Three new sesquiterpenoid glucosides of Ficus pumila fruit

As the glycosyl constituents of Ficus pumila L. fruits (Moraceae), three new sesquiterpenoid glucosides, pumilasides A, B and C were isolated together with benzyl beta-D-glucopyranoside, (E)-2-methyl-2-butenyl beta-D-glucopyranoside and rutin. Their structures were characterized as (1S,4S,5R,6R,7S,10S)-1,4,6-trihydroxyeudesmane 6-O-beta-D-glucopyranoside, (1S,4S,5S,6R,7R,10S)-1,4-dihydroxymaaliane 1-O-beta-D-glucopyranoside and 10 alpha, 11-dihydroxycadin-4-ene 11-O-beta-D-glucopyranoside by spectral and chemical methods.     

Six new dammarane-type triterpene saponins from the leaves of Panax ginseng

Six new minor saponins, together with known ginsenosides, were isolated from the leaves of Panax ginseng. The new saponins were named as ginsenoside-Rh5, -Rh6, -Rh7 -Rh8, -Rh9 and -Rg7, and their structures were elucidated on the basis of chemical and physicochemical evidence to be as follows: ginsenoside-Rh5: 3beta,6alpha,12beta,24zeta-tetrahydroxy-dammar-20(22),25-diene 6-O-beta-D-glucopyranoside (1), -Rh6: 3beta,6alpha12beta,20(S)-tetrahydroxy-25-hydroperoxy-dammar-23-ene 20-O-beta-D-glucopyranoside (2), -Rh7: 3beta,7beta,12beta,20(S)-tetrahydroxy-dammar-5,24-diene 20-O-beta-D-glucopyranoside (3), -Rh8: 3beta,6alpha,20(S)-trihydroxy-dammar-24-ene-12-one 20-O-beta-D-glucopyranoside (4), -Rh9: 3beta,6alpha,20(S)-trihydroxy-12beta,23-epoxy-dammar-24-ene 20-O-beta-D-glucopyranoside (5) and -Rg7: 3-O-beta-D-glucopyranosyl 3beta,12beta,20(S),24(R)-tetrahydroxy-dammar-25-ene 20-O-beta-D-glucopyranoside (6).     

Glycosides of Atractylodes lancea

Five sesquiterpenoid glycosides (two guaiane-type glycosides and three eudesmane-type glucosides) and a glucoside of an acetylene derivative were newly isolated from the water-soluble portion of the methanolic extract of Atractylodes lancea rhizome together with 26 known compounds. Their structures were characterized as atractyloside A 14-O-beta-D-fructofuranoside, (1S,4S,5S,7R,10S)-10,11,14-trihydroxyguai-3-one 11-O-beta-D-glucopyranoside, (5R,7R,10S)-isopterocarpolone beta-D-glucopyranoside, cis-atractyloside I, (2R,3R,5R,7R,10S)-atractyloside G 2-O-beta-D-glucopyranoside, and (2E,8E)-2,8-decadiene-4,6-diyne-1,10-diol 1-O-beta-D-glucopyranoside on the basis of chemical and spectroscopic investigation. The presence of six characteristic guaiane-type glucosides in both rhizomes of A. lancea and Atractylodes japonica suggested a close chemotaxonomic relationship between them.     

Two new glycosides from the whole plants of Glechoma hederacea L

Two new glycosides, 7S,7'S,8R,8'R-icariol A(2)-9-O-beta-D-glucopyranoside (1) and 4-allyl-2-hydroxyphenyl 1-O-beta-D-apiosyl-(1-->6)-beta-D-glucopyranoside (2), were isolated from the dried whole plants of Glechoma hederacea L. (Labiatae) together with four known compounds, cistanoside E (3), dihydrodehydrodiconiferyl alcohol 4-O-beta-D-glucopyranoside (4), apigenin 7-O-beta-D-glucuronopyranoside (5) and luteolin 7-O-beta-D-glucopyranoside (6). The structures of the new compounds were elucidated on the basis of chemical and spectral analysis.     

