Two new cytotoxic triterpenoid saponins from the roots of Clematis argentilucida

Bioassay-guided fractionation of the n-BuOH extract of the roots of Clematis argentilucida led to the isolation of two new triterpenoid saponins along with a known one, cussonside B (3). By extensive spectral analysis and chemical evidences, the structures of the two new saponins were determined to be 3β-O-[β-D-ribopyranosyl-(1→3)-α-L-rhamnopyranosyl-(1→2)-α-L-arabinopyranosyl] hederagenin-11,13-dien-28-oic acid (1) and 3β-O-{β-D-ribopyranosyl-(1→3)-α-L-rhamnopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-β-D-xylopyranosyl} oleanolic acid (2), respectively. Saponin 1 is the first example of triterpenoid saponins with two double bonds located at C-11 and C-13 in the aglycone from the genus Clematis. The two new saponins exhibited significant cytotoxicity against human leukemia HL-60 cell lines, human hepatocellular carcinoma Hep-G2 cell lines and human glioblastoma U251MG cell lines with a range of IC(50) values from 2.74 to 25.40μM, while 3 showed inactivity against all of the three cancer cell lines.     

New triterpenoid saponins from Leontice smirnowii

Three new triterpene saponins, leonticins I (1), J (2) and L (3) were isolated from the tubers of Leontice smirnowii. On the basis of spectroscopic methods, including 2D NMR experiments (DEPT, gs-COSY, gs-HMQC, gs-HMBC and gs-HSQC-TOCSY), mass spectrometry (HR-ESI-MS) and chemical degradation, the structures of the new compounds were elucidated as 3-O-β-D-glucopyranosyl-(1 → 3)-[β-D-xylopyranosyl-1 → 2)]-α-L-arabinopyranosyl-28-O-[α-L-rhamnopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranosyl]-3β-hydroxy-30-norolean-12,20(29)-dien-28-oic acid (1), 3-O-[β-D-xylopyranosyl-(1 → 3)-β-D-galactopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 3)-α-L-arabinopyranosyl]-28-O-[α-L-rhamnopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranosyl]-3β-hydroxy-30-norolean-12,20(29)-dien-28-oic acid (2) and 3-O-[β-D-xylopyranosyl-(1 → 3)-β-D-galactopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 3)]-[β-D-xylopyranosyl-(1 → 2)]-α-L-arabinopyranosyl]-28-O-[α-L-rhamnopyranosyl-(1 → 4)-β-D-glucopyranosyl-(1 → 6)-β-D-glucopyranosyl]-3β-hydroxy-30-norolean-12,20(29)-dien-28-oic acid (3), respectively. The aglycone 3β-hydroxy-30-norolean-12,20(29)-dien-28-oic acid was observed for the first time in Leontice species.     

New ursane-type triterpenoid saponins from the stem bark of Schefflera heptaphylla

Phytochemical investigation on the stem bark of Schefflera heptaphylla led to the isolation of five new ursane-type triterpenoid saponins (1–5). Their structures were determined on the basis of spectroscopic and chemical methods. It is noteworthy in this study that the genins of all compounds are reported for the first time. All compounds isolated from this plant were evaluated for their inhibitory activities on lipopolysaccharide-induced nitric oxide production in RAW264.7 cells, and compounds 2 and 5 showed weak anti-inflammatory activities under their non-cytotoxic concentrations.     

New antioxidant and antiglycation active triterpenoid saponins from the root bark of Aralia taibaiensis

Four new oleanane type triterpenoid saponins (1-4) and a known saponin (5) were isolated from the root bark of Aralia taibaiensis Z.Z. Wang et H.C. Zheng. The structures of the four new compounds were elucidated as 3-O-{β-d-glucopyranosyl-(1 → 2)-[β-d-glucopyranosyl-(1 → 3)]-β-d-glucurono-pyranosyl}-olean-11,13(18)-diene-28-oic acid 28-O-β-d-glucopyranosyl ester (1), 3-O-{β-d-gluco-pyranosyl-(1 → 3)-[α-l-arabinofuranosyl-(1 → 4)]-β-d-glucuronopyranosyl}-olean-11,13(18)-diene-28-oic acid 28-O-β-D-glucopyranosyl ester (2), 3-O-{β-d-glucopyranosyl-(1 → 2)-[α-l-arabinofuranosyl-(1 → 4)]-β-d-glucuronopyranosyl}-oleanolic acid 28-O-β-D-glucopyranosyl ester (3) and 3-O-{β-d-glucopyranosyl-(1 → 2)-[β-d-glucopyranosyl-(1 → 3)]-β-d-glucuronopyranosyl}-oleanolic acid 28-O-β-d-glucopyranosyl ester (4), on the basis of extensive spectral analysis and chemical evidence. Compounds 1-5 exhibited moderate effects on antioxidant and antiglycation activities, which correlated with treatment of diabetes mellitus.     

