Steroidal saponins and alkaloids from the bulbs of Lilium brownii var. colchesteri

The fresh bulbs of Lilium brownii var. colchesteri were found to contain five steroidal saponins: 26-O-beta-D-glucopyranosylnuatigenin 3-O-alpha-L-rhamnopyranosyl-(1----2)-beta-D-glucopyranoside (6), 26-O-beta-D-glucopyranosylnuatigenin 3-O-alpha-L-rhamnopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----4)]- beta-D-glucopyranoside (7), brownioside (8), deacylbrownioside (9) and 27-O-(3-hydroxy-3-methylglutaroyl)isonarthogenin 3-O-alpha-L-rhamnopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----4)- beta-D-glucopyranoside (10); and two steroidal alkaloids: beta 1-solamargine (11) and solasodine 3-O-alpha-L-rhamnopyranosyl-(1----2)-O-[beta-D-glucopyranosyl-(1----4)- beta-D-glucopyranoside (12); along with several phenolic constituents. Compounds 7, 10 and 12 are new naturally-occurring compounds.     

Structures of two new fibrinolytic saponins from the seed of Luffa cylindrica Roem

Two new fibrinolytic saponins, lucyosides N and P, were isolated from the seeds of Luffa cylindrica Roem. (Cucurbitaceae). On the basis of chemical and spectral evidence, lucyoside N was characterized as 3-O-beta-D-galactopyranosyl-(1----2)-beta-D-glucuronopyranosyl-28- O-beta-D-xylopyranosyl-(1----4)-[beta-D-glucopyranosyl-(1----3)]-alpha-L -rhamnopyranosyl-(1----2)-alpha-arabinopyranosyl quillaic acid. Lucyoside P was characterized as a gypsogenin glycoside with the same sugar moiety as lucyoside N.     

New saponins from the seeds of Aesculus chinensis

Eight new acylated polyhydroxyoleanene triterpenoidal saponins, aesculiosides A-H (1-8), along with four known ones, have been isolated from the seeds of Aesculus chinensis. On the basis of extensive NMR studies, the structures of the new compounds were determined to be 21-O-tigloylprotoaescigenin 3-O-[beta-D-glucopyranosyl-(1-->2)][beta-D-glucopyranosyl-(1-->4)]- beta-D-glucuronopyranosyl acid (1), 21-O-angeloylprotoaescigenin 3-O-[beta-D-glucopyranosyl- (1-->2)][beta-D-glucopyranosyl-(1-->4)]-beta-D-glucuronopyranosyl acid (2), 21,22-O-ditigloylprotoaescigenin 3-O-[beta-D-glucopyranosyl-(1-->2)][beta-d-glucopyranosyl- (1-->4)]-beta-D-glucuronopyranosyl acid (3), 21-O-tigloyl-22-O-angeloylprotoaescigenin 3-O-[beta-D-glucopyranosyl- (1-->2)][beta-D-glucopyranosyl-(1-->4)]-beta-D-glucuronopyranosyl acid (4), 21,22-O-ditigloylprotoaescigenin 3-O-[beta-D-glucopyranosyl- (1-->2)][beta-D-glucopyranosyl-(1-->4)]-methyl beta-d-glucuronopyranosate (5), 21-O-tigloyl-22-O-angeloylprotoaescigenin 3-O-[beta-D-glucopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->4)]-methy l beta-D-glucuronopyranosate (6), 21-O-tigloyl-28-O-acetylprotoaescigenin 3-O-[beta-D-glucopyranosyl-(1-->2)][beta-D-glucopyranosyl-(1-->4)]-methy l beta-D-glucuronopyranosate (7) and 21-O-angeloyl-28-O-acetylprotoaescigenin 3-O-[beta-D-glucopyranosyl-(1-->2)][beta-D-glucopyranosyl-(1-->4)]-methy l beta-D-glucuronopyranosate (8).     

New triterpenoid saponins from Maesa tenera.

