxytirucall-8-en-21-oic acid (6), 3alpha,24R,25-trihydroxytirucall-8-en-21-oic acid (7), 3alpha,25-dihydroxytirucall-8-en-21-oic acid (8), and methyl 3alpha,25-dihydroxytirucall-8-en-21-oate (9), together with alpha-elemolic acid methyl ester (1), were isolated from the roots of Ozoroa insignis. Their structures were elucidated on the basis of spectroscopic evidence.     

Polyhydroxyserratane triterpenoids from Diphasiastrum complanatum

Serratane triterpenoids were identified from Diphasiastrum complanatum (L.) Holub, including serratane-3alpha,14alpha,15alpha,20beta,21beta,24,29-heptol (1), 3alpha,20beta,21beta-trihydroxyserrat-14-en-24-oic acid (2), 3beta,20beta,21beta-trihydroxyserrat-14-en-24-oic acid (3), 3alpha,20beta,21beta-trihydroxy-16-oxoserrat-14-en-24-oic acid (4), and 16-oxolyclanitin-29-yl E-4'-hydroxyl-3'-methoxycinnamate (5) on the basis of their spectroscopic data as well as nine known analogs.     

Pregnane, coumarin and lupane derivatives and cytotoxic constituents from Helicteres angustifolia

2alpha,7beta,20alpha-Trihydroxy-3beta,21-dimethoxy-5-pregnene (1), 6,7,9alpha-trihydroxy-3,8,11alpha-trimethylcyclohexo-[d,e]-coumarin (2), 3beta-hydroxy-27-benzoyloxylup-20(29)-en-28-oic acid (3), and 3beta-hydroxy-27-benzoyloxylup-20(29)-en-28-oic acid methyl ester (4), along with 24 known compounds were isolated and structurally characterized from roots and aerial parts of Helicteres angustifolia (Sterculiaceae). In a preliminary bioassay, the two cucurbitacin derivatives, cucurbitacin D and J exhibited significant inhibitory activities against the growth of both hepatocellular carcinoma BEL-7402 cells and malignant melanoma SK-MEL-28 cells in vitro.     

ent-Kaurenoic acids from Mikania hirsutissima (Compositae)

Four ent-kaurenoic acid derivatives, 2beta,16alpha,17-trihydroxy-ent-kauran-19-oic acid (1), 3beta,16alpha,17-trihydroxy-ent-kauran-19-oic acid (2), 11alpha,15beta-dihydroxy-7-O-beta-d-glucopyranosyl-ent-kaur-16-en-19-oic acid (3) and 1alpha,15beta-dihydroxy-7-O-beta-d-glucopyranosyl-ent-kaur-16-en-19-oic acid (4), were isolated together with five known compounds, 1,5-dicaffeoyl-quinic acid (5), 2-O-glucosyloxy-4-methoxy-cinnamic acid (6), phenethyl alcohol glucoside (7), phenethyl-1-O-beta-d-apiofuranosyl (1-->2) beta-d-glucopyranoside (sayaendoside) (8) and 3,6-dihydroxy-beta-ion-9-ol (9) from the 50% aqueous acetone extract of the aerial parts of Mikania hirsutissima DC. (Compositae). Compounds 1-9 were tested for their proliferative activity toward peripheral blood mononuclear cells (hPBMC); compounds 1 and 2 showed significant activity (43.8% and 36.7%, at 100 microM, respectively) on the lymphocyte.     

