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.     

Acetylated triterpene saponins from the Thai medicinal plant, Sapindus emarginatus

From the pericarps of Sapindus emarginatus (Sapindaceae), three new acetylated triterpene saponins were isolated together with hederagenin and five known triterpene saponins, as well as one known sweet acyclic sesquiterpene glycoside, mukurozioside IIb. The structures of new compounds were elucidated as hederagenin 3-O-(2-O-acetyl-beta-D-xylopyranosyl)-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside, 23-O-acetyl-hederagenin 3-O-(4-O-acetyl-beta-D-xylopyranosyl)-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside and oleanolic acid 3-O-(4-O-acetyl-beta-D-xylopyranosyl)-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside by chemical and spectroscopic data.     

Saponins and other constituents from the leaves of Aralia elata

A new triterpenoid saponin, together with five known saponins, were isolated from the nonpolar n-hexane fraction of the leaves of Aralia elata. The structure of the new saponin, durupcoside C, was elucidated as hederagenin 3-O-beta-D-glucopyranosyl(1-->3)-beta-D-glucopyranosyl(1-->3)-alpha-L-arabinopyranoside on the basis of spectroscopic analysis. The known saponins were characterized as 3-O-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranosyl hederagenin 28-O-beta-D-xylopyranosyl(1-->6)-beta-D-glucopyranosyl ester, hederagenin 3-O-beta-D-glucopyranosyl(1-->3)-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside, oleanolic acid 3-O-beta-D-glucopyranosyl(1-->3)-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside, hederagenin 3-O-alpha-L-rhamnopyranosyl(1-->2)-alpha-L-arabinopyranoside (alpha-hederin), and hederagenin 3-O-beta-D-glucopyranosyl(1-->3)-alpha-L-arabinopyranoside (collinsonidin). In addition, two known lipids, Arisaema glyceride 3 and ceramide mixtures were also isolated and characterized. Collinsonidin and two known lipids were isolated for the first time from this plant.     

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.     

Five new triterpenoid saponins from the roots of Platycodon grandiflorum

Five new triterpenoid saponins, platycoside H [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23-tetrahydroxyolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], platycoside I [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23-tetrahydroxyolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], platycoside J [3-O-beta-D-glucopyranosyl-2beta,3beta,16alpha,23-tetrahydroxyolean-12-en-28-oic acid 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], platycoside K [3-O-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23,24-pentahydroxyolean-12-en-28-oic acid], and platycoside L [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-2beta,3beta,16alpha,23,24-pentahydroxyolean-12-en-28 oic acid], and three known triterpenoid saponins, platycoside F, platycoside B, and platycoside C, were isolated from the roots of Platycodon grandiflorum A. DC. Their chemical structures were elucidated on the basis of their spectral data and chemical evidence.     

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.     

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).     

Three new oleanene glycosides from Sophora flavescens.

Three new oleanene glycosides, sophoraflavosides II-IV (2-4) were isolated together with sophoraflavoside I (1) as the corresponding methyl ester forms from Sophorae Radix, the fresh roots of Sophora flavescens AITON (Leguminosae). Their structures have been elucidated as oxytrogenin 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-galactopyranosyl-(1-->2)-beta -D- glucuronopyranoside (2), 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-galactopyranosyl-(1-->2)-beta -D-glucuronopyranosyl oxytrogenin 22-O-alpha-L-arabinopyranoside (3) and 3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-galactopyranosyl-(1-->2)-beta -D-glucuronopyranosyl oxytrogenin 22-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranoside (4), along with unambiguous characterization as 3 beta,22 beta,24-trihydroxyolean-12-en-29-oic acid for their sapogenol, named oxytrogenin (5) on the bases of chemical reactions and spectral analyses.     

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).     

Two new triterpenoid saponins from Platycodon grandiflorum.

Two new triterpenoid saponins, platycoside D [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->6)-beta-D- glucopyranosyl-2 beta, 3 beta, 16 alpha, 23-tetrahydroxyolean-12-ene-28-oic acid 28-O-beta-D- apiofuranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnop yranosyl- (1-->2)-alpha-L-arabinopyranoside] and platycoside E [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl- (1-->6)-beta-D-glucopyranosyl-2 beta,3 beta,16 alpha,23,24-pentahydroxyolean-12-ene-28-oic acid 28-O-beta-D-apiofuranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alp ha-L- rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside] were isolated from the roots of Platycodon grandiflorum. Structural determination is based on spectral and chemical evidence.     

New A-ring lactone triterpenoid saponins from the roots of Platycodon grandiflorum

Three new A-ring lactone triterpenoid saponins, platycoside M-1 [3-O-beta-D-glucopyranosyl platycogenic acid A lactone], platycoside M-2 [3-O-beta-D-glucopyranosyl platycogenic acid A lactone 28-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], and platycoside M-3 [3-O-beta-D-glucopyranosyl platycogenic acid A lactone 28-O-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], were isolated from the roots of Platycodon grandiflorum A. DC. Their chemical structures were elucidated on the basis of their spectral data and chemical evidence.     

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).     

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.     

Cardiac glycosides from Erysimum cheiranthoides

Three new cardiac glycosides named cheiranthoside VIII (1), cheiranthoside IX (2) and cheiranthoside X (3) were isolated from the seeds of Erysimum cheiranthoides. Based on spectroscopic data, the structures of 1-3 were characterized as strophanthidin 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-antiaropyranoside, cheiranthidin 3-O-beta-D-glucopyranosyl-(1-->4)-beta-D-boiviopyranoside and cheiranthidin 3-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-digitoxopyranoside, respectively. The aglycone moiety possessing a carboxyl group at C-10 of 2 and 3 was regarded to be determined for the first time.     

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.     

Triterpenoid saponins from Lysimachia davurica

Three new saponins were isolated from the whole plants of Lysimachia davurica. On the basis of 1D and 2D NMR ((1)H-(1)HCOSY, HMBC, HMQC, and TOCSY) techniques, MS, and hydrolysis, their structures were found to be 3-O-beta-D-glucopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->4)]-alpha-L-arabinopyranosyl-13,28-epoxy-3beta-hydroxy-16-oleanaone (1), 3-O-beta-D-glucopyranosyloxyuronic acid-(1-->2)-beta-D-xylopyranosyl-cyclamiretin A (2), and 3-O-beta-D-glucopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-cyclamiretin A (3), respectively. Compounds 2 and 3 showed significant cytotoxicities against human A-2780 cells.     

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.     

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.     

Triterpenoid saponins from the fruits of Akebiae quinata

Three new triterpenoid saponins together with eight known compounds have been isolated from the fruits of Akebiae quinata. On the basis of the spectroscopic and physiochemical evidence, the new compounds were elucidated as 3-O-beta-D-xylopyranosyl-(1-->2)-alpha-L-arabinopyranosyl gypsogenin, 3-O-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl gypsogenin and 3-O-beta-D-xylopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl gypsogenin.