Triterpene glycosides from the bark of Robinia pseudo-acacia L. I.

From the bark of Robinia pseudo-acacia L., five new triterpene glycosides, robiniosides A-D (3, 5-7) and compound III (4), were isolated and their structures were elucidated as 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl(1-->2)-beta-D- glucuronopyranosyl 3 beta,22 beta-dihydroxyolean-12-en-29-oic acid (3), 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-galactopyranosyl(1-->2)-beta-D -glucuronopyranosyl 3 beta,22 beta,24-trihydroxyolean-12-en-29-oic acid (4), whose sapogenol was unambiguously characterized and designated as oxytrogenin, 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl(1-->2)-beta-D glucuronopyranosyl oxytrogen (5), 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D galactopyranosyl(1-->2)-beta-D-glucuronopyranosyl oxytrogenin 22-O-alpha-L-rhamnopyranoside (6), 3-O-alpha-L- rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl(1-->2)-beta-D-glucuronop yranosyl oxytrogenin 22-O-alpha-L-rhamnopyranoside (7), respectively, together with two known triterpene glycosides, kaikasaponin III (1) and 3-O-alpha-L-rhamnopyranosyl(1-->2)-beta-D-galactopyranosyl(1-->2)-beta-D - glucuronopyranosyl 3 beta,22 beta-dihydroxyolean-12-en-29-oic acid (2).     

New furostanol saponins from Allium ascalonicum L

An analysis of the polar extracts from Allium ascalonicum L. led to the isolation of two new furostanol saponins (compound 1 and 2) and two known furostanol saponins (compound 3 and 4). On the basis of 1D and 2D NMR (including (1)H, (13)C NMR, (1)H--(1)H COSY, HSQC, TOCSY, HMBC, and NOESY), FAB-MS spectrometry, and chemical methods, their structures were elucidated as (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5alpha-furost-2-one-3beta, 5, 6beta, 26-tetraol-3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (ascalonicoside C, 1), (25R)-26-O-beta-D-glucopyranosyl-22-methoxy-5alpha-furost-2-one-3beta, 5, 6beta, 26-tetraol- 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside (ascalonicoside D, 2), (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5-ene-furostan-3beta, 26-diol-3-O-alpha-L-rhamnopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->4)-[alpha-L-rhamnopyranosyl-(1-->2)]-beta-D-glucopyranoside (dichotomin, 3), and (25R)-26-O-beta-D-glucopyranosyl-22-hydroxy-5-ene-furostan-3beta, 26-diol-3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-arabinofuranosyl-(1-->4)]-beta-D- glucopyranoside (parisaponin I, 4).     

Pregnane- and furostane-type oligoglycosides from the seeds of Allium tuberosum

Two furostane-type steroidal oligoglycosides (1, 2), together with a new pregnane-type oligoglycoside (3), were obtained from the seeds of Allium tuberosum ROTTLER. On the basis of spectroscopic analysis, the structures of three new oligoglycosides (1-3) were elucidated as 26-O-beta-D-glucopyranosyl-(25R)-3beta,22xi,26-trihydroxyl-5alpha-furostane 3-O-beta-chacotrioside, 26-O-beta-D-glucopyranosyl-(25S)-3beta,5beta,6alpha,22xi,26-pentahydroxyl-5beta-furostane 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranoside, and 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl 3beta,5beta,6alpha,16beta-tetrahydroxypregnane 16-(5-O-beta-D-glucopyranoyl-4(S)-methyl-5-hydroxypentanoic acid) ester, respectively.     

Steroidal glycosides and aromatic compounds from Smilax riparia

Two new steroidal glycosides named riparosides A (1) and B (2), and two aromatic compounds (3, 4), together with four known flavonoid derivatives have been isolated from the EtOH extract of the rhizomes and roots of Smilax riparia A. DC. The structure of riparoside A (1) was determined to be 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->6)]-beta-D-glucopyranosyl 3beta,20alpha-dihydroxy-5alpha-furost-22(23)-ene 26-O-beta-D-glucopyranoside. Riparoside B (2) was characterized as 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->6)]-beta-D-glucopyranosyl 3beta,16beta-dihydroxy-5alpha-pregnan-20-one 16-O-[5-O-beta-D-glucopyranosyl 5-hydroxy-4-methyl-pentanoic acid]-ester 26-O-beta-D-glucopyranoside. Compounds 3 and 4 were elucidated as a sucrosyl ferulic acid ester and 7-O-methyl-10-oxythymol gentiobioside, respectively.     

