Transglycosylation to ginseng saponins by cyclomaltodextrin glucanotransferases

Ten new alpha-glucosylginsenosides were found to be synthesized from dextrin and four ginsenosides, -Rb1, -Rc, -Re, and -Rg1, by the successive actions of B. stearothermophilus cyclomaltodextrin glucanotransferase and Rhizopus glucoamylase. Seven of them were isolated in the pure state by extraction with n-butanol saturated with water, silica gel column chromatography, and high pressure liquid chromatography, and identified as 3-O-[alpha-D-glcp-(1-->4)-beta-D-glcp-(1-->2)-beta-D-glcp]-20-O-[beta-D-glcp-(1-->6)-beta-D-glcp]-20(S)-protopanaxadiol, 3-O-[beta-D-glcp-(1-->2)-beta-D-glcp]-20-O-[alpha-D-glcp-(1-->4)-beta-D-glcp-(1-->6)-beta-D-glcp]-20(S)-protopanaxadiol, 3-O-[alpha-D-glcp-(1-->4)-beta-D-glcp-(1-->2)-beta-D-glcp]-20-O-[alpha-L-araf-(1-->6)-beta-D-glcp]-20(S)-protopanaxadiol, 3-O-[beta-D-glcp-(1-->2)-beta-D-glcp]-20-O-[(4G-alpha-D-glcp)-alpha-L-araf-(1-->6)-beta-D-glcp]-20(S)-protopanaxadiol, 6-O-[alpha-L-rhap-(1-->2)-beta-D-glcp]-20-O-[alpha-D-glcp-(1-->4)-beta-D-glcp]-20(S)-protopanaxatriol, 6-O-[alpha-D-glcp-(1-->4)-beta-D-glcp]-20-O-(beta-D-glcp)-20(S)-protopanaxatriol, and 6-O-[alpha-D-glcp-(1-->3)-beta-D-glcp]-20-O-(beta-D-glcp)-20(S)-protopanaxatriol, by spectroscopy (FAB-MS, IR, 1H-NMR and 13C-NMR) and hydrolysis products in 50% acetic acid. The bitterness of these alpha-glucosyl-ginsenosides was less than that of ginsenosides.     

Spirostanol saponins of Allium porrum L.

An investigation of the extracts from bulbs of Allium porrum L. has led to the isolation of four spirostanol saponins. Two of them are new compounds and have been identified as: (25R)-5 alpha-spirostan-3 beta, 6 beta-diol 3-O-{O-beta-D-glucopyranosyl-(1-->2)-O-[beta-D-xylopyranosyl-(1-->3)]-O- beta -D-glucopyranosyl-(1-->4)-beta-D-galactopyranoside} (3) and (25R)-5 alpha-spirostan-3 beta,6 beta-diol 3-O-{O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->2)-O- [beta-D-xylopyranosyl-(1-->3)]-O-beta-D-glucopyranosyl-(1-->4)-beta-D- galactopyranoside} (4). The isolated compounds were evaluated for their antifungal activity.     

New steroid glycosides from the starfish Fromia milleporella

Two new steroid glycosides from the starfish Fromia milleporella collected in the Seychelles were isolated and characterized: milleporoside A, (20R, 24R)-29-O-[3-O-methyl-beta-D-xylopyranosyl-(1-->4)-3-O-methyl-beta-D-xylopyranosyl]-24-ethyl-5alpha-cholestane-3beta,4beta,6alpha,8,15beta,16beta,29-heptaol, and milleporoside B, (20R, 24R)-(22E)-28-O-[3-O-methyl-beta-D-xylopyranosyl-(1-->4)-3-O-methyl-beta-D-xylopyranosyl]-24-methyl-5alpha-cholest-22-ene-3beta,4beta,6alpha,8,15beta,16beta,28-heptaol. The structures of the glycosides were determined from their spectra and a comparison with spectral characteristics of known compounds. These compounds exhibit a moderate cytostatic activity toward the embryos of the sea urchin Strongylocentrotus intermedius.     

