Chalcone glycosides from aerial parts of Brassica rapa L. ‘hidabeni’, turnip

A phytochemical investigation of the aerial parts of Brassica rapa L. ‘hidabeni’, turnip resulted in the isolation of three new chalcone glycosides, 4′-O-β-d-glucopyranosyl-4-hydroxy-3′-methoxychalcone (1), 4′-O-β-d-glucopyranosyl-3′,4-dimethoxychalcone (2) and 4,4′-di-O-β-d-glucopyranosyl-3′-methoxychalcone (3) along with three known glycosides. The structures of the three newly isolated chalcone glycosides were elucidated on the basis of 1D and 2D NMR and mass spectroscopy.     

Two new dianthramide glucosides with cardiomyocytes protective activity from Aconitum carmichaelii

Two new dianthramide glucosides, N-(2′-β-d-glucopyranosyl-5′-hydroxysalicyl)-4-hydroxy-3-methoxyanthranilic acid methyl ester (1) and N-(2′-β-d-glucopyranosyl-5′-hydroxysalicyl)-4-hydroxyanthranilic acid methyl ester (2), together with five known glycosides, were isolated from the lateral roots of Aconitum carmichaelii. Their structures were elucidated by spectroscopic analyses. In the in vitro assays, compounds 1 and 2 showed activity against pentobarbital sodium-induced cardiomyocytes damage by recovering beating rhythm and increasing the cell viability.     

Dihydrofurocoumarin glucosides from Angelica archangelica and Angelica silvestris

A water-soluble root extract of Angelica archangelica subsp. litoralis afforded, in addition to adenosine, coniferin and the two known dihydrofurocoumarin glycosides, apterin and 1′-O-β-d-glycopyranosyl-(S)-marmesin (marmesinin), two new dihydrofuranocoumarin glycosides, 1′-O-β-d-glucopyranosyl-(2S, 3R)-3-hydroxymarmesin, and 2′-β-d-glucopyranosyloxymarmesin. For the latter a 2S-configuration was demonstrated, the stereochemistry at position 1′ remaining undefined. Roots of A. silvestris similarly afforded 1′-O-β-d-glucopyranosyl-(2S, 3R)-3-hydroxymarmesin. By correlation with the aglycone 2S,3R)-3-hydroxymarmesin obtained in this work, the absolute configurations (2S,3R) were established for the known dihydrofurocoumarin diesters smirniorin and smirnioridin.     

Synthesis of quercetin glycosides and their melanogenesis stimulatory activity in B16 melanoma cells

4′-O-β-d-Glucopyranosyl-quercetin-3-O-β-d-glucopyranosyl-(1→4)-β-d-glucopyra-noside (3) was isolated from Helminthostachys zeylanica root extract as a melanogenesis acceleration compound and was synthesized using rutin as the starting material. Related compounds were also synthesized to understand the structure–activity relationships in melanin biosynthesis.Melanogenesis activities of the glycosides were determined by measuring intracellular melanin content in B16 melanoma cells. Among the synthesized quercetin glycosides, quercetin-3-O-β-d-glucopyranoside (1), quercetin-3-O-β-d-glucopyranosyl-(1→4)-β-d-glucopyranoside (2), and 3 showed more potent intracellular melanogenesis acceleration activities than theophyline used as positive control in a dose-dependent manner with no cytotoxic effect.     

The complex of O-glucosylzeatin derivatives formed in Populus species

When zeatin was supplied to excised leaves of Populus alba, the principal metabolites formed were adenosine, O-β-d-glucopyranosyl-cis-zeatin (derived from cis-zeatin in the commercial zeatin used), O-β-d-glucopyranosylzeatin, and two new metabolites, namely, O-β-d-glucopyranosyldihydrozeatin and O-β-d-glycopyranosyl-9-β-d-ribofuranosyldihydrozeatin, the structures of which were confirmed by unambiguous synthesis. Chromatographic studies indicated that adenosine 5′-phosphate, zeatin 7-glucopyranoside, zeatin 9-glucopyranoside, dihydrozeatin and zeatin 9-riboside were minor metabolites. The principal metabolites of zeatin 9-riboside in P. nigra leaves were the new metabolites O-β-d-glucopyranosyl-9-β-d-ribofuranosylzeatin (synthesized chemically) and O-β-d-glucopyranosl-9-β-d-ribofuranosyldihydrozeatin.     

