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.     

A new kaempferol diglycoside from Datura suaveolens Humb. & Bonpl. ex. Willd

A new flavonol glycoside, kaempferol 3-O-alpha-L-arabinopyranosyl-7-O-beta-D-glucopyranoside (1), has been isolated from methanol extract of leaves of Datura suaveolens (Solanaceae), along with six other known compounds, which include kaempferol 3-O-alpha-L-arabinopyranoside (2), 3-phenyl lactic acid, 3-(3-indolyl) lactic acid, and its methyl ester, physalindicanol A and physalindicanol B. The structural elucidation of 1 and characterization of the known compounds are based on detailed spectral analysis (ESI-FTICR-MS and 2D-NMR). This is the first report of isolation of these compounds from this plant.     

A new coumestan from Tephrosia calophylla

A new coumestan, tephcalostan (1) has been isolated from the whole plant of Tephrosia calophylla BEDD. together with two known flavonoids, 7-O-methylglabranin (2) and kaempferol 3-O-beta-D-glucopyranoside (3). The structure of tephcalostan was elucidated as 5'-(R)-8, 9-methylenedioxy-5'-isopropenyl-4', 5'-dihydrofurano[2', 3':2, 3]coumestan by extensive one-and two-dimensional (1D- and 2D-)-NMR techniques including (1)H-(1)H correlation spectroscopy (COSY), heteronuclear single quantum coherence (HSQC), heteronuclear multiple bond connectivity (HMBC) and nuclear Overhauser enhancement spectroscopy (NOESY) experiments.     

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.     

Ardisiphenols and other antioxidant principles from the fruits of Ardisia colorata

Novel alkylphenols, ardisiphenols A-C (1-3) and a novel bergenin derivative, demethoxybergenin (10) were isolated from the fruits of Ardisia colorata (Myrsinaceae), together with known alkylresorcinols (4-6), embelin (7), myricetin (8), quercetin (9), bergenin (11), norbergenin (12), kaempferol (13), quercetin-3-O-beta-D-glucopyranoside (14) and gallic acid (15). Their structures were determined by NMR, MS(/MS) analyses and other spectroscopic methods. Ardisiphenols showed moderate scavenging activities toward 1,1-diphenyl-2-picrylhydrazyl (DPPH) radicals and showed cytotoxicity against the murine breast cancer cell line, FM3A.     

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.     

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.     

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).     

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.     

Bioconversion of 7-Hydroxyflavanone: Isolation, Characterization and Bioactivity Evaluation of Twenty-One Phase I and Phase II Microbial Metabolites

Microbial metabolism of 7-hydroxyflavanone (1) with fungal culture Cunninghamella blakesleeana (ATCC 8688a), yielded flavanone 7-sulfate (2), 7,4'-dihydroxyflavanone (3), 6,7-dihydroxyflavanone (4), 6-hydroxyflavanone 7-sulfate (5), and 7-hydroxyflavanone 6-sulfate (6). Mortierella zonata (ATCC 13309) also transformed 1 to metabolites 2 and 3 as well as 4'-hydroxyflavanone 7-sulfate (7), flavan-4-cis-ol 7-sulfate (8), 2',4'-dihydroxychalcone (9), 7,8-dihydroxyflavanone (10), 8-hydroxyflavanone 7-sulfate (11), and 8-methoxy-7-hydroxyflavanone (12). Beauveria bassiana (ATCC 7159) metabolized 1 to 2, 3, and 8, flavanone 7-O-β-D-O-4-methoxyglucopyranoside (13), and 8-hydroxyflavanone 7-O-β-D-O-4-methoxyglucopyranoside (14). Chaetomium cochlioides (ATCC 10195) also transformed 1 to 2, 3, 9, together with 7-hydroxy-4-cis-ol (15). Mucor ramannianus (ATCC 9628) metabolized 1 in addition to 7, to also 4,2',4'-trihydroxychalcone (16), 7,3',4'-trihydroxyflavanone (17), 4'-hydroxyflavanone 7-O-α-L-rhamnopyranoside (18), and 7,3',4'-trihydroxy-6-methoxyflavanone (19). The organism Aspergillus alliaceus (ATCC 10060) transformed 1 to metabolites 3, 16, 7,8,4'-trihydroxyflavanone (20), and 7-hydroxyflavanone 4'-sulfate (21). A metabolite of 1, flavanone 7-O-β-D-O-glucopyranoside (22) was produced by Rhizopus oryzae (ATCC 11145). Structures of the metabolic products were elucidated by means of spectroscopic data. None of the metabolites tested showed antibacterial, antifungal and antimalarial activities against selected organisms. Metabolites 4 and 16 showed weak antileishmanial activity.     