Two new triterpenoid saponins, maetenosides A and B were isolated from the aerial parts of Maesa tenera and were respectively defined as 3-O-[beta-D-glucopyranosyl-(1-->2)-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-galactopyranosyl-(1-->3)][beta-D-glucopyranosyl-(1-->2)]-beta-D-glucuronopyranosyl camelliagenin A 22-O-angelate (1) and 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-beta-D-galactopyranosyl-(1-->3)][beta-o-glucopyranosyl-(1-->2)]-beta-D-glucuronopyranosyl camelliagenin A 22-O-angelate (2). Their structures were established on the basis of chemical and spectroscopic methods.     

Minor triterpenoid saponins from Ardisia crenata

Two minor triterpenoid saponins, ardisicrenoside G [3 beta-O-{alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->4)- [beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl}-16 alpha,28-dihydroxyolean-12-en-30-oic acid] and ardisicrenoside H [3 beta-O-{beta-D-xylopyranosyl-(1-->2)-beta-D- glucopyranosyl-(1-->4)-[beta-D-glucopyranosyl-(1-->2)]-alpha-L- arabinopyranosyl}-16 alpha,28-dihydroxyolean-12-en-30-oic acid] were isolated from the roots of Ardisia crenata. Structural assignments are based on NMR, MS and chemical reactions.     

Phenylethanoid and iridoid glycosides from Veronica persica

A new phenylethanoid glycoside, persicoside (1) and three known phenylethanoid glycosides, acteoside (2), isoacteoside (3) and lavandulifolioside (4) were isolated from the aerial parts of Veronica persica. On the basis of spectral analyses, the structure of the new compound was elucidated to be 3,4-dihydroxy-beta-phenylethoxy-O-[beta-D-glucopyranosyl-(1-->2)]-[beta-D-glucopyranosyl-(1-->3)]-4-O-caffeoyl-beta-D-glucopyranoside. Persicoside (1) and acteoside (2) exhibited radical scavenging activity against 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical. Beside phenylethanoid glycosides, a hexitol, dulcitol (5) and seven known iridoid glucosides, aucubin (6), veronicoside (7), amphicoside (8), 6-O-veratroyl-catalpol (9), catalposide (10), verproside (11) and verminoside (12) were isolated.     

Studies on the constituents of Luffa acutangula Roxb. I. Structures of acutosides A--G, oleanane-type triterpene saponins isolated from the herb.

From the herb of Luffa acutangula ROXB. (Cucurbitaceae), seven oleanane-type triterpene saponins, acutosides A--G, were isolated and their structures were determined. Acutoside A is oleanolic acid 3-O-beta-D-glucopyranosyl-(1----2)-beta-D-glucopyranoside. Acutosides B, D, E, F and G have a common prosapogenin structure, acutoside A, and only differ in the structures of the ester-linked sugar moieties. Acutoside B is a 28-O-[O-beta-D-xylopyranosyl-(1----4)-O-alpha-L-rhamnopyranosyl-(1----2) -alpha-L-arabinopyranosyl] ester, D is a 28-O-[O-beta-D-xylopyranosyl-(1----3)-O-beta-D-xylopyranosyl-(1----4)-O- alpha-L-rhamnopyranosyl-(1----2)-alpha-L-arabinopyranosyl] ester, E is a 28-O-[O-alpha-L-arabinopyranosyl-(1----3)-O-beta-D-xylopyranosyl-( 1----4)-O-alpha-L-rhamnopyranosyl-(1----2)-alpha-L-arabinopyranosyl] ester, F is a 28-O-[O-beta-D-xylopyranosyl-(1----3)-[O-beta-D-xylopyranosyl-(1----4)-O -alpha-L-rhamnopyranosyl-(1----2)-alpha-L-arabinopyranosyl] ester, and G is a 28-O-beta-D-xylopyranosyl-(1----3)-[O-alpha-L-arabinopyranosyl-(1- ---3)-O-beta-D-xylopyranosyl-(1----4)]-O-alpha-L- rhamnopyranosyl-(1----2)-alpha-L-arabinopyranosyl] ester. Acutoside C is a machaelinic acid (=21 beta-hydroxyoleanolic acid) saponin having the same sugar moiety as that of acutoside B.     