Chemical constituents from the roots of Acanthus ilicifolius var. xiamenensis

Chemical investigation of Acanthus ilicifolius var. xiamenensis led to the isolation of eleven compounds, and their structures were identified to be 2-benzoxazolinone (1), 2-hydroxy-2H-1,4-benzoxazin-3(4H)-one (2), (2R)-2-O-β-d-glucopyranosyl-2H-1,4-benzox azin-3(4H)-one (3), (2R)-2-O-β-d-glucopyranosyl-4-hydroxy-2H-1,4-benzoxazin-3(4H)-one (4), (2R)-2-O-β-d-glucopyranosyl-7-hydroxy-2H-1,4-benzoxazin-3(4H)-one (5), lyoniside (6), 3′-methoxy-luteolin-7-O-β-d-glucopyranoside (7), β-sitosterol-3-O-β-d-glucopyranoside (8), stigmasterol octadecanoate (9), β-sitosterol octadecanoate (10), stigmasterol-3-O-β-d-glucopyranoside (11) on the basis of mass and NMR spectra. This is the first report on the occurrence of compound 6 and 7 in Acanthaceae. This work also represents the first phytochemical work on the roots of A. ilicifolius var. xiamenensis.     

Furocoumarin glucosides of Angelica archangelica subspecies Litoralis

From the roots of Angelica archangelica subsp. litoralis three new furocoumarin glycosides, tert. O-β-d-glucopyranosyl-(R)-byakangelicin, sec.-O-β-d-glucopyranosyl-(R)-byakangelicin and tert.-O-β-d-glucopyranosyl-(R)-isobyakangelicin were isolated and their structures established mainly by spectroscopic methods. Additionally, tert.-O-β-d-glucopyranosyl-(R)-heraclenol was obtained and characterized.     

New triterpene saponins from Phryna ortegioides

Four new and three known oleanane-type saponins have been isolated from the methanolic extract of Phryna ortegioides, a monotypic and endemic taxon of Caryophyllaceae.The structures of the new compounds were determined as gypsogenic acid 28-O-β-d-glucopyranosyl-(1→2)-O-β-d-glucopyranosyl-(1→6)-O-β-d-glucopyranosyl ester (1), 3-O-α-l-arabinofuranosyl-gypsogenic acid 28-O-β-d-glucopyranosyl-(1→3)-O-[β-d-glucopyranosyl-(1→6)]-O-β-d-glucopyranosyl ester (2), 3-O-α-l-arabinofuranosyl-gypsogenic acid 28-O-β-d-glucopyranosyl-(1→3)-O-[β-d-glucopyranosyl-(1→2)-O-β-d-glucopyranosyl-(1→6)-O-]-β-d-glucopyranosyl ester (3), 3-O-α-l-arabinofuranosyl-16α-hydroxyolean-12-en-23,28-dioic acid-28-O-β-d-glucopyranosyl-(1→3)-O-[β-d-glucopyranosyl-(1→2)-O-β-d-glucopyranosyl-(1→6)]-O-β-d-glucopyranosyl ester (4). Their structures were established by a combination of one- and two-dimensional NMR techniques, and mass spectrometry. Noteworthy, none of isolated compounds possesses as aglycone moiety gypsogenin, considered a marker of Caryophyllaceae family.The cytotoxic activity of the isolated compounds was evaluated against three cancer cell lines including A549 (human lung adenocarcinoma), A375 (human melanoma) and DeFew (human B lymphoma) cells. Only compound 6 showed a weak activity against A375 and DeFew cell lines with IC₅₀ values of 77 and 52 μM, respectively. None of the other tested compounds, in a range of concentrations between 12.5 and 100 μM, caused a significant reduction of the cell number.     

Three new 18,19-seco-ursane glycosides from Elsholtzia bodinieri

Chromatographic separation of an extract of the aerial part of Elsholtzia bodinieri resulted in the isolation of three new 18,19-seco-ursane glycosides, bodiniosides E-G (1–3). Their structures were elucidated as 2α,12β,23-trihydroxy-3-(β-d-glucopyranosyl)-19-oxo-18,19-seco-urs-13(18)-en-28-O-β-d-glucopyranosyl ester (1), 3-β-d-glucopyranosyl-19-β-d-glucopyranosyl-12β,21-dihydroxy-18,19-seco-urs-13(18)-en-28-oic acid (2), and 2α,12β,21-trihydroxy-3-β-d-glucopyranosyl-19-β-d-glucopyranosyl-18,19-seco-urs-13(18)-en-28-oic acid (3), respectively, by extensive NMR techniques, including 1D- and 2D-NMR experiments, as well as comparing with spectral data with those of the known analogues.     