Polyoxypregnane glycosides from Caralluma retrospiciens

Six related polyoxypregnane glycosides were isolated and characterised from Caralluma retrospiciens leaves. The compounds were identified as 12beta-benzoyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[3-O-methyl-6-deoxy-beta-D-allopyranosyl-(1 --> 4)-beta-D-cymaropyranosyl-(1 --> 4)-]-beta-D-cymaropyranoside], 12beta-benzoyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-allopyranosyl-(1 --> 4)-beta-D-cymaropyranosyl-(1 --> 4)-beta-D-cymaropyranoside], 12beta-benzoyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranoside], 12beta-benzoyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranoside], 12beta-benzoyloxy-11alpha-isovaleroyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranosyl-(1 --> 4)-3-O-methyl-6-deoxy-beta-D-galactopyranoside], and 12beta-benzoyloxy-11alpha-isovaleroyloxy-8beta,14beta-dihydroxypregn-20-one-3-O-[beta-D-glucopyranosyl (1 --> 4)-3-O-methyl-6-deoxy-beta-D-allopyranosyl-(1 --> 4)-beta-D-cymaropyranosyl-(1 --> 4)-beta-D-cymaropyranoside]. The structures were determined by detailed analysis of one- and two-dimensional NMR spectra as well as by chemical means. The compounds showed cytotoxic activities towards brine shrimp having IC50 values of 1.19 x 10(-4), 8.83 x 10(-5), 2.64 x 10(-4), 2.26 x 10(-4), 2.39 x 10(-4) and 1.70 x 10(-4) M, respectively. This is the first report of the isolation of these compounds from a natural source.     

Two diastereomeric saponins with cytotoxic activity from Albizia julibrissin

Two diastereomeric saponins, julibrosides J1 (1) and J9 (2), both of which show cytotoxic activity, were obtained from the stem bark of Albizia julibrissin Durazz. On the basis of chemical and spectral evidence [L.B. Ma et al., Carbohydr. Res., 281 (1996) 35-46], the structure of 1 was revised as 3-O-[beta-D-xylopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6) -beta-D-glucopyranosyl]-21-O-[(6S)-2-trans-2-hydroxymethyl-6-methyl-6-O- [4-O-((6R)-2-trans-2,6-dimethyl-6-O-(beta-D-quinovopyranosyl)-2,7- octadienoyl)-beta-D-quinovopyranosyl]-2,7-octadienoyl] acacic acid-28-O-beta-D-glucopyranosyl-(1-->3)-[alpha-L-arabinofuranosyl-(1-->4 )]-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl ester. The diastereoisomer 2 of 1 was identified as 3-O-[beta-D-xylopyranosyl-(1-->2)-alpha-L-arabinopyranosyl-(1-->6) -beta-D-glucopyranosyl]-21-O-[(6S)-2-trans-2-hydroxymethyl-6-methyl-6-O- [4-O-((6S)-2-trans-2,6-dimethyl-6-O-(beta-D-quinovopyranosyl)-2,7- octadienoyl)-beta-D-quinovopyranosyl]-2,7-octadienoyl] acacic acid-28-O-beta-D-glucopyranosyl-(1-->3)-[alpha-L-arabinofuranosyl-(1-->4 )]-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl ester. Saponin 2 is a new saponin named julibroside J9. Both julibrosides J1 and J9 show good inhibitory action against the KB cancer cell line in vitro.     

Neolignan glycosides from Symplocos caudata

A phytochemical investigation of the roots of Symplocos caudata Wall (Symplocaceae) resulted in isolation and characterization of four optical isomers of a neolignan glycoside (1-4), a lignan lactone glycoside (5), a phenylpropanoid glycoside (6), as well as two known compounds (7, 8). Their structures were elucidated as (7S,8S)-threo-7,9,9'-trihydroxy-3,3'-dimethoxy-8-O-4'-neolignan-4-O-beta-d-glucopyranoside (1), (7R,8R)-threo-7,9,9'-trihydroxy-3,3'-dimethoxy-8-O-4'-neolignan-4-O-beta-d-glucopyranoside (2), (7R,8S)-erythro-7,9,9'-trihydroxy-3,3'-dimethoxy-8-O-4'-neolignan-4-O-beta-d-glucopyranoside (3), (7S,8R)-erythro-7,9,9'-trihydroxy-3,3'-dimethoxy-8-O-4'-neolignan-4-O-beta-d-glucopyranoside (4), 8R,8'R-matairesinol-4-O-beta-d-xylopyranosyl-(1-->2)-O-beta-d-glucopyranoside (5), 1-O-[beta-d-xylopyranosyl-(1-->6)-O-beta-d-glucopyranosyl]-2,6-dimethoxy-4-propenyl-phenol (6), matairesinoside (7), and (R)-1-O-(beta-d-glucopyranosyl)-2-[2-methoxy-4-(omega-hydroxypropyl)-phenoxyl]-propan-3-ol (8) on the basis of spectroscopic data (1D and 2D NMR, MS and CD) and chemical evidence.     