Three triterpenoid saponins from the roots of Polygala japonica Houtt

Three new triterpenoid saponins polygalasaponins LI-LIII (1-3) with two acylation groups in oligosaccharide chain, together with three known saponins were isolated from the roots of Polygala japonica Houtt. (4-6). The neuroprotective effects of these compounds on neuron-like PC12 cells were evaluated in vitro. Compounds 5 and 6 show neuroprotective effects in Aβ(25-35) model at the concentration of 10μM.     

Triterpenoid saponins from Clematis tangutica and their cardioprotective activities

Phytochemical investigation of the whole plants of Clematis tangutica led to the isolation of three new triterpenoid saponins (1–3), together with four known saponins (4–7). Their structures were determined by extensive spectral analysis and chemical evidences. Compounds 1–7 were evaluated for their cardioprotective activities in cardiomyocytes anoxia/reoxygenation (A/R) model. The results showed that those saponins exhibited cardioprotective effects by decreasing the levels of creatine kinase-MB (CK-MB) and lactate dehydrogenase (LDH).     

Oleanane-type triterpenoid saponins from Xanthoceras sorbifolia Bunge

Phytochemical analysis of the extract from the seed oil leavings of Xanthoceras sorbifolia Bunge led to the isolation of five new oleanane-type triterpeniod saponins, sorbifoliasides G–K (1–5). Their structures were elucidated on the basis of spectroscopic analysis and chemical derivatization. To our knowledge, compound 5 is the first example of a naturally occurring 3,28-O-bisdesmosic triterpenoid saponin with olefinic linkages at C12 and C15. The cytotoxicity of all compounds against ten selected human cancer cell lines was assayed.     

Plant growth regulation effects of triterpenoid saponins

 To investigate structure–activity relations between the sugar chain structures of triterpenoid saponins and their plant growth regulation effects, several monodesmosidic saponins with betulin as an aglycon were synthesized by chemical and enzymic reactions. Three triterpenoids (betulin, betulinic acid, oleanolic acid) and synthesized betulin glycosides were submitted to germination and growth regulation tests on alfalfa seeds. We concluded the following. Betulin had a slight growth inhibitory effect on alfalfa radicles. Betulin glycosides exhibited stronger effects than betulin, and betulin glycosides with two to four glucose residues as a sugar moiety had the greatest inhibitory activity. These characteristics of growth inhibitory effects were considerably different from those of phenolic compounds so far reported. Some betulin glycosides also showed a significant growth regulation effect on alfalfa hypocotyls. However, hypocotyl growth was less affected than radicle growth for all betulin glycosides. Among the triterpenoids, betulinic acid had stronger growth inhibitory effects on alfalfa radicles than betulin, suggesting the importance of the carboxyl group at the C-28 position for the inhibitory effects of lupane-type triterpenoids. On the other hand, no germination regulation effects on alfalfa seeds were observed for any of the betulin glycosides or triterpenoids examined. Received: October 9, 2001 / Accepted: February 15, 2002 Acknowledgments This work was supported in part by a research grant (Development of Highly Functional Materials by Structural Modification of Carbohydrates) from the Ministry of Agriculture, Forestry, and Fisheries of Japan. We thank Saori Kudo for her assistance in isolating compounds by chromatography. Correspondence to:S. Ohara     

Phenylpropanoid glycosides and triterpenoid of Pedicularis kansuensis Maxim

Phytochemical investigation of the ethanol extract of Pedicularis kansuensis Maxim. led to the isolation of one new triterpenoid and two new phenylpropanoid glycosides, along with ten known compounds. Their structures were established by extensive 1D and 2D NMR, as well as other spectrum analysis. Biological evaluation of the three new compounds against Hela cell and Hep-6 cell with MIC values ranging from 9 to 20 μg/ml.     