Triterpene saponins from Chenopodium quinoa Willd

Twenty triterpene saponins (1-20) have been isolated from different parts of Chenopodium quinoa (flowers, fruits, seed coats, and seeds) and their structures have been elucidated by analysis of chemical and spectroscopic data including 1D- and 2D-NMR. Four compounds (1-4) were identified: 3beta-[(O-beta-d-glucopyranosyl-(1-->3)-alpha-l-arabinopyranosyl)oxy]-23-oxo-olean-12-en-28-oic acid beta-d-glucopyranoside (1), 3beta-[(O-beta-d-glucopyranosyl-(1-->3)-alpha-l-arabinopyranosyl)oxy]-27-oxo-olean-12-en-28-oic acid beta-d-glucopyranoside (2), 3-O-alpha-l-arabinopyranosyl serjanic acid 28-O-beta-d-glucopyranosyl ester (3), and 3-O-beta-d-glucuronopyranosyl serjanic acid 28-O-beta-d-glucopyranosyl ester (4). The following known compounds have not previously been reported as saponin constituents from the flowers and the fruits of this plant: two bidesmosides of serjanic acid (5,6), four bidesmosides of oleanolic acid (7-10), five bidesmosides of phytolaccagenic acid (11-15), four bidesmosides of hederagenin (16-19), and one bidesmoside of 3beta,23,30-trihydroxy olean-12-en-28-oic acid (20). The cytotoxicity of these saponins and their aglycones was tested in HeLa cells. Induction of apoptosis in Caco-2 cells by bidesmosidic saponins 1-4 and their aglycones I-III was determined by flow cytometric DNA analysis. The saponins with an aldehyde group were most active. The relationships between structure and cytotoxic activity of saponins and their aglycones are discussed.     

Constituents of the fungi Daedalea quercina and Daedaleopsis confragosa var. tricolor

Phytochemical examination of solvent extracts of the wood-rotting fungi Daedalea quercina and Daedaleopsis confragosa var. tricolor led to the isolation of five new triterpene derivatives and some known fungal constituents. All structures were identified by one- and two-dimensional NMR spectroscopy and mass spectrometry. From Daedalea quercina, the new natural products 16-O-acetylpolyporenic acid C, 16alpha-acetoxy-24-methylene-3-oxolanost-8-en-21-oic acid, (+)-24-methylene-3,23-dioxolanost-8-en-26-oic acid, (+)-3beta,12beta-dihydroxy-24-methyl-23-oxolanost-8-en-26-oi c acid and 12beta,23-epoxy-3alpha,23-dihydroxy-24-methyllanost-8- en-26-oic acid could be isolated. From Daedaleopsis confragosa var. tricolor, the compounds 3alpha-carboxyacetoxyquercinic acid, 3alpha-carboxyacetoxy-24-methylene-23-oxolanost-8-en-2 6-oic acid and 5alpha,8alpha-epidioxyergosta-6,22-dien-3beta-ol were identified. These are the first described triterpene derivatives isolated from this fungus.     

Synthesis of ester-linked lithocholic acid dimers

Four lithocholic acid dimers were synthesised via esterification. The ester-linked dimer, 3-oxo-5beta-cholan-24-oic acid (cholan-24-oic acid methyl ester)-3-yl ester, (3alpha,5beta), was obtained by condensation of methyl lithocholate with 3-oxo-5beta-cholan-24-oic acid. Borohydride reduction of this ester-linked dimer gave 3alpha-hydroxy-5beta-cholan-24-oic acid (cholan-24-oic acid methyl ester)-3-yl ester, (3alpha,5beta), which was acetylated to 3alpha-acetoxy-5beta-cholan-24-oic acid (cholan-24-oic acid methyl ester)-3-yl ester, (3alpha,5beta). Reaction of methyl lithocholate with oxalyl chloride yielded the oxalate dimer, bis(5beta-cholan-24-oic acid methyl ester)-3alpha-yl oxalate.     

Synthesis of 3 alpha,6 beta,7 alpha,12 beta- and 3 alpha,6 beta,7 beta,12 beta-tetrahydroxy-5 beta-cholanoic acids.