Triterpenoid saponins from the fruits and galls of Sapindus mukorossi

Six saponins, sapinmusaponin K (1) [hederagenin-3-O-(3-O-acetyl-alpha-L-arabinopyranosyl)-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], sapinmusaponin L (2) [hederagenin-3-O-(4-O-acetyl-alpha-L-arabinopyranosyl)-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabino-pyranoside], sapinmusaponin M (3) [hederagenin-3-O-(2,3-O-diacetyl-beta-D-xylopyranosyl)-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], sapinmusaponin N (4) [hederagenin-3-O-(2,4-O-diacetyl-beta-D-xylopyranosyl)-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside], sapinmusaponin O (5) [3,7,20(S)-trihydroxydammar-24-ene-3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranoside], and sapinmusaponin P (6) [3,7,20(R)-trihydroxydammar-24-ene-3-O-alpha-L-rhamnopyranosyl-(1-->2)-beta-d-glucopyranoside], along with seven known saponins (7-13), were isolated from fruits and the galls of Sapindus mukorossi. Their structures were elucidated by 1D and 2D NMR spectroscopic techniques and acid hydrolysis. Biological evaluation indicated that saponins 1-4 and 7-13 showed moderate cytotoxicity against several human tumor cell lines.     

Further saponins from Meryta lanceolata

Five new oleanane-type saponins along with 11 known ones were isolated from the leaves and stems of Meryta lanceolata. The new saponins were characterised by spectroscopic analysis including FAMS, 1 and 2D NMR experiments and the results of hydrolysis as 3-O-[beta-d-glucopyranosyl-(1-->2)-beta-d-glucuronopyranosyl] hederagenin 28-O-[alpha-l-rhamnopyranosyl-(1-->4)-beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranosyl] ester, 3-O-[beta-d-glucopyranosyl-(1-->2)-beta-d-glucuronopyranosyl] oleanolic acid 28-O-[alpha-l-rhamnopyranosyl-(1-->4)-beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranosyl]ester, 3-O-[beta-d-glucopyranosyl-(1-->2)-beta-d-glucuronopyranosyl] oleanolic acid 28-O-[alpha-l-rhamnopyranosyl-(1-->4)-beta-d-6-O-acetyl glucopyranosyl-(1-->6)-beta-d-glucopyranosyl]ester, 3-O-[beta-d-glucopyranosyl-(1-->3)-beta-d-glucopyranosyl-(1-->3)-alpha-l-arabinopyranosyl] oleanolic acid 28-O-[alpha-l-rhamnopyranosyl-(1-->4)-beta-d-glucopyranosyl-(1-->6)-beta-d-glucopyranosyl] ester and 3-O-[beta-d-glucopyranosyl-(1-->2)-beta-d-glucuronopyranosyl] hederagenin, respectively.     

Acetylated glucuronide triterpene bidesmosidic saponins from Symplocos glomerata

Nine new bidesmosidic 3-O-glucuronide oleanane triterpenoid saponins were isolated from the stem bark of Symplocos glomerata King along with two known saponins, salsoloside C and copteroside E, and two major lignans, (-)-pinoresinol and (-)-pinoresinol-4'-O-beta-D-glucopyranoside. The structures of the new saponins were established using one- and two-dimensional NMR spectroscopy and mass spectrometry as, 3-O-[beta-D-xylopyranosyl(1-->4)-[2-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[beta-D-xylopyranosyl(1-->4)-[3-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[beta-D-xylopyranosyl (1-->4)-[2,3-O-diacetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[alpha-L-arabinopyranosyl(1-->4)-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[alpha-L-arabinopyranosyl (1-->4)-[2-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[[beta-D-xylopyranosyl (1-->2)]-[beta-D-xylopyranosyl (1-->4)]-[3-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[[beta-D-glucopyranosyl (1-->2)]-[beta-D-xylopyranosyl (1-->4)]-[3-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, 3-O-[[beta-D-glucopyranosyl (1-->2)]-[alpha-L-arabinofuranosyl (1-->4)]-[3-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-oleanolic acid, and 3beta-O-[beta-D-xylopyranosyl(1-->4)-[2-O-acetyl]-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-morolic acid. The EtOH and EtOAc extracts of the stem bark showed no cytotoxic activity. At a concentration of 370 microg/ml, the saponin mixture showed haemolytic activity and caused 50% haemolysis of a 10% suspension of sheep erythrocytes.     