Antioxidative flavanone glycosides from the branches and leaves of Viscum coloratum

Two new flavanone glucosides, (2S)-homoeriodictyol 7,4'-di-O-beta-D-glucopyranoside (4) and (2R)-eriodictyol 7,4'-di-O-beta-D-glucopyranoside (5) were isolated from the branches and leaves of Viscum coloratum (KOMAR) NAKAI (Loranthaceae), along with three known flavanone glucosides: (2S)-homoeriodictyol 7-O-beta-D-glucopyranoside (1), (2S)-eriodictyol 7-O-beta-D-glucopyranoside (2), and (2S)-naringenin 7-O-beta-D-glucopyranoside (3). The structures of these compounds were elucidated using spectroscopic methods. The antioxidant activities of these isolated compounds were evaluated by colorimetric methods based on their scavenging effects on hydroxyl radicals and superoxide anion radicals, respectively. All the compounds showed potent albeit varied degrees of antioxidative activities and the structure-activity relationship is discussed.     

Five new nortropane alkaloids and six new amino acids from the fruit of Morus alba LINNE growing in Turkey

Investigation of the constituents of the fruits of Morus alba LINNE (Moraceae) afforded five new nortropane alkaloids (1-5) along with nor-psi-tropine (6) and six new amino acids, morusimic acids A-F (7-12). The structures of the new compounds were determined to be 2alpha,3beta-dihydroxynortropane (1), 2beta,3beta-dihydroxynortropane (2), 2alpha,3beta,6exo-trihydroxynortropane (3), 2alpha,3beta,4alpha-rihydroxynortropane (4), 3beta,6exo-dihydroxynortropane (5), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (7), (3R)-3-hydroxy-12-[(1S,4S)-4-[(1S)-1-hydroxyethyl]-pyrrolidin-1-yll-dodecanoic acid (8), (3R)-3-hydroxy-12-1(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid-3-O-beta-D-glucopyranoside (9), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-methyl-piperidin-1-yll-dodecanoic acid (10), (3R)-3-hydroxy-12-[(1R,4R,5S)-4-hydroxy-5-hydroxymethyl-piperidin-1-yl]-dodecanoic acid-3-O-beta-D-glucopyranoside (11), and (3R)-3-hydroxy-12-[(1R,4S,5S)-4-hydroxy-5-methyl-piperidin-1-yl]-dodecanoic acid (12) on the basis of spectral and chemical data.     

Antiallergic agents from natural sources. 3. Structures and inhibitory effects on nitric oxide production and histamine release of five novel polyacetylene glucosides from Bidens parviflora WILLD

Five new polyacetylene glucosides, bidensyneosides A1, A2, B, C (1-4), and 3-deoxybidensyneoside B (5), have been isolated from the air-dried whole plant of Bidens parviflora WILLD. The structures were identified based on spectroscopic analysis, physicochemical properties, and application of the modified Mosher method to be 3(R),8(E)-8-decene-4,6-diyne-1,3-diol 1-O-beta-D-glucopyranoside (1), deca-3(R),8(Z) 8-decene-4,6-diyne-1,3-diol 1-O-beta-D-glucopyranoside (2), 3(R)-deca-4,6,8-triyne-1,3-diol 1-O-beta-D-glucopyranoside (3), 3(R),8(E)-8-decene-4,6-diyne-1,3,10-triol 1-O-beta-D-glucopyranoside (4), and 8(E)-8-decene-4,6-diyne-1,10-diol 1-O-beta-D-glucopyranoside (5), respectively. These compounds inhibited nitric oxide (NO) production in lipopolysaccharide and interferon-gamma activated murine macrophages (RAW264.7) and also inhibited histamine release from rat mast cells stimulated by the antigen-antibody reaction.     

Structure elucidation and NMR spectral assignments of three new lignan glycosides from Akebia trifoliata

Three new lignan glycosides (1-3) were isolated from the stems of Akebia trifoliata. Their structures were elucidated as (7R,8R,7'R,8'R)3,3',5,5'tetramethoxy-4,4'dihydroxy-7,9':7',9-diepoxylignan-4-O-beta-D-glucopyranoside (1), (7S,8S,8'R)-4,4',9-trihydroxy-3,3',5,5'-tetramethoxy-7,9'-epoxylignan-7'-one 9-O-beta-D-glucopyranoside (2), (7R,8R,8'S)-4,4',9-trihydroxy3,3',5,5'-tetramethoxy-7,9'-epoxylignan-7'-one 9-O-beta-D-glucopyranoside (3) by spectral analyses, primarily NMR, MS and CD. The NMR assignments for the compounds were carried out using 1H, 13C, DEPT, COSY, HSQC, HMBC and ROESY NMR experiments.     