New oleanane-type saponins: Leptocarposide B-D,from Ludwigia leptocarpa (Onagraceae)

Three new oleanane-type saponins, leptocarposide B-D (1–3), were isolated from the whole plant of Ludwigia leptocarpa (Nutt.) Hara, together with ten known compounds 4–13.The structures of these compounds were determined by interpretation of their spectral data, mainly HR-TOFESIMS, 1D-NMR (¹H, ¹³C) and 2D-NMR (¹H–¹H COSY, HSQC, HMBC, and NOESY), and by comparison with the literature data. The structures of the new compounds were established as 28-O-β-d-xylopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-[α-l-arabinopyranosyl-(1 → 3)]-4-O-(3′-hydroxybutanoyloxy-3-hydroxybutanoyloxy)-β-d-fucopyranosyl zanhic acid (1); 3-O-β-d-glucopyranosyl-28-O-β-d-xylopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-4-O-(3′-hydroxybutanoyloxy-3-hydroxybutanoyloxy)-β-d-fucopyranosyl medicagenic acid (2); 3-O-β-d-glucopyranosyl-(1 → 4)-β-d-glucopyranosyl-28-O-β-d-xylopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-[α-l- arabinopyranosyl-(1 → 3)]-4-O-(3′-hydroxybutanoyloxy-3-hydroxybutanoyloxy)-β-d-fucopyranosyl zanhic acid (3).     

Triterpene glycosides from red ginseng marc and their anti-inflammatory activities

Three new triterpene glycosides ursan-3β,19α,22β-triol-3-O-β-d-glucopyranosyl (2′→1″)-β-d-glucopyranoside (1), ursan-3α,11β-diol-3-O-α-d-glucopyranosyl-(6′→1″)-α-d-glucopyranosyl-(6″→1‴)-α-d-glucopyranosyl-(6‴→1‴′)-α-d-glucopyranoside (2) and lanost-5,24-dien-3β-ol-3-O-β-d-glucopyranosyl-(6′→1″)-β-d-glucopyranosyl-(6″→1‴)-β-d-glucopyranoside (3), together with one known compound were isolated and identified from the marc of red ginseng. Their structures were elucidated by spectroscopic data analysis. Compounds (1–3) were investigated for anti-inflammatory effects using the RAW 264.7 macrophage cell line. In the cell proliferation assay, lipopolysaccharide stimulation decreased cell proliferation of RAW 264.7 macrophage cells, but the suppression of cell proliferation was significantly protected by treatment with compounds 2 and 3. Compounds 2 and 3 had a suppressive effect on the production of nitric oxide (NO), and they inhibited mRNA expression of proinflammatory mediators such as inducible nitric oxide synthase, and cyclooxygenase-2, and proinflammatory cytokines such as two interleukins and tumor necrosis factor-α. These findings suggest that compounds 2 and 3 have potential anti-inflammatory activities.     

Polyphenols of Eucalyptus sideroxylon wood

Twenty-three major components were detected in the methanol extractives of the heartwood of Eucalyptus sideroxylon. The components identified include resveratrol, resveratrol-β-glucoside, 3,3′-di- and 3,3′,4-tri-o-methylellagic acids and their glucosides. The 3,3′-di-o-methylellagic acid 4′-glucoside isolated had properties significantly different from those previously reported for this compound. Also present were gailic acid, catechin, ellagic acid, an unidentified stilbene, the ellagitannins D-6 and D-13, polymerized leucocyanidin and an oily material. The sapwood contained gailic acid, small amounts of ellagitannins and ellagic acids and traces of other components. The heartwood extractives of related eucalypt species were also examined.     

Cytokinins in immature seeds of Dolichos lablab

Five cytokinins, trans-zeatin, 9-β-d-ribofuranosyl-trans-zeatin, 9-β-d-ribofuranosyl-cis-zeatin, 6-(trans-4-O-β-d-glucopyranosyl-3-methyl-2-butenylamino)purine and 6-(trans-4-O-β-d-glucopyranosyl-3-methyl-2-butenylamino)-9-β-d-ribofuranosylpurine were identified from immature seeds of Dolichos lablab.     