Triterpenoid saponins from Oreopanax guatemalensis

Seven oleanane-type saponins were isolated from the leaves and stems of Oreopanax guatemalensis, together with ten known saponins of lupane and oleanane types. The new saponins were respectively characterized as 3-O-alpha-L-arabinopyranosyl echinocystic acid 28-O-[alpha- L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester, 3-O-beta-D-glucopyranosyl 3beta-hydroxy olean-11,13(18)-dien-28-oic 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]3beta-hydroxy olean-11,13(18)-dien-28-oic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester, 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]3beta, 23 dihydroxy olean-18-en-28-oic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-6-O-acetyl glucopyranosyl-(1-->6)-beta-D-glucopyranosyl]ester, 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl] hederagenin 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-[beta-D-xylopyranosyl-(1-->2 )-]beta-D-glucopyranosyl]ester, 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]hederagenin 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-[beta-D-glucopyranosyl-(1-->2)-]beta-D-glucopyranosyl] ester and 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl] hederagenin 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-[alpha-L-arabinofuranosyl-(1-->2)]-beta-D-glucopyranosyl] ester. The structures were determined by spectral analyses. The NMR assignments were made by means of HOHAHA, 1H-1H COSY, HMQC, HMBC spectra and NOE difference studies.     

Triterpenoid saponins from Meryta lanceolata

Four new oleanane-type saponins and a known one were isolated from the leaves and stems of Meryta lanceolata. The new saponins were characterised by spectroscopic means and chemical hydrolysis as 3-O-[beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->3)-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl]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)-beta-D-glucopyranosyl-(1-->3)-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl]oleanolic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-6-O-acetyl glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester, 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->3)-alpha-L-arabinopyranosyl]oleanolic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester and 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl-(1-->3)-beta-D-glucopyranosyl-(1-->3)-alpha-L-arabinopyranosyl]echinocystic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester. The NMR assignments were made by means of HOHAHA, 1H-1H COSY, HMQC, HMBC and NOE difference studies.     

Pyruvated galactose and oligosaccharides from Erwinia chrysanthemi Ech6 extracellular polysaccharide

The acidic extracellular polysaccharide of Ech6 was depolymerized by fuming HCl. The pyruvated sugars were isolated and characterized by methods that included a combination of low-pressure gel-filtration and high-pH anion-exchange chromatographies, methylation linkage analyses, mass (GC-MS and MALDI-TOF MS) and 1H NMR (1D and 2D) spectroscopies. The following pyruvated sugars were obtained: 4,6-O-(1-carboxyethylidene)-D-Galp; 4,6-O-(1-carboxyethylidene)- alpha-D-Galp-(1-->4)-beta-D-GlcAp-(1-->3)-D-Galp; 4,6-O-(1-carboxyethylidene)-alpha-D-Galp-(1-->4)-alpha-D-GlcAp- (1-->3)-alpha-D-Galp-(1-->3)-L-Fucp; 4,6-O-(1-carboxyethylidene)-alpha-D-Galp-(1-->4)-beta-D-GlcAp-(1-->3) -alpha-D-Galp-(1-->3)-L-[beta-D-Glcp-(1-->4)]-Fucp. These oligosaccharides present potential haptenes for the development of specific antibodies and confirm the partial structure proposed previously for the extracellular polysaccharide from Erwinia chrysanthemi Ech6 [Yang, B. Y.; Gray, J. S. S.; Montgomery, R. Int. J. Biol. Macromol., 1994, 16, 306-312].     

Saponins and acylated saponins from Dizygotheca kerchoveana

Four new triterpenoid saponins were isolated from the leaves and stem of branches of Dizygotheca kerchoveana along with seven known ones. The new saponins were respectively characterized as 3-O-[beta-D-glucopyranosyl-(1-->3)]-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl echinocystic acid, 3-O-[beta-D-glucopyranosyl-(1-->3)]-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl echinocystic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester, 3-O-[beta-D-3-O-trans-p-coumaroyl-glucopyranosyl-(1-->3)]-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl echinocystic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester and 3-O-[beta-d-3-O-cis-p-coumaroyl-glucopyranosyl-(1-->3)]-[beta-D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl echinocystic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester. Their structures were elucidated by 1D and 2D NMR experiments, FAB-MS as well as chemical means.     