Studies on the constituents of Aster scaber Thunb. III. Structures of scaberosides B7, B8 and B9, minor oleanolic acid glycosides isolated from the root.

Three new oleanolic acid 3,28-O-bisdesmosides, scaberosides B7, B8 and B9, were isolated as minor saponins from the root of Aster scaber THUNB. (Compositae), and their structures were determined based on spectral and chemical evidence as follows. Scaberoside B7 is 3-O-beta-D-glucopyranosyluronic acid oleanolic acid 28-[O-beta-D-apiofuranosyl-(1----3)-[O-beta-D-xylopyranosyl-(1---- 4)-O-alpha-L-rhamnopyranosyl-(1----2)-alpha-L-arabinopyranosyl] ester, scaberoside B8, 3-O-beta-D-glucopyranosyl oleanolic acid 28-[O-beta-D-xylopyranosyl-(1----4)-O-alpha-L-rhamnopyranosyl-(1----2)-a lpha-L-arabinopyranosyl] ester, and scaberoside B9, 3-O-beta-D-glucopyranosyluronic acid oleanolic acid 28-[O-alpha-L-rhamnopyranosyl-(1----2)-[O-beta-D-xylopyranosyl-(1----6)] -beta-D-glucopyranosyl] ester. Scaberosides B7 and B9 were obtained as their methyl esters.     

Molluscicidal triterpenoidal saponin from Lysimachia sikokiana

The main molluscicidal activity of the methanol extract of Lysimachia sikokiana is due to several triterpenic saponins called sakuraso-saponins. The most active component was isolated from the aerial parts and elucidated as 3-O-beta-xylopyranosyl-(1----2)-beta-glucopyranosyl-(1----4)- [beta-glucopyranosyl-(1----2)]-alpha-arabinopyranosyl protoprimulagenin A, named lysikoianoside 1, on the basis of 1H- and 13C-nuclear magnetic resonance spectral data and methylation analysis results.     

Study on the constituents of Desmodium styracifolium

Two triterpenoid saponins (1 and 2) were isolated from Desmodii Herba [the dried whole plants of Desmodium styracifolium (Osbeck) Merr. (Leguminosae)] and their chemical structures were characterized as soyasaponin I and a new saponin, 3-O-[alpha-L-rhamnopyranosyl-(1----2)-beta-D-galactopyranosyl- (1----2)-beta-D-glucuronopyranosyl]soyasapogenol E, respectively, by chemical and spectroscopic means.     

Norlanostane and lanostane glycosides from the bulbs of Chionodoxa luciliae and their cytotoxic activity

Ten lanostane glycosides (1-10), including two new norlanostane glycosides (2 and 7) and a new lanostane glycoside with a spirolactone ring system (9), were isolated from the fresh bulbs of Chionodoxa luciliae (Liliaceae). The structures of the new compounds were determined on the basis of extensive spectroscopic analysis and the results of hydrolytic cleavage to be (23S)-3beta-[(O-beta-D-apiofuranosyl-(1-->2)-O-[beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosyl)oxy]-17alpha,23-epoxy-28,29-dihydroxy-27-norlanost-8-en-24-one (2), (23S)-17alpha,23-epoxy-29-hydroxy-3beta-[(O-alpha-L-rhamnopyranosyl-(1-->2)-O-[O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosyl)oxy]-27-norlanost-8-ene-15,24-dione (7), and (23S,25R)-17alpha,23-epoxy-29-hydroxy-3beta-[(O-alpha-L-rhamnopyranosyl-(1-->2)-O-[beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranosyl)oxy]lanost-8-en-23,26-olide (9), respectively. The cytotoxic activity of the isolated compounds against HSC-2 human oral squamous cell carcinoma cells are also reported.     