Three new triterpenoid saponins from root of Gardenia jasminoides Ellis

Three new compounds (Gardeniside A–C), 11α,12α-epoxy-3β-[(O-β-D-glucuronopyranoside-6′-O-methly ester)oxy]olean-28,13-olide (1), siaresinolic acid 3-O-β-D-glucuronopyranoside-6′-O-methly ester (2), and 3-O-β-D- glucuronopyranoside-6′-O-methly ester-siaresinolic acid-28-O-β-D- glucopyranoside (3), with seven known compounds oleanolic acid 3-O-β-D- glucuronopyranoside-6′-O-methly ester (4), oleanolic acid 3-O-β-D- glucuropyranoside (5), hederagenin 3-O-β-D- glucuronopyranoside-6′-O- methly ester (6), chikusetsusaponin IVa methyl ester (7), chikusetsusaponin (8), chikusetsusaponin IVa butyl ester (9), siaresinolic acid 28-o-β-d-glucopyranosyl ester (10) were isolated from the root of Gardenia jasminoides Ellis. Six compounds (1, 4–7, and 9) showed cytotoxic activities against HeLa, A549, MCF-7 and A354-S2 cell lines.     

Structure elucidation of two triterpenoid saponins from rhizome of Anemone raddeana Regel

Two new 27-hydroxy-oleanolic acid type triterpenoid saponins, raddeanoside 20 (1) and raddeanoside 21(2) were isolated from the rhizome of Anemone raddeana Regel. The structures of the two compounds were elucidated as 27-hydroxy-oleanolic acid 3-O-α-l-rhamnopyranosyl(1→2) [β-d-glucopyranosyl (1→4)]-α-l-arabinopyranoside (1) and 3-O-α-l-rhamnopyranosyl (1→2)-α-l-arabinopyranosyl-27-hydroxy-oleanolic acid 28-O-α-l-rhamnopyranosyl(1→4)-β-d-glucopyranosyl (1→6)-β-d-glucopyranoside (2) on the basis of chemical and spectral evidence.     

Structure elucidation and complete NMR spectral assignment of two triterpenoid saponins from Radix Hedysari

A new oleanane-type triterpenoid saponin with a carbonyl group at C-15, named polybosaponin A (1), together with a known triterpenoid saponin, dehydrosoyasaponin I (2), were isolated from Radix Hedysari. On the basis of one- and two-dimensional NMR and high resolution electrospray ionization mass spectrometry, the structure of 1 were elucidated and the ¹H and ¹³C NMR spectral signals were assigned totally. In addition, the complete assignment of ¹H NMR signals and revision of incorrect assignment of ¹³C NMR signals for 2 were also achieved based on one- and two-dimensional NMR spectrometry.     

New antibacterial triterpenoid saponin from Lactuca scariola

A new antibacterial triterpenoid saponin, 3beta-O-[alpha-L-rhamnopyranosyl]-30-norolean-12,19-diene-28-oic acid 28-O-[beta-D-glucopyranosyl-(1-->4)-O-beta-D-galactopyranosyl]-ester (1); has been isolated from the stems of Lactuca scariola. Its structure was determined by chemical degradations and spectral analysis.     

Three new oleanane triterpenoid saponins acetylated with monoterpenoid acid from Albizia julibrissin

Three new minor oleanane triterpenoid saponins acetylated with monoterpenoid acid, julibroside J₃₂, julibroside J₃₅ and julibroside J₃₆, along with one new natural product, prosapogenin 9, were isolated from the stem bark of Albizia julibrissin. Their structures were elucidated on the basis of the chemical and spectroscopic evidences.     

A cytotoxic triterpenoid saponin from under-ground parts of Gypsophila pilulifera Boiss.& Heldr

A cytotoxic triterpenoid saponin was isolated from the under-ground parts of Gypsophila pilulifera Boiss.& Heldr. (Caryophyllaceae) naturally grow in the southwestern region of the Turkey. The structures of saponin was elucidated as 3-O-β-D-galactopyranosyl-(1→2)-[β-D-xylopyranosyl-(1→3)]-β-D-glucuronopyranosyl quillaic acid 28-O-β-D-glucopyranosyl-(1→3)-[β-d-xylopyranosyl-(1→4]-α-l-rhamnopyranosyl-(1→2)-β-D-fucopyranosyl ester on the basis of extensive spectral analysis and chemical evidence. The separated triterpenoid saponin was isolated from Gypsophila pilulifera for the first time. The saponin compound displayed significant cytotoxicity against A549 cell line with IC(50) values >16μM.     