New steroidal saponins from rhizomes of Costus spiralis

Two new steroidal saponins were isolated from the rhizomes of Costus spiralis Rosc. Their structures were established as (3beta,25R)-26-(beta-D-glucopyranosyloxy)-22-hydroxyfurost-5-en-3-yl O-D-apio-beta-D-furanosyl-(1-->2)-O-[alpha-L-rhamnopyranosyl-(1-->4)]-beta-D-glucopyranoside (1) and (3beta,25R)-26-(beta-D-glucopyranosyloxy)-22-hydroxyfurost-5-en-3-yl O-D-apio-beta-D-furanosyl-(1-->4)-O-[alpha-L-rhamnopyranosyl-(1-->2)]-beta-D-glucopyranoside (2). Their structural identifications were performed using detailed analyses of 1H and 13C NMR spectra including 2D NMR spectroscopic techniques (DEPT, COSY, HETCOR and COLOC) and chemical conversions. The steroidal saponins were evaluated for anti-inflammatory activity.     

Withanolide glycosides from Dunalia australis.

Four new withanolide glycosides, (20R,22R)-O-(3)-[beta-D- xylopyranosyl(1----3), beta-D-xylopyranosyl(1----4)]-beta-D-glucopyranosyl-3 beta,20-dihydroxy-1 alpha-acetoxy-witha-5,24-dienolide, (20R,22R)-O-(3)-[beta-D-xylopyranosyl(1----3), beta-D-glucopyranosyl(1----4)]-beta-D-glucopyranosyl-3 beta,20-dihydroxy-1 alpha-acetoxy-witha-5,24-dienolide, (20R,22R)-O-(3)-[beta-D- glucopyranosyl(1----3), beta-D-glucopyranosyl(1----4)]-beta-D-glucopyranosyl- 3 beta,20-dihydroxy-1 alpha-acetoxy-witha-5,24-dienolide and (20R,22R)-O-(3)-[beta-D-glucopyranosyl(1----3), beta-D- glucopyranosyl(1----4)]-beta-D-glucopyranosyl-3 beta, 12 beta,20-trihydroxy- 1 alpha,acetoxy-witha-5,24-dienolide, named dunawithanines C, D, E and F, respectively, were isolated from Dunalia australis. Their structures were elucidated on the basis of spectral and chemical evidence, especially NMR data of the peracetates.     

Furostanol saponins and quercetin glycosides from the leaves of Helleborus viridis L

Phytochemical analysis of the polar extracts of the leaves of Helleborus viridis (Ranunculaceae) resulted in the isolation of two new furostanol saponins (25R)-26-[(alpha-L-rhamnopyranosyl)oxy]-22alpha-methoxyfurost-5-en-3beta-yl O-beta-D-glucopyranosyl-(1-->3)-O-[6-acetyl-beta-D-glucopyranosyl-(1-->3)]-O-beta-D-glucopyranoside (1) and (25R)-26-[(alpha-L-rhamnopyranosyl)oxy]-22alpha-methoxyfurost-5-en-3beta-yl O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranosyl-(1-->3)-O-beta-D-glucopyranoside (2) and three new quercetin glycosides, quercetin 3-O-(2-E-caffeoyl)-alpha-L-arabinopyranosyl-(1-->2)-beta-D-galactopyranoside-7-O-beta-d-glucopyranoside (3), quercetin 3-O-(2-E-caffeoyl)-alpha-L-arabinopyranosyl-(1-->2)-beta-D-galactopyranoside (4), and quercetin 3-O-alpha-L-arabinopyranosyl-(1-->2)-beta-D-galactopyranoside (5). The structures of the new compounds were determined by spectroscopic analysis, including 2D NMR data and mass spectrometry.     