Studies on Balanites aegyptiaca fruits, an antidiabetic Egyptian folk medicine

An aqueous extract of mesocarps of the fruits of Balanites aegyptiaca exhibited a prominent antidiabetic activity by oral administration in streptozotocin induced diabetic mice. From one of the active fractions of this extract, two new steroidal saponins were isolated, and their structures were determined as 26-O-beta-D-glucopyranosyl-(25R)-furost-5-ene-3 beta,22,26-triol 3-O-[alpha-L-rhamnopyranosyl-(1----2)]-[beta-D-xylopyranosyl-(1---- 3)]-[alpha-L-rhamnopyranosyl-(1----4)]-beta-D-glucopyranoside and its 22-methyl ether. In addition, two known saponins, 26-O-beta-D-glucopyranosyl-(25R)-furost-5-ene-3 beta,22,26-triol 3-O-(2,4-di-O-alpha-L-rhamnopyranosyl)-beta-D-glucopyranoside and its methyl ether were isolated and identified. It was revealed that the individual saponins did not show antidiabetic activity, while the recombination of these saponins resulted in significant activity. From an ethanolic extract of the epicarps, two known flavonol glycosides, isorhamnetin-3-O-robinobioside and isorhamnetin-3-O-rutinoside were isolated and identified.     

Structures of two new steroidal glycosides, soladulcosides A and B from Solanum dulcamara

The structures of two new steroidal glycosides named soladulcosides A and B, isolated from the aerial parts of Solanum dulcamara including new sapogenols, were elucidated as (22R, 25R)-3 beta, 15 alpha, 23 alpha-trihydroxy-5 alpha-spirostan-26-one 3-O-alpha-L-rhamnopyranosyl-(1----2)-beta-D-glucopyranoside and (22R, 25R)-3 beta,23 alpha-dihydroxy-5 alpha-spirostan-26-one 3-O-alpha-L-rhamnopyranosyl-(1----2)-[alpha-L-rhamnopyranosyl-(1----4)]- beta-D-glucopyranoside, respectively.     

Glycosides of benzyl and salicyl alcohols from Alangium chinense

From the water-soluble fraction of the dried leaves of Alangium chinense, three new glycosides, benzyl alcohol beta-D-glucopyranosyl-(1 --> 2)-[beta-D-xylopyranosyl-(1 --> 6)]-beta-D-glucopyranoside, 2'-O-beta-D-glucopyranosylsalicin, and 2'-O-beta-D-glucopyranosyl-6'-O-beta-D-xylopyranosylsalicin were isolated along with seven known glycosides. The structures of the new compounds were determined by spectroscopic and chemical means.     

A new steroidal saponin from Agave attenuata

A new steroidal saponin was isolated from the leaves of Agave attenuata. Its structure was established as (3beta,beta,25S)-spirostan-3-yl O-beta-D-glucopyranosyl-(1 --> 2)-beta-D-glucopyranosyl-(1 --> 2)-O-[beta-D-glucopyranosyl-(1 --> 3)]-beta-D-glucopyranosyl-(1 --> 4)-beta-D-galactopyranoside. The structural identification was performed using detailed analyses of 1H- and 13C-NMR spectra including 2D NMR spectroscopic techniques (COSY, HETCOR, and COLOC) and chemical conversions. The hemolytic activity of the steroidal saponin was evaluated using an in vitro assay.     

