Lignans from the stems of Sambucus williamsii and their effects on osteoblastic UMR106 cells

Three new lignans, sambucunol A (8) ((+)-erythro-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(4-hydroxy-3-methoxycinnamoyloxypropanyl)-2-hydroxyphenoxy]-1, 3-propanediol), sambucunol B (9) ((+)-threo-1-(4-hydroxyl-3-methoxyphenyl)-2-[4-(4-hydroxy-3-methoxy-cinnamoyloxy propanyl)-2-hydroxyphenoxy]-1, 3-propanediol) and buddlenol G (10) (2-{4-[2, 3-dihydro-3-hydroxymethyl-7-hydroxy-5-(4-hydroxy-3-methoxycinnamoyloxypropanyl)-2-benzofuranyl]-2,6-dimethoxyphenoxy}-1-(4- hydroxy-3-methoxyphenyl) -1, 3-propanediol), along with seven known ones, including ( - )-syringaresinol (1), ( - )-pinoresinol (2), 1, 2-bis(4-hydroxy-3-methoxy phenyl)-1, 3-propanediol (3), ( - )-erythro-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(3-hydroxy propanyl)-2-methoxyphenoxy]-1, 3-propanediol (4), ( - )-threo-1-(4-hydroxy-3-methoxyphenyl)-2-[4-(3-hydroxypropanyl)-2-methoxy phenoxy]-1, 3-propanediol (5), ( - )-lariciresinol (6) and ( - )-dihydrodehydrodiconiferyl alcohol (7), were isolated from the 60% ethanol extract of stems of Sambucus williamsii Hance by chromatographic methods. Their structures were established by spectral analysis. The effects of isolated compounds on the osteoblast-like UMR106 cell proliferation and ALP activities were determined. Compounds 2, 7 and 10 showed stimulating effects both on UMR106 cell proliferation and ALP activity. Compounds 1, 3, 6 and 8 stimulated UMR106 cell proliferation, while compounds 4 and 5 induced ALP activity in UMR106 cell.     

Aromatic acid derivatives from the lateral roots of Aconitum carmichaelii

Seven new aromatic acid derivatives (1–7), together with five known analogs, were isolated from the lateral roots of Aconitum carmichaelii. Structures of the new compounds were determined by spectroscopic and chemical methods as 4-methyl ( ? )-(R)-hydroxyeucomate (1), 4-butyl ( ? )-(R)-hydroxyeucomate (2), 4-butyl-1-methyl (+)-(R)-2-O-(4′-hydroxy-3′-methoxybenzoyl)malate (3), 1-butyl-4-methyl (+)-(R)-2-O-(4′-hydroxy-3′-methoxybenzoyl)malate (4), dimethyl (+)-(R)-2-O-(4′-hydroxy-3′-methoxybenzoyl)malate (5), dimethyl (+)-(R)-2-O-(4′-hydroxybenzoyl)malate (6), and methyl ( ± )-3-(4′-hydroxy-3′-methoxyphenyl)-3-sulfopropionate (7), respectively. Compounds 1 and 2 are 2-benzylmalates (eucomate derivatives), 3–6 belong to 2-O-benzoylmalates, and 7 is a rare phenylpropionate containing a sulfonic acid group. The absolute configurations of eucomate derivatives were confirmed by X-ray crystallographic analysis of 4-methyl eucomate (11).     

Aromatic glycosides from the flower buds of Lonicera japonica

Six new glycosides (1–6) have been isolated from the flower buds of Lonicera japonica. Their structures including the absolute configurations were determined by spectroscopic and chemical methods as ( ? )-2-hydroxy-5-methoxybenzoic acid 2-O-β-d-(6-O-benzoyl)-glucopyranoside (1), ( ? )-4-hydroxy-3,5-dimethoxybenzoic acid 4-O-β-d-(6-O-benzoyl)-glucopyranoside (2), ( ? )-(E)-3,5-dimethoxyphenylpropenoic acid 4-O-β-d-(6-O-benzoyl)-glucopyranoside (3), ( ? )-(7S,8R)-(4-hydroxyphenylglycerol 9-O-β-d-[6-O-(E)-4-hydroxy-3,5-dimethoxyphenylpropenoyl]-glucopyranoside (4), ( ? )-(7S,8R)-(4-hydroxy-3-methoxyphenylglycerol 9-O-β-d-[6-O-(E)-4-hydroxy-3,5-dimethoxyphenylpropenoyl]-glucopyranoside (5), and ( ? )-4-hydroxy-3-methoxyphenol β-d-{6-O-[4-O-(7S,8R)-(4-hydroxy-3-methoxyphenylglycerol-8-yl)-3-methoxybenzoyl]}-glucopyranoside (6), respectively.     