Glucuronide triterpene saponins from Bersama engleriana

Five 3-O-glucuronide triterpene saponins (1-5) were isolated from the stem bark of Bersama engleriana Gurke along with two known saponins, polyscias saponin C and aralia saponin 15, and one major C-glycoside xanthone, mangiferin. The structures of the saponins were established mainly by means of spectroscopic methods (one- and two-dimensional NMR spectroscopy as well as FAB-, HRESI-mass spectrometry) as 3-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl]-betulinic acid (1), 3-O-[beta-D-glucopyranosyl-(1-->2)-[beta-D-galactopyranosyl-(1-->3)]-beta-D-glucuronopyranosyl]-oleanolic acid (2), 3-O-[beta-D-glucopyranosyl-(1-->3)-beta-D-glucuronopyranosyl]-28-O-[beta-D-xylopyranosyl-(1-->6)-beta-d-glucopyranosyl]-oleanolic acid (3), 3-O-[beta-D-galactopyranosyl-(1-->3)-beta-D-glucuronopyranosyl]-28-O-[beta-D-glucopyranosyl-(1-->4)-beta-D-glucopyranosyl]-oleanolic acid (4), and 3-O-[beta-d-glucopyranosyl-(1-->3)-beta-D-galactopyranosyl-(1-->3)-beta-D-glucuronopyranosyl]-28-O-[beta-d-xylopyranosyl-(1-->6)-beta-D-glucopyranosyl]-oleanolic acid (5).     

Glycosides from Phlomis lunariifolia

An aliphatic alcohol glycoside, lunaroside 1-octen-3-yl [O-beta-apiofuranosyl-(1-->6)-O-[beta-glucopyranosyl-(1-->2)]-beta-glucopyranoside, a phenylethanoid glycoside, lunariifolioside 2-(3,4-dihydroxyphenyl)ethylO-beta-apiofuranosyl-(1-->6)-O-[O-beta-apiofuranosyl-(1-->4)-alpha-rhamnopyranosyl-(1-->3)]-4-O-(E)-caffeoyl-beta-glucopyranoside and a flavone glycoside, luteolin 7-O-[4-O-acetyl-alpha-rhamnopyranosyl-(1-->2)]-beta-glucuronopyranoside, were isolated from the aerial parts of Phlomis lunariifolia, in addition to 15 known glycosides. Their structures were elucidated on the basis of extensive 1D and 2D NMR spectroscopic interpretation and chemical degradation.     

New flavonoid glycosides from Aconitum naviculare (Brühl) Stapf, a medicinal herb from the trans-Himalayan region of Nepal

Three new flavonoid glycosides, 3-O-[beta-D-glucopyranosyl-(1-->3)-(4-O-trans-p-coumaroyl)-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyl]-7-O-[beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl]kaempferol, 3-O-[beta-D-glucopyranosyl-(1-->3)-(4-O-trans-p-coumaroyl)-alpha-L-rhamnopyranosyl-(1-->6)-beta-D-glucopyranosyl]-7-O-[beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl]quercetin and 7-O-[beta-D-glucopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl]quercetin were isolated from the aqueous extract of the aerial parts of Aconitum naviculare. Their structures were elucidated by spectral analysis (HRAPI-TOF MS, 1H, 13C NMR, HMQC, HMBC, DFQ-COSY, ROESY and TOCSY).     

Triterpenoid saponins from the stem bark of Elattostachys apetala

Six new triterpenoid saponins have been isolated from the stem bark of Elattostachys apetala together with four known triterpenoid saponins. Three of these new compounds are glycosides of a newly described genin, 29-hydroxyhederagenin (1). On the basis of spectral evidence, the structures of the new saponins were concluded to be alpha-hederin 28-O-[alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl] ester (2), sapindoside B 28-O-[alpha-L-rhamnopyranosyl-(1-->2)-beta-D-glucopyranosyl] ester (3), 3-O-beta-D-xylopyranosyl astrantiasaponin VII (4), 3-O-[alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]-28-O-[beta-D-glucopyranosyl-(1-->2)-[beta-D-glucopyranosyl-(1-->6)]-beta-D-glucopyranosyl]-29-hydroxyhederagenin (5), 3-O-[alpha-L-arabinopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]-28-O-[beta-D-glucopyranosyl(1-->2)-[beta-D-glucopyranosyl(1-->6)]-beta-D-glucopyranosyl]-29-hydroxyhederagenin (6), and 3-O-[beta-D-xylopyranosyl-(1-->3)-alpha-L-rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranosyl]-28-O-[beta-D-glucopyranosyl-(1-->2)-beta-D-gluco pyranosyl-(1-->6)]-beta-D-glucopyranosyl]-29-hydroxyhederagenin (7).