The X-ray crystal structure of 6-deoxy-α-l-sorbofuranose. Conformational analysis of ketohexofuranosides and their comparison with ribofuranosides and arabinofuranosides

The crystal and molecular structure of 6-deoxy-l-sorbose have been determined by the application of multisolution methods and refined to an R-index of 0.063 for 560 reflections, using three-dimensional intensity data collected on a Picker automatic diffractometer. The compound crystallizes in the space group P2₁2₁2₁ with unit-cell dimensions a = 18.470 (10), b = 7.636 (10), and c = 5.371 (8) Å; Z = 4. The molecule occurs as the α-furanose form, which is also the preponderant tautomer in solution. The puckering of the furanoid ring is C-3′-exo-C-4′-endo (₃T⁴) [equivalent to C-2′-exo-C-3′-endo (₂T³) in the numbering for d-ribose], with P and τ_m angles of -6.5 and 42.7° respectively. Conformational analysis of the known ketofuranosides shows that the ₃T⁴ (₂T³ in d-ribose numbering) puckering mode, which is typical of α-nucleosides, is favored, in contrast to the favored ³T₂ or ²T₃ puckering mode for the β-d-ribonucleosides and β-d-arabinonucleosides. The conformational differences among furanoid rings are mainly influenced by the configuration at the anomeric carbon atom. The favored orientation about the C-2′-C-1′ bond (O-5′-C-2′-C-1′-O-1′)of the ketofuranosidesis — gauche. All four hydroxyl groups are involved in donor-acceptor hydrogen bonding, and O-4′-8 appears to be involved in a bifurcated hydrogen bond to O-2′ and O-3′ of neighboring molecules.     

Endgültige struktur von schaftosid aus Silene schafta

Schaftoside, an apigenin-di-C-glycoside from Silene schafta was identified by oxidative degradation and spectroscopic investigations as 6-O-β-d-glucopyranosyl-8-α-l-arabinopyranosylapigenin. Its main isomerization product (isochaftoside) is identical with synthetic 6-C-α-l-arabinopyranosyl-8-β-d-glucopyranosylapigenin.     

Beshornin and beshornoside,steroidal saponins of Beshorneria yuccoides

Two new saponins beshornin and beshornoside have been isolated from the methanolic extract of Beshorneria yuccoides leaves and their structures elucidated. Beshornin is 3-O-[α-l-rhamnopyranosyl-(1 → 4)-β-d-glucopyranosyl- (1 → 2)-[α-l-rhamnopyranosyl-(1 -+ 4)-P-D-glucopyranosyl-(1 → 3)]-β-d-glucopyranosyl-(1 → 4)-β-d- galactopyranosyl-(25R)-5α-spirostan-3β-ol, whereas beshornoside is 3-O-[α-l-rhamnopyranosyl-(1 → 4)- β-d)-glycopyranosyl-(1 → 2)]-[α-l-rhamnopyranosyl-(1 → 4)-β-d-glucopyranosyl-(1 → 3)]-β-d-glucopyranosyl- (1 → 4)-β-d-galactopyranosyl 26-O-[β-d]-glucopyranosyl-(25R)-5α-furostan-3β,22α,26-triol.     

Triterpene glycosides from Agrostemma gracilis

Four triterpene saponins, agrostemmosides A–D were isolated from the methanol extract of Agrostemma gracilis. The structures of the compounds were determined as 3-O-β-d-xylopyranosyloleanolic acid 28-O-β-d-glucopyranosyl-(1 → 2)-[β-d-xylopyranosyl-(1 → 6)]-β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranosyl ester, 3-O-α-l-rhamnopyranosyl-(1 → 2)-β-d-xylopyranosyloleanolic acid 28-O-β-d-glucopyranosyl-(1 → 2)-[β-d-xylopyranosyl-(1 → 6)]-β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranosyl ester, 3-O-β-d-xylopyranosylechinocystic acid 28-O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranosyl ester, 3-O-β-d-xylopyranosylechinocystic acid 28-O-β-d-glucopyranosyl-(1 → 2)-[β-d-xylopyranosyl-(1 → 6)]-β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranosyl ester by a combination of one- and two-dimensional NMR techniques, and mass spectrometry. To the best of our knowledge this is the first phytochemical report on A. gracilis, and echinocystic acid saponins were encountered for the first time in Caryophyllaceae family.     