Structure elucidation and NMR spectral assignments of four neolignan glycosides with enantiometric aglycones from Osmanthus ilicifolius

Four new 8-O-4' type neolignan glycosides with enantiometric aglycones, (7S,8R)-erythro-guaiacylglycerol-beta-O-4'-sinapyl ether 9-O-beta-D-glucopyranoside (1), (7R,8S)-erythro-guaiacylglycerol-beta-O-4'-sinapyl ether 9-O-beta-D-glucopyranoside (2), (7S,8R)-erythro- syringylglycerol-beta-O-4'-sinapyl ether 9-O-beta-D-glucopyranoside (3) and (7R,8S)-erythro- syringylglycerol-beta-O-4'-sinapyl ether 9-O-beta-D-glucopyranoside (4), were isolated from the leaves of Osmanthus ilicifolius. Their structures were established on the basis of NMR, circular dichroism (CD), MS and chemical data. The NMR assignments for the compounds were carried out using (1)H, (13)C, COSY, HMQC, HMBC and NOESY NMR experiments.     

A new neolignan glycoside from the leaves of Acer truncatum

A new neolignan glycoside, (7R,8R)-7,8-dihydro-9'-hydroxyl-3'-methoxyl- 8-hydroxymethyl-7-(4-hydroxy-3-methoxyphenyl)-1'-benzofuranpropanol 9'-O-beta-D- glucopyranoside (1) was isolated from the leaves of Acer truncatum along with (7R,8R)-7,8-dihydro-9'-hydroxyl-3'-methoxyl-8-hydroxymethyl-7-(4-O-alpha-L-rhamno- pyranosyloxy-3-methoxyphenyl)-1'-benzofuranpropanol (2), schizandriside (3), lyoniresinol (4), berchemol (5), (-)-pinoresinol-4-O-beta-D-glucopyranoside (6), hecogenin (7), chlorogenic acid (8) and neochlorogenic acid (9). Their structures were elucidated on the basis of extensive spectroscopic data. The absolute configuration of compounds 1 was established by its CD spectrum. The antibacterial activities of compounds 1-7 were evaluated.     

Megastigmane glucosides from Equisetum debile and E. diffusum

A new megastigmane diglucoside, (3S,5R,6S,7E,9S)-megastigman-7-ene-5,6-epoxy-3,9-diol 3,9-O-beta-D-diglucopyranoside (3), was isolated from the aerial portion of Equisetum debile along with macarangioside D (debiloside A), sammangaoside A, (6R,9S)-3-oxo-alpha-ionol 9-O-beta-D-glucopyranoside, debiloside B, kaempferol 3-O-sophoroside, kaempferol 3,7-O-beta-D-diglucopyranoside, kaempferol 3-O-sophoroside-7-O-beta-D-glucopyranoside, phenylethyl O-beta-D-glucopyranoside, (Z)-3-hexenyl O-beta-D-glucopyranoside, (7S,8R)-dehydrodiconiferyl 4-O-beta-D-glucopyranoside, and L-tryptophan. The absolute configuration at C-6 of the original structure of debilo-side A was revised to 6R-configuration, and was identical with macarangioside D (1). From the aerial portion of E. diffusum, four compounds, sammangaoside A, kaempferol 3-O-sophoroside and L-tryptophan and (3S,5R,6S,7E,9S)-megastigman-7-ene-5,6-epoxy-3,9-diol 3-O-beta-D-glucopyranoside were identified. The spectroscopic data of (3S,5R,6S,7E,9S)-megastigman-7-ene-5,6-epoxy-3,9-diol 3-O-beta-D-glucopyranoside (13) were found to be identical with corchoionoside A (9R-isomeric compound). The structure of corchoionoside A was also discussed. Structure determinations were based on physical data and spectroscopic evidence.     