Chemical synthesis of 3 alpha,6 beta,7 alpha,12 beta- and 3 alpha,6 beta,7 beta,12 beta-tetrahydroxy-5 beta-cholan-24-oic acids is described. 3 alpha,12 beta-Dihydroxy-5 beta-chol-6-en-24-oic acid used as the starting material in the synthesis was prepared via oxidation of 3 alpha,12 alpha-dihydroxy-5 beta-chol-6-en-24-oic acid 3-hemisuccinate at C-12 followed by reduction with potassium/tertiary amyl alcohol. alpha-Epoxidation of the ester diacetate of 3 alpha,12 beta-dihydroxy-5 beta-chol-6-en-24-oic acid with m-chloroperbenzoic acid followed by cleavage of the epoxide with acetic acid and alkaline hydrolysis yielded 3 alpha,6 beta,7 alpha,12 beta-tetrahydroxy-5 beta-cholan-24-oic acid (overall yield 25%). N-Methylmorpholine-N-oxide-catalyzed osmium tetroxide oxidation of the ester diacetate of 3 alpha,12 beta-dihydroxy-5 beta-chol-6-en-24-oic acid followed by alkaline hydrolysis yielded 3 alpha,6 beta,7 beta,12 beta-tetrahydroxy-5 beta-cholan-24-oic acid (overall yield 33%). The structures of the synthesized bile acids were confirmed from their proto nuclear magnetic resonance and mass spectral fragmentation patterns.     

Constituents of various wood-rotting basidiomycetes

Phytochemical investigation of n-hexane and methanol extracts of fruiting bodies of the wood-rotting fungi Fomitopsis pinicola. Ganoderma lipsiense, Fomes fomentarius and Gloeophyllum odoratum led to the isolation and identification of several triterpene derivatives and some aromatic compounds derived from lignin. These are the new natural products, namely, pinicolic acid E (16alpha-hydroxy-3-oxolanosta-8,24-dien-21-oic acid) and pinicolol C (3-oxolanosta-7,9(11),24-trien-15alpha,21-diol) from the crust of F. pinicola, ganoderenic acid D [(E)-7beta-hydroxy-3,11,15,23-tetraoxolanosta-8,20(22)-di en-26-oic acid] and ganoderic acid N (7beta,20-dihydroxy-3,11,15,23-tetraoxolanost-8-en-26-oic acid) from G. lipsiense and ergosterol peroxide (5alpha,8alpha-epi-dioxyergost-6-en-3beta-ol) as well as ergost-7-en-3-one from F. fomentarius. From G. odoratum, dehydroeburicoic acid [24-methylene-3-oxolanosta-7,9(11)-dien-21-oic acid], the dimethylacetal of 4,4,14alpha-trimethyl-24-oxo-5alpha-chol-8-en-21-oic acid and some aromatic compounds, of which 1-(4'-methoxyphenyl)-1,2-ethandiol is a new natural product, were isolated. Furthermore, a complete set of 13C NMR data of the steryl esters 3beta-linoleyloxyergosta-7,24(28)-diene, 3beta-linoleyloxyergosta-7,24-diene and 3beta-linoleyloxyergost-7-ene, which could be identified as a mixture in all investigated fungi, could be recorded. It was proved by HPLC and TLC investigations, that the crust on top of the fruiting bodies of F. pinicola consists of lanostane derivatives.     

Triterpene saponins and iridoid glucosides from galium rivale

Three new glycosides of the oleanene-type triterpenes, rivalosides C-E (1-3), along with three known triterpene saponins, momordin IIb (4) and rivalosides A-B (5-6), and five known iridoid glucosides: monotropein, scandoside, deacetylasperulosidic acid, geniposidic acid and asperulosidic acid, were isolated from aerial parts of Galium rivale. The structures of the new compounds were elucidated by spectral methods and chemical means as 2alpha-acetoxy-3alpha, 19alpha-dihydroxy-olean-12-en-28-oic acid 28-O-beta-D-glucopyranosyl-(1--> 6)-beta-D-glucopyranoside, 2alpha,3alpha, 19alpha-trihydroxy-olean- 12-en-28-oic acid 28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranoside and 3-O-beta-D-glucuronopyranosyl-24-hydroxy-olean-12-en-28-oic acid 28-O-beta-D-glucopyranoside, for rivalosides C-E, respectively. The taxonomic significance of the rivalosides in G. rivale was discussed.