Two new nortriterpenoid saponins from Salicornia bigelovii Torr. and their cytotoxic activity

Investigation of characteristic constituents of Salicornia bigelovii Torr. led to isolation of two new 30-nortriterpenoid glycosides, Bigelovii A (1), Bigelovii B (2), together with two known 30-nortriterpenoid glycosides 3-4 and three known oleanane-type triterpenoid glycosides 5-7. The structures of new compounds were elucidated by extensive 1D and 2D NMR, and MS spectroscopic analysis, and chemical evidences. All compounds were isolated for the first time from Chenopodiaceae. Thus compounds 1-4 were evaluated for their cytotoxicity and compouds 1, 3 showed moderate activity against four cell lines, HL-60 (promyelocytic leukemia), MCF-7 (breast carcinoma), HepG2 (liver carcinoma) and A549 (lung carcinoma), with IC(50) values of 6.18, 78.08, 13.64 and >100μM for 1; 31.87, >100, ~100, >100μM for 3, respectively.     

New triterpene saponins from the root of Ilex pubescens

Two new triterpene glycosides named ilexpublesnin A (1) and ilexpublesnin B (2) were isolated from the root of Ilex pubescens. Their structures were determined as 3-O-(β-d-xylopyranosyl)-28-O-(β-d-glucopyranosyl)-3β, 19α-dihydroxyurs-23-oxo-12-en-28-oic acid (1) and 28-O-(β-d-xylopyranosyl-(2 → 1)-β-d-glucopyranosyl)-3β, 19α-dihydroxyurs-23-oxo-12-en-28-oic acid (2) on the basis of chemical and spectroscopic methods.     

New pregnane saponins from Ecdysanthera rosea and their cytotoxicity

Two new pregnane saponins elucidated as ecdysantheroside A (1) and ecdysantheroside B (2) and six known compounds (3-8) based on spectral data (MS, IR, 1D and 2D NMR) were isolated from the stem bark of Ecdysanthera rosea. The cytotoxicity against six cell lines of these compounds was tested by MTT assay. The results revealed that compounds 5 and 7 showed cytotoxicity against all the cell lines. Compound 2 showed cytotoxicity against cells A549, MDA435, HepG2, and HUVEC, while compound 4 showed cytotoxicity against cells A549, CEM, and HUVEC. Compound 6 had cytotoxicity against the others except cell HepG2.     

New cytotoxic diarylheptanoids from the rhizomes of Alpinia officinarum Hance

Two new dimeric diarylheptanoids, named Alpinin C (1) and D (2), a new natural product of diarylheptanoid (3) along with three known diarylheptanoids (4–6) were isolated from the rhizomes of Alpinia officinarum Hance. Their structures were elucidated based on extensive spectroscopic analyses (1D and 2D NMR, HRTOFMS, IR). The isolated compounds were evaluated for their cytotoxicity against human tumor cell lines HepG2, MCF-7, T98G and B16-F10. Compound 1 showed selective cytotoxicity against cell lines of MCF-7 and T98G, while compound 6 showed significant cytotoxicity to the all tested tumor cell lines with IC₅₀ in the range from 8.46 to 22.68 μmol/L.     

New cytotoxic quinolone alkaloids from fruits of Evodia rutaecarpa

Three new quinolone alkaloids, 1-methyl-2-[7-hydroxy-(E)-9-tridecenyl]-4(1H)-quinolone (1), 1-methyl-2-[(Z)-4-nonenyl]-4(1H)-quinolone (2), 1-methyl-2-[(1E,5Z)-1,5-undecadienyl]-4(1H)-quinolone (3) and one new natural product, 1-methyl-2-[(E)-1-undecenyl]-4(1H)-quinolone (4), were isolated from the dried and nearly ripe fruits of Evodia rutaecarpa (Juss.) Benth., along with thirteen known compounds (5-17). In addition, one new artificial product, 1-methyl-2-[7-carbonyl-(E)-9-tridecenyl]-4(1H)-quinolone (1A) was also obtained. The structures of these compounds were determined by spectroscopic analyses. The cytotoxic activities of all of the compounds against the human cancer cell lines HL-60, N-87, H-460, and Hep G(2) cells were evaluated by MTT assay. The results showed that these alkaloids inhibited cell proliferation with IC(50) values between 14μM and 22μM.