Steroidal oligoglycosides from the seeds of Allium tuberosum

Three new spirostanol steroidal oligoglycosides, together with a known oligoglycoside, were obtained from the seeds of Allium tuberosum after enzymatic hydrolysis of furostanol saponin fraction by beta-glucosidase. On the basis of spectroscopic analysis, the structure of new spirostanol oligoglycosides were elucidated as (25S)-spirost-5-ene-2alpha,3beta-diol 3-O-alpha-L-rhamnopyranosyl-(1-->4)-[alpha-L-rhamnopyranosyl-(1-->2)]-be ta-D-glucopyranoside, (25S)-spirostane-3beta,5beta,6alpha-triol 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranoside, and (25S)-5beta-spirostane-3beta,6alpha-diol 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranoside.     

Latifolosides I and J, two new triterpenoid saponins from the bark of Ilex latifolia

Two new triterpenoid saponins, latifoloside I (1), 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl 3beta,21alpha,28-trihydroxy-urs-12-ene 21-O-beta-D-glucopyranoside; latifoloside J (2), 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl-3beta,21alpha-dihydroxy-ursolic acid 21-O-beta-D-glucopyranoside, along with two known compounds, latifoloside C (3) and latifoloside E (4), were isolated from the bark of Ilex latifolia THUNB. Structure assignments were established on the basis of spectroscopic data and chemical evidence.     

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.     

Four new oleanane saponins from Anemone anhuiensis

Four new oleanane triterpene saponins, anhuienosides C-F, together with three known saponins, were isolated from the rhizomes of Anemone anhuiensis (Ranunculaceae). The structures of anhuienosides C-F were elucidated as 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-xylopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3-O-beta-D-xylopyranosyl oleanolic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl oleanolic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3-O-beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-xylopyranosyl oleanolic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, respectively.     

Studies on the constituents of Clematis species. VIII. Triterpenoid saponins from the aerial part of Clematis tibetana KUNTZ

From the aerial part of Clematis tibetana, two new hederagenin 3,28-O-bisdesmosides called clematibetosides A and C, and a new gypsogenin 3,28-O-bisdesmoside called clematibetoside B, have been isolated together with ten known saponins. The structures of the new saponins have been elucidated based on chemical and spectral evidence as follows: clematibetoside A, 3-O-(2-O-caffeoyl)-beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->4)-beta-D-ribopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl hederagenin 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyraside; clematibetoside B, 3-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl gypsogenin 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside; clematibetoside C, 3-O-beta-D-ribopyranosyl hederagenin 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranoside.     

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.     

Five new bidesmoside triterpenoid saponins from Stauntonia chinensis

Eleven triterpenoid saponins (1-11) were isolated from Stauntonia chinensis DC. (Lardizabalaceae), including five new compounds, yemuoside YM(21-25) (1-3, 6, 7) structures of which were elucidated by chemical methods and a combination of MS, 1D- and 2D- NMR experiments including DEPT, (1)H--(1)H COSY, HSQC, HMBC, TOCSY, and NOESY as 3-O-alpha-L-arabinopyranosyl-(1 --> 3)-[alpha-L-rhamnopyranosyl-(1 --> 2)-]alpha-L-arabinopyranosyl-akebonicacid-28-O-alpha-L-rhamnopyranosyl-(1 --> 4)-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (1), 3-O-beta-D-xylopyranosyl-(1 --> 3)-alpha-L-rhamnopyranosyl-(1 --> 2)-alpha-L-arabinopyranosyl-akebonic acid-28-O-alpha-L-rhamnopyranosyl-(1 --> 4)-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (2), 3-O-beta-D-glucopyranosyl-(1 --> 3)-alpha-L-arabinopyranosyl-akebonic acid-28-O-alpha-L-rhamnopyranosyl-(1 --> 4)-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (3), 3-O-alpha-L-arabinopyranosyl-(1 --> 3)-[alpha-L-rhamnopyranosyl-(1 --> 2)-]alpha-L-arabinopyranosyl-akebonic acid-28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (6), 3-O-alpha-L-arabinopyranosyl-(1 --> 3)-[alpha-L-arabinopyranosyl-(1 --> 2)-]alpha-L-arabinopyranosyl-akebonic acid-28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (7).     

Lupane-triterpene glycosides from the leaves of Acanthopanax gracilistylus

A novel lupane-triterpene glycoside, called wujiapioside B (1), was isolated from the leaves of Acanthopanax gracilistylus (Araliaceae) together with three known lupane-triterpene glycosides, acankoreoside C (2), acantrifoside A (3) and 3-epibetulinic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (4). Based on spectroscopic data, the chemical structure of 1 was determined as 3alpha,23-dihydroxy-lup-20(29)-en-28-oic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester. Compounds 2-3 were obtained for the first time from this plant and compound 4 has not been isolated from Acanthopanax genus yet.     