Six new withanolide-type steroids from the leaves of Solanum cilistum

Six new withanolide-type steroids, designated cilistols v, t, i, j, y and w (1-6, respectively), were obtained from the leaves of Solanum cilistum. Their respective structures were characterized by spectroscopic means as follows: Cilistol v (1) was (22R,24Z)-1alpha,3beta,22,26-tetrahydroxyergost-5,24-diene 26-O-beta-D-glucopyranoside, which is regarded as the precursor of other withanolide-type steroids included in this title plant. Cilistol t (2) was (22R,24S,25R,26S)-24,25;22,26-diepoxy-1alpha,3beta,26-trihydroxyergost-5-ene 26-O-beta-D-glucopyranoside, and cilistols j (3) and i (4) corresponded to the substances probably formed by the cleavage of the epoxy ring at C-24 and 25 of 2. Cilistol y (5) was 3-O-sulphonyl (22R,24S,25R,26R)-1-oxo-24,25; 22,26-diepoxy-3beta,17alpha,26-trihydroxyergost-5-ene 26-O-beta-D-glucopyranoside, and cilistol w (6) corresponded to the substance obtained by the fission of the epoxy ring at C-24 and 25 of 5. The occurrence of these withanolide type steroids from Solanum genera is rare and worthy of note.     

New alpha-tetralonyl glucosides from the fruit of Juglans mandshurica

Five new alpha-tetralonyl glucosides, juglanosides A-E (1-5) were isolated from the fresh rejuvenated fruit of Juglans mandshurica. Their structures were elucidated as (4S)-4-hydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (1), (4S)-4,5-dihydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (2), (4S)-4,6-dihydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (3), (4S)-4,5,8-trihydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (4), and (4S)-4,5,8-trihydroxy-alpha-tetralone 5-O-beta-D-glucopyranoside (5) on the basis of spectroscopic analysis and chemical evidence.     

Withanolide derivatives from the roots of Withania somnifera and their neurite outgrowth activities

Five new withanolide derivatives (1, 9-12) were isolated from the roots of Withania somnifera together with fourteen known compounds (2-8, 13-19). On the basis of spectroscopic and physiochemical evidence, compounds 1 and 9-12 were determined to be (20S,22R)-3 alpha,6 alpha-epoxy-4 beta,5 beta,27-trihydroxy-1-oxowitha-24-enolide (1), 27-O-beta-D-glucopyranosylpubesenolide 3-O-beta-D-glucopyranosyl (1-->6)-beta-D-glucopyranoside (withanoside VIII, 9), 27-O-beta-D-glucopyranosyl (1-->6)-beta-D-glucopyranosylpubesenolide 3-O-beta-D-glucopyranosyl (1-->6)-beta-D-glucopyranoside (withanoside IX, 10), 27-O-beta-D-glucopyranosylpubesenolide 3-O-beta-D-glucopyranoside (withanoside X, 11), and (20R,22R)-1 alpha,3 beta,20,27-tetrahydroxywitha-5,24-dienolide 3-O-beta-D-glucopyranoside (withanoside XI, 12). Of the isolated compounds, 1, withanolide A (2), (20S,22R)-4 beta,5 beta,6 alpha,27-tetrahydroxy-1-oxowitha-2,24-dienolide (6), withanoside IV (14), withanoside VI (15) and coagulin Q (16) showed significant neurite outgrowth activity at a concentration of 1 microM on a human neuroblastoma SH-SY5Y cell line.     

Four new steroid constituents from the waste residue of fibre separation from Agave americana leaves

Three new steroidal saponins, named agamenosides H-J (1-3), and a new cholestane steroid agavegenin D (4) were isolated from the waste residue of fibre separation from Agave americana leaves, together with six known steroids. Structures of the new compounds 1-4 were deduced to be (22S,23S,24R,25S)-24-[(beta-D-glucopyranosyl)oxy]-5alpha-spirostane-3beta,6alpha,23-triol 6-O-beta-D-glucopyranoside (1), (22S,23S,24R,25S)-5alpha-spirostane-3beta,23,24-triol 24-O-beta-D-glucopyranoside (2), (22S,23S,25R,26S)-23,26-epoxy-5alpha-furostane-3beta,22,26-triol 26-O-beta-D-glucopyranoside (3), and (22S,25S)-5alpha-cholestane-3beta,16beta,22,26-tetrol (4), respectively, by means of spectroscopic analysis, including extensive 1D and 2D NMR data, and the results of hydrolytic cleavage.     