A new thiophene and two new monoterpenoids from Xanthium sibiricum

Three new compounds (1–3), together with six known compounds (4–9), were isolated from the fruits of Xanthium sibiricum. The structures and the absolute configurations of sibiricumthionol (1), (+)-(5Z)-6-methyl-2-ethenyl-5-hepten-1,2,7-triol [(+)-2], ( ? )-(5Z)-6-methyl-2-ethenyl-5-hepten-1,2,7-triol [( ? )-2], (2E,4E,1′S, 2′R, 4′S, 6′R)-dihydrophaseic acid (3), (+)-xanthienopyran [(+)-4] and ( ? )-xanthienopyran [( ? )-4] were established by extensive spectroscopic analyses, X-ray crystallographic analysis, ECCD analysis and ECD calculations. Caffeic acid (7) and caffeic acid ethyl ester (8) weekly inhibited α-glucosidase enzymatic activity by 44.5% and 40.2%, respectively, at 40 μM. Protocatechuic acid (9) selectively exhibited cytotoxicity against HepG2 cell lines, with an IC₅₀ value of 2.92 μM.     

Two new coumarins from the seeds of Solanum indicum

Two new coumarins, (E)-2-(4-hydroxy-3-methoxybenzylidene)-5-methoxy-2H-[1,4]dioxino[2,3-h]chromene-3,9-dione (indicumin E, 1) and 7-hydroxy-6,8-dimethoxy-3-(4′-hydroxy-3′-methoxyphenyl)-coumarin (2), together with two known coumarins isofraxidin (3) and fraxetin (4), were isolated from the Solanum indicum seeds. Their structures were established on the basis of 1D and 2D spectroscopic data. Compound 1 was the rarest coumarinolignoid known to date.     

New phenolic glycosides from Pilea cavaleriei

Five new phenolic glycosides, 2-hydroxy-(2′E)-prenyl benzoate-2,4′-di-O-β-d-glucopyranoside (1), 2-hydroxy-(2′E)-prenyl benzoate-2-O-α-l-arabinopyranosyl-(1 → 6)-β-d-glucopyranoside (2), 4-methylphenol-1-O-α-l-rhamnopyranosyl-(1 → 6)-β-d-glucopyranoside (3), 4-methylphenol-1-O-α-l-arabinopyranosyl-(1 → 6)-β-d-glucopyranoside (4), and 3,5-dimethoxyphenol-1-O-β-d-apiofuranosyl-(1 → 2)-β-d-glucopyranoside (5), together with six known glycosides (6–11), were isolated from the n-BuOH fraction of the EtOH extract of Pilea cavaleriei Levl subsp. cavaleriei. Their structures were elucidated by extensive spectroscopic analysis, including 1D and 2D NMR spectroscopy as well as HR-ESI-MS, and chemical evidences. All these compounds were isolated from the genus Pilea for the first time.     

Norlignans from Pouzolzia zeylanica var. microphylla and their nitric oxide inhibitory activity

Five new compounds, pouzolignan F [4-hydroxy-3-(3,5-dihydroxyphenyl)-2-[bis(4-hydroxy-3-methoxyphenyl)methyl]butyl acetate] (1), pouzolignan G [4-hydroxy-3-(3,5-dihydroxyphenyl)-2-[(4-hydroxy-3,5-dimethoxyphenyl)(4-hydroxy-3-methoxyphenyl)methyl]butyl acetate] (2), pouzolignan H [1,4-dihydroxy-3-(3,5-dihydroxyphenyl)-2-[bis(4-hydroxy-3-methoxyphenyl)methyl]butane] (3), pouzolignan I [1,4-dihydroxy-3-(3,5-dihydroxyphenyl)-2-[(4-hydroxy-3,5-dime thoxyphenyl)-(4-hydroxy-3-methoxyphenyl)methyl]butane] (4), and pouzolignan J [1,4-dihydroxy-3-(3,5-dihydroxyphenyl) -2-[(3,4,5-trimethoxyphenyl)(4-hydroxy-3-methoxyphenyl)methyl]butane] (5), along with two known compounds, indolyl-3-carboxylic acid (6) and uracil (7), were isolated from the aerial parts of Pouzolzia zeylanica (L.) Benn. var. microphylla (Wedd.) W.T.Wang. The structures of these compounds were characterized based on spectroscopic methods, including IR, NMR (¹H–¹H COSY, HSQC, HMBC, and NOESY), and HR-ESI/TOF-MS experiments. All the new norlignans were assayed for inhibitory activity against lipopolysaccharide (LPS)-induced nitric oxide (NO) production in mouse peritoneal macrophages.     