A new steroidal saponin from Dioscorea cayenensis

The new 26-O-beta-D-glucopyranosyl-3beta,26-dihydroxy-20,22-seco-25(R)-furost-5-en-20,22-dione-3-O-alpha-L-rhamnopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->4)-[alpha-L-rhamnopyranosyl-(1-->2)]-beta-D-glucopyranoside (1), along with the known methyl protodioscin (2), asperoside (3) and prosapogenin A of dioscin (4) were isolated from the rhizomes of Dioscorea cayenensis LAM.-HOLL (Dioscoreaceae). Their structures were established mainly on the basis of 600 MHz 2D-NMR spectral data. 4 exhibited antifungal activity against the human pathogenic yeasts Candida albicans, C. glabrata and C. tropicalis (MICs of 20.8, 6.25, 25 microg/ml, respectively), whereas saponins 1-3 were inactive.     

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.     

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.     

Isolation and structure of monomethylated GM3-type ganglioside molecular species from the starfish Luidia maculata

Two monomethylated GM(3)-Type ganglioside molecular species, 1 and 2, have been obtained from the polar lipid fraction of the chloroform/methanol extract of the starfish Luidia maculata. The structures of these gangliosides have been determined on the basis of chemical and spectroscopic evidence as 1-O-[8-O-methyl-(N-acetyl-alpha-D-neuraminosyl)-(2-->3)-beta-D-galactopyranosyl-(1-->4)-beta-D-glucopyranosyl]-ceramide (1) and 1-O-[8-O-methyl-(N-glycolyl-alpha-D-neuraminosyl)-(2-->3)-beta-D-galactopyranosyl-(1-->4)-beta-D-glucopyranosyl]-ceramide (2). The ceramide moieties were composed of heterogeneous unsubstituted fatty acid, 2-hydroxy fatty acid, sphingosine and phytosphingosine units. Compound 1, designated as LMG-3, represents new ganglioside molecular species. Compound 2 was a known ganglioside molecular species.     

1H and 13C NMR spectral data of new saponins from Cordia piauhiensis

Two new bidesmoside triterpenoid saponins were isolated from stems of Cordia piauhiensis. Their structures, characterized as 3-O-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl pomolic acid 28-O-beta-D-glucopyranosyl ester (1) and 3-O-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (2), were unequivocally established after extensive NMR (1H, 13C, DEPT 135 degrees, COSY, HSQC, HMBC, TOCSY, and NOESY) studies.     

Complete 1H and 13C NMR assignments for two new monodesmoside saponins from Pentaclethra macroloba (Willd.) Kuntze

A detailed NMR study and full assignments of the 1H and 13C spectral data for two novel triterpenoid saponins isolated from the stem bark of Pentaclethra macroloba (Willd.) Kuntze are described. Their structures were established using a combination of 1D and 2D NMR techniques including 1H,1H-COSY, TOCSY, NOESY, gs-HMQC and gs-HMBC, and also electrospray ionization mass spectrometry and chemical methods. The structures were established as 3beta-O-([O-beta-D-glucopyranosyl-(1-->2)-O-beta-D-glucopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)]-[O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->4)])-alpha-L-arabinopyranosylhederagenin (1) and 3beta-O-)[O-beta-D-glucopyranosyl-(1-->2)-O-beta-D-glucopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->3)-O-alpha-L-rhamnopyranosyl-(1-->2)]-[O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->4)])-alpha-L-arabinopyranosyloleanolic acid (2).     

Four new triterpene glycosides from Nigella damascena

Four new triterpene glycosides, named nigellosides A, B, C, and D, were from the air-dried aerial parts of Nigella damascena L. (Ranunculaceae), and the structures were elucidated on the basis of spectroscopic data including 2D NMR spectra and chemical evidence. Their chemical structures have been characterized as 3-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl gypsogenin 28-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3-O-beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl gypsogenin 28-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-xylopyranosyl hederagenin 28-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, and 3-O-beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-xylopyranosyl hederagenin 28-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester.     

Two triterpenoid saponins from Neonauclea sessilifolia

From the dried roots of Neonauclea sessilifolia (Rubiaceae), two new triterpenoid saponins, 3-O-beta-D-glucopyranosyl-(1-->2)-beta-D-quinovopyranosyl quinovic acid (1) and 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-quinovopyranosyl pyrocincholic acid 28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (2), were isolated, together with five known saponins. The structures of the new saponins were determined by spectroscopic and chemical means.