Isoflavone glycosides from the root wood of Erythrina latissima

The molecular structures of 3 isoflavone glycosides isolated from the root wood of Erythrina latissima were established as 4'-hydroxyisoflavone-7-O-beta-D-glucopyranoside (compound 1); 4'-hydroxyisoflavone-7-O-alpha-L-rhamnosyl (1-->6)-beta-D-glucopyranoside (compound 2); and a new compound 4', 8-dimethoxy isoflavone-7-O-alpha-L-rhamnosyl (1-->6) glucopyranoside (8-O-methylretusin-7-O-alpha-L-rhamnosyl (1-6)-beta-D-glucopyranoside) (compound 3).     

Three new and antitumor anthraquinone glycosides from Lasianthus acuminatissimus MERR

Three new anthraquinone glycosides, lasianthuoside A (1), B (2), and C (3), were isolated from the root of Lasianthus acuminatissimus MERR., The structural elucidation of these anthraquinones was mainly established on the basis of 1D and 2D NMR and HR-MS spectroscopic analysis. Ten known compounds, damnacanthol (4), damnacanthol 11-methyl ether (5), damnacanthol-3-O-beta-D-primeveroside (6), asperuloside (7), asperulosidic acid (8), deacetyl asperulosidic acid (9), a nonglycosidic iridoid (10), 2,6-dimethoxy-4-hydroxyphenol-1-O-beta-D-glucopyranoside (11), tachioside (methoxyhydroquinone-4-O-beta-D-glucopyranoside) (12), and isotachioside (methoxyhydroquinone-1-O-beta-D-glucopyranoside) (13) were also identified for the first time from this plant in the course of the phytochemical and spectroscopic investigation. In addition to this report, a preliminary evaluation of 13 compounds in treating rheumatoid arthritis and antitumor effects of six anthraquinones are presented.     

Microbial metabolism. Part 6. Metabolites of 3- and 7-hydroxyflavones

Fermentation of 3-hydroxyflavone (1) with Beauveria bassiana (ATCC 13144) yielded 3,4'-dihdroxyflavone (3), flavone 3-O-beta-D-4-O-methylglucopyranoside (4) and two minor metabolites. 7-Hydroxyflavone (2) was transformed by Nocardia species (NRRL 5646) to 7-methoxyflavone (5) whilst Aspergillus alliaceus (ATCC 10060) converted it to 4',7-dihydroxyflavone (6). Flavone 7-O-beta-D-4-O-metylglucopyranoside (7) and 4'-hydroxyflavone 7-O-beta-D-4-O-methylglucopyranoside (8) were the metabolic products of 7-hydroxyflavone (2) when fermented with Beauveria bassiana (ATCC 7159). One of the minor metabolites of 3-hydroxyflavone (1) was tentatively assigned a beta'-chalcanol structure (9). Compounds 4, 7 and 8 are reported as new compounds. Structure elucidation of the metabolites was based on spectroscopic data.     

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.     