Highly glycosylated flavonols with an O-linked branched pentasaccharide from Iberis saxatilis (Brassicaceae)

Four flavonol glycosides isolated from non-flowering leafy shoots of Iberis saxatilis (Brassicaceae) were characterised by spectroscopic and chemical methods as saxatilisins A–D, the 3-O-β-d-glucopyranosyl-(1 → 3)-α-l-rhamnopyranosyl-(1 → 2)[β-d-glucopyranosyl-(1 → 2)-α-l-rhamnopyranosyl-(1 → 6)]-β-d-glucopyranoside, 3-O-β-d-glucopyranosyl-(1 → 3)-α-l-rhamnopyranosyl-(1 → 2)[α-l-rhamnopyranosyl-(1 → 6)]-β-d-glucopyranoside, 3-O-(6-O-E-sinapoyl)-β-d-glucopyranosyl-(1 → 3)-α-l-rhamnopyranosyl-(1 → 2)[β-d-glucopyranosyl-(1 → 2)-α-l-rhamnopyranosyl-(1 → 6)]-β-d-glucopyranoside, and 3-O-(6-O-E-feruloyl)-β-d-glucopyranosyl-(1 → 3)-α-l-rhamnopyranosyl-(1 → 2)[β-d-glucopyranosyl-(1 → 2)-α-l-rhamnopyranosyl-(1 → 6)]-β-d-glucopyranoside of isorhamnetin (3,5,7,4′-tetrahydroxy-3′-methoxyflavone), respectively. Analysis of ²J_HC correlations detected with the H2BC (heteronuclear two-bond correlation) pulse sequence aided the unambiguous assignment of glycosidic resonances in the ¹H and ¹³C NMR spectra of these compounds. Saxatilisins A, C, and D, are the first flavonol glycosides to be described with a pentasaccharide chain at a single glycosylation site. Several pentaglycosides of kaempferol and quercetin, tentatively assigned as saxatilisin analogues from LC–MS/MS analyses, were present as minor constituents of the extracts.     

Two new penterpenoid saponins and a new diterpenoid glycoside from Hemsleya chinensis

Two new penterpenoid saponins, hemsloside-Ma4 (1) hemsloside-Ma5 (2), and a new diterpenoid glycoside, hemsloside-Ma6 (3), were isolated from the rhizomes of Hemsleya chinensis. By detailed analysis of the NMR spectra and chemical methods, the structures of new compounds were determined to be 3-O-β-l-arabinopyranosyl-(1 → 3)-O-(6′-methyl ester)-β-d-glucuropyranosyl-oleanolic acid-28-O-β-d-glucopyranosyl-(1 → 6)-O-β-d-glucopyranoside (1), 3-O-β-l-arabinopyranosyl-(1 → 3)-O-(6′-methyl ester)-β-d-glucuropyranosyl-oleanolic acid-28-O-β-d-xylopyranosyl-(1 → 6)-O-β-d-glucopy-ranoside (2), and 13ϵ-hydroxylabda-8(17), 14-dien-18-oic acid-18-O-α-l-rhamnopyranosyl-(1 → 2)-O-β-d-glucopyranosyl-(1 → 4)-O-α-l-rhamnopyranoside (3). Diterpenoid-type compound (3) was isolated from Hemsleya genus for the first time.     

Saponins in aerial parts of Helleborus viridis L.

In the search of natural compounds inhibiting methane production in ruminants three novel steroidal saponins have been isolated from the aerial parts of Helleborus viridis L. Their structures have been established based on spectral analyses as: (25R)-26-O-β-d-glucopyranosyl-5β-furostan-3β,22α,26-triol 3-O-β-d-glucopyranosyl-(1 → 6)-O-β-d-glucopyranoside, (25R)-26-O-β-d-glucopyranosyl-5α-furostan-3β,22α,26-triol 3-O-β-d-glucopyranosyl-(1 → 6)-O-β-d-glucopyranoside and (25R)-26-O-β-d-glucopyranosyl-furost-5-ene-1β,3β,22α,26-tetraol 1-O-{α-l-rhamnopyranosyl-(1 → 2)-O-[β-d-glucopyranosyl-(1 → 3)]-6-O-acetoxy-β-d-glucopyranoside}.