A new 5,11-epoxymegastigmane glucoside from Acanthus ilicifolius

From a China mangrove plant Acanthus ilicifolius Linn., a new compound, 5,11-epoxymegastigmane glucoside (1) was isolated along with one known compound of megastigmane glucosides, (6S, 9S)-roseoside (2). The structure of compound 1 was determined on the basis of 1D- and 2D-NMR techniques (DEPT, COSY, HMBC, HMQC, NOESY) and HR-FABMS. The structure of 1 was established as (1S, 3S, 5R, 6R, 7E)-5,11-epoxy-3-hydroxymegastigman-7-en-9-one-3-O-beta-D-glucopyranoside.     

Megastigmane, benzyl and phenethyl alcohol glycosides, and 4,4'-dimethoxy-beta-truxinic acid catalpol diester from the leaves of Premna subscandens MERR

Extensive isolation work on the n-BuOH-soluble fraction obtained from the leaves of Premna subscandens, collected on Ishigaki island, Okinawa, afforded six compounds. Two were identified as megastigmane glucosides, 7-(3,5-dihydroxy-1,1,5-trimethylcyclohexylidene)-9-methylprop++ +-8-enyl 9-O-beta-D-glucopyranoside and 3-hydroxy-5,6-epoxy-beta-ionol 9-O-beta-D-glucopyranoside. The structures of the remaining four new compounds were elucidated to be a 2'-O-beta-D-apiofuranosyl derivative of 3-hydroxy-5,6-epoxy-beta-ionol 9-O-beta-D-glucopyranoside, named premnaionoside, benzyl alcohol beta-D-(2'-O-beta-D-xylopyranosyl)glucopyranoside, phenethyl alcohol beta-D-(2'-O-beta-D-glucopyranosyl)glucopyranoside, and 4,4'-dimethoxy-beta-truxinic acid catalpol diester by spectroscopic analyses.     

New iridoid glucosides from the aerial parts of Verbena brasiliensis

Two new iridoid glucosides, verbenabraside A (1) and verbenabraside B (2), were isolated from the aerial parts of Verbena brasiliensis VELL., along with six known iridoid glucosides, gelsemiol 3-O-beta-D-glucoside (3), verbraside (4), 9-hydroxysemperoside (5), griselinoside (6), aralidioside (7), and 6alpha-hydroxyforsythide dimethyl ester (8), three known phenylethanoid glycosides, 2-phenylethyl O-beta-D-xylopyranosyl-(1-->2)-beta-D-glucopyranoside (9), acteoside (10), and leucosceptoside A (11), two known lignan glucosides, dihydroxymethyl-bis(3,5-dimethoxy-4-hydroxyphenyl) tetrahydrofuran-9 (or 9')-O-beta-glucopyranoside (12) and (+)-lyoniresinol 3alpha-O-beta-D-glucopyranoside (13), a known methyl salicylate glucoside, methyl 2-O-beta-D-glucopyranosylbenzoate (14), and two known sterols, beta-sitosterol 3-O-beta-D-glucopyranoside (15) and beta-sitosterol (16). Their chemical structures were determined on the basis of spectroscopic data. Compound 1 exhibited stronger scavenging effect on the stable free radical 1,1-diphenyl-2-picrylhydrazyl than that of alpha-tocopherol.     

New calamenene sesquiterpenes from Tarenna madagascariensis

Four calamenene sequiterpenes, (+)-(7R,10S)-15-hydroxycalamenene (3), (+)-(7R,10S)-2,15-dihydroxycalamenene (4), (+)-(7R,10S)-2-hydroxy-15-calamenal (5), (+)-(7R,10S)-15-calamenal (6), along with the amorphane sesquiterpene (+)-(1S,6R,7R,10S)-1-hydroxy-3-oxo-amorph-4-ene (16), have been isolated from the Madagascan shrub Tarenna madagascariensis (Rubiaceae) and their structures determined by spectroscopic methods and chemical correlations. Furthermore, five known related sesquiterpenes [(+)-(7R,10S)-2-hydroxycalamenene (1), (+)-(7R,10S)-3-hydroxycalamenene (2), (-)-alpha-cadinol (13), cadinenal (14), 6-epicadinenal (15)], and three known lignans [(-)-hinokinin, (-)-dihydrocubebin, (-)-cubebin] were also isolated from the same plant. This is the first report of compounds 3, 4, 5, 6, and 16 from a natural source.