Phenolics of Moringa oleifera leaves

Five flavonol glycosides characterised as kaempferide 3-O-(2',3'-diacetylglucoside), kaempferide 3-O-(2'-O-galloylrhamnoside), kaempferide 3-O-(2'-O-galloylrutinoside)-7-O-alpha-rhamnoside, kaempferol 3-O-[beta-glucosyl-(1 --> 2)]-[alpha-rhamnosyl-(1 --> 6)]-beta-glucoside-7-O-alpha-rhamnoside and kaempferol 3-O-[alpha-rhamnosyl-(1 --> 2)]-[alpha-rhamnosyl-(1 --> 4)]-beta-glucoside-7-O-alpha-rhamnoside together with benzoic acid 4-O-beta-glucoside, benzoic acid 4-O-alpha-rhamnosyl-(1 --> 2)-beta-glucoside and benzaldehyde 4-O-beta-glucoside have been isolated from methanolic extract of Moringa oleifera leaves. Also obtained from the same extract were known compounds, kaempferol 3-O-alpha-rhamnoside, kaempferol, syringic acid, gallic acid, rutin and quercetin 3-O-beta-glucoside. Their structures were determined using spectroscopic methods as well as comparison with data from known compounds.     

Pentacyclic triterpenoids from the aerial parts of Lantana camara

Three new pentacyclic triterpenoids, camaryolic acid (1), methylcamaralate (2) and camangeloyl acid (3) and six known compounds beta-sitosterol 3-O-beta-D-glucopyranoside (4), octadecanoic acid (5), docosanoic acid (6), palmitic acid (7), camaric acid (8) and lantanolic acid (9) were isolated from the aerial parts of Lantana camara. Structures of the new compounds were elucidated by spectroscopic and chemical methods.     

3,4-Dihydroxy-7,8-dihydro-beta-ionone 3-O-beta-D-glucopyranoside and other glycosidic constituents from apple leaves

3,4-Dihydroxy-7,8-dihydro-beta-ionone 3-O-beta-D-glucopyranoside 1 has been isolated from a methanolic extract of apple (Malus domestica) leaves by XAD-2 adsorption chromatography and subsequent purification by high speed countercurrent chromatography (HSCCC) and HPLC. Under acidic conditions this glycoside gives rise to a number of volatile compounds including 1,1,6-trimethyl-1,2-dihydronaphthalene (TDN) 2, which is known as an off-flavor compound in wine. In the course of the study, six additional glycoconjugates were isolated from apple leaves, i.e. roseoside 3, 3-oxo-alpha-ionol beta-D-glucopyranoside 4, benzoic acid beta-D-glucose ester 5, kaempferol 3-O-rhamnoside 6, (+)-syringaresinol beta-D-glucopyranoside 7 and 4-hydroxy-5-(3'-methyl-2'-butenyl)-benzoic acid methylester 3-beta-D-glucopyranoside 8. The latter compound has been isolated for the first time in nature. In order to avoid the 'kerosene-off-flavor' caused by TDN, the methanolic extract has been subjected to yeast fermentation. This treatment reduced the amount of TDN formed and resulted in an improved flavor impression of the methanolic extract.     

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.     

Lupane-triterpenes from Bupleurum flavum

Two new triterpenoids, lup-20(29)-en-3 alpha, 28-diol (1) and lup-20(29)-en-3 alpha, 28,30-triol (2), have been isolated from aerial parts of Bupleurum flavum, a native plant of the Eastern Mediterranean area (Bulgaria, Greece, and Turkey). Their structures were elucidated by spectral analysis. The known compounds betulin, betulinic acid, jasminol, together with the lignan nemerosin and eight flavonoids (kaempferol, isokaempferide, gossipetin, quercetin, luteolin, isorhamnetin 3-O-beta-D-glucopyranoside, isorhamnetin 3-rutinoside, and rutin) were also characterized.     

Two new monoterpene glycosides and trypanocidal terpenoids from Dracocephalum kotschyi

From the whole plant of Dracocephalum kotschyi BOISS., two new monoterpene glycosides (9, 10), together with seven known terpenoids and a phytosterol (1-8), were isolated. Their structures were determined to be limonen-10-al (1), geranial (2), neral (3), beta-sitosterol (4), oleanolic acid (5), ursolic acid (6), p-mentha-8-en-1,2-diol (7), colosolic acid (8), limonen-10-ol 10-O-beta-D-glucopyranoside (9), and limonen-10-ol 10-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranoside (10). Compounds 1 (3.1 microM), 2 (3.1 microM), 3 (3.1 microM), 5 (6.2 microM), 6 (6.2 microM), and 8 (6.2 microM) were effective against epimastigotes of Trypanosoma cruzi.