Pancreatic lipase-inhibiting triterpenoid saponins from Gypsophila oldhamiana

Three new triterpenoid saponins, gypsosaponins A-C (1-3), were isolated from the roots of Gypsophila oldhamiana (Caryophyllaceae). Their structures were established as 3-O-beta-D-galactopyranosyl-(1-->2)-[beta-D-xylopyranosyl-(1-->3)]-beta-D-glucuronopyranosyl quillaic acid 28-O-alpha-L-arabinopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-fucopyranoside (1), 3-O-beta-D-galactopyranosyl-(1-->2)-[beta-D-xylopyranosyl-(1-->3)]-methyl-beta-D-glucuronopyranosyl gypsogenin 28-O-beta-D-glucopyranosyl-(1-->3)-[beta-D-xylopyranosyl-(1-->4)]-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-fucopyranoside (2), and 23-O-beta-D-glucopyranosyl gypsogenic acid 28-O-beta-D-glucopyranosyl-(1-->3)-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranoside (3), on the basis of various spectroscopic analyses and chemical degradations. The biological activities of 1-3 were examined inhibitory activity against pancreatic lipase, which showed inhibition of 58.2%, 99.2% and 50.3% at concentration of 1 mg/ml, respectively.     

Antitumor activity of Pulsatilla koreana saponins and their structure-activity relationship

Seventeen saponins isolated from the root of Pulsatilla koreana were examined for their in vitro cytotoxic activity against the human solid cancer cell lines, A-549, SK-OV-3, SK-MEL-2, and HCT15, using the SRB assay method, and their in vivo antitumor activity using BDF1 mice bearing Lewis lung carcinoma (LLC). The saponins 5-17, with a free acidic functional group at C-28 of aglycon, exhibited moderate to considerable cytotoxic activity, however, the saponins 1-4, esterified with a trisaccharide at C-28 of aglycon, did not exhibit cytotoxic activity (ED50; >300 microM). Among them, oleanolic acid 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->4)]-alpha-L-arabinopyranoside (10) exhibited the most potent cytotoxic activity (ED50; 2.56, 2.31, 1.57, 8.36 microM, respectively). In vivo test, hederagenin 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->4)]-alpha-L-arabinopyranoside (6, Inhibition Ratio, IR; 66.9%) exhibited more potent antitumor activity than taxol (IR; 35.8%) and doxorubicin (IR; 62.1%). Also, hedragenin 3-O-beta-D-glucopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside (17, IR; 50.3%) exhibited potent antitumor activity. These two saponins were identically comprised of a hederagenin aglycon moiety and a sugar sequence O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside at C-3 of the hederagenin, suggesting that the two elements are essential factors for the antitumor activity.     

Ardisimamillosides G and H,two new triterpenoid saponins from Ardisia mamillata

Two new triterpenoid saponins, ardisimamilloside G (1), 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->4)-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl]-13beta,28-epoxy-16-oxo-oleanan-3beta,30-diol and ardisimamilloside H (2), 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->4)-alpha-L-arabinopyranosyl]-3beta-hydroxy-13beta,28-epoxy-16-oxo-oleanan-30-al, were isolated from the roots of Ardisia mamillata HANCE. Structure assignments were established on the basis of spectral data and chemical evidence.     

Eucosterol oligoglycosides isolated from Scilla scilloides and their anti-tumor activity

Two new eucosterol oligoglycosides, 15-deoxo-30-hydroxyeucosterol 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[(beta-D-glucopyranosyl-(1-->3)]-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranoside (scillanoside L-1, 1) and 3beta,31-dihydroxy-17alpha,23-epoxy-5alpha-lanost-8-en-23,26-olactone 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->3)]-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6)-beta-D-glucopyranoside (scillanoside L-2, 2), were isolated from the bulbs of Scilla scilloides, together with four that were known (3-6), have been isolated from the bulbs of Scilla scilloides. The structures of the new compounds were determined on the basis of spectroscopic and chromatographic methods, and some chemical transformations were discussed. Amongst the isolated compounds, 3 showed the most significant cytotoxicity against tumor cells tested several types with ED(50) value of 1.53-3.06 nM. In vivo experiments, 3 apparently increased the life span of mice bearing Sarcoma 180 tumor cell with T/C value of 239% at dose of 3 mg/kg.