Cytotoxic stilbenes from the roots of Paphiopedilum godefroyae

Two new stilbenes, 2-(3′,5′-dimethoxyphenyl)-6-hydroxy-5-methoxybenzofuran (1) and 3′-hydroxy-2,5′-dimethoxystilbene (2), together with seven known stilbenes (3, 5–10) and one flavanone (4), were isolated from the roots of Paphiopedilum godefroyae. Their chemical structures were determined on the basis of their spectroscopic data. These isolated compounds were evaluated for their cytotoxicity against human small cell lung cancer (NCI-H187) cell lines and an arylbenzofuran derivative, 5,6-dimethoxy-2-(3-hydroxy-5-methoxyphenyl)benzofuran (6), was shown to be strongly cytotoxic with an IC₅₀ value of 5.10 μM.     

New long-chain hydroxyalkyl ferulates from the root bark of Lycium chinense Mill.

Two new long-chain hydroxyalkyl ferulates, (E)-22-hydroxydocosyl 3-(4-hydroxy-3-methoxyphenyl)acrylate (lyciumol A, 1) and (E)-20-hydroxyeicosyl 3-(4-hydroxy-3-methoxyphenyl)acrylate (lyciumol B, 2), together with eight known compounds, were isolated from the root bark of Lycium chinense Mill. Their structures were elucidated by spectroscopic methods, including 1D, 2D NMR, and HR-ESI-MS analysis.     

Two new aromatic compounds from the resin of Styrax tonkinensis (Pier.) Craib

Two new aromatic compounds, trans-(tetrahydro-2-(4-hydroxy-3-methoxyphenyl)-5-oxofuran-3-yl)methyl benzoate (1), 3-(4-hydroxy-3-methoxyphenyl)-2-oxopropyl benzoate (2) and one new natural product, 4-((E)-3-ethoxyprop-1-enyl)-2-methoxyphenol (3) together with five known aromatic compounds have been isolated from the resin of Styrax tonkinensis (Pier.) Craib. Their structures were determined by physical and spectroscopic methods.     

Secondary metabolites from the roots of Phlomis umbrosa

The phytochemical study of the roots of Phlomis umbrosa Turcz afforded a new phenylethanoid glycoside, 3-hydroxy-4-methoxy-β-phenylethoxy-O-[2,3-diacetyl-α-l-rhamnopyranosyl-(1 → 3)]-4-O-cis-feruloyl-[β-d-apiofuranosyl-(1 → 6)]-β-d-glucopyranoside (1), and two new 28-noroleanane-derived spirocyclic triterpenoids, phlomishexaol C (2) and phlomishexaol D (3). Their structures were elucidated on the basis of 1D and 2D NMR analyses, in combination with high-resolution MS experiment.     

Four new glucosides from the aerial parts of Mediasia macrophylla

As part of our chemical studies on the medical plants in Uzbekistan aimed at searching for new drug leads, we have examined the aerial parts of Mediasia macrophylla. This has resulted in the isolation of four new glucosides, together with 30 known compounds. The structures of new compounds were elucidated as (1′S)-(4-hydroxyphenyl) ethane-1′,2′-diol 2′-O-β-glucopyranoside (1), 3-(4′-methoxyphenyl)-propanol 1-O-β-glucopyranoside (2), 2-methoxy-3-hydroxy-5-(E)-propenyl-phenol 1-O-β-glucopyranoside (3), 1-O-angeloyl-β-glucopyranose (4), on the basis of spectral analysis.     

Three triterpenoid saponins acylated with monoterpenic acid from Gymnocladus chinensis

A new triterpenoid saponin acylated with monoterpenic acid, together with two known triterpenoid saponins, has been isolated from the fruit of Gymnocladus chinensis Baill. Their structures were elucidated as 2β,23-dihydroxy-3-O-α-L-rhamnopyranosyl-21-O-{(6S)-2-trans-2,6-dimethyl-6-O-[3-O-(β-D-glucopyranosyl)-4-O-((6S)-2-trans-2,6-dimethyl-6-hydroxy-2,7-octadienoyl)-β-L-arabinopyranosyl]-2,7-octadienoyl}-acacic acid 28-O-β-D-xylopyranosyl-(1 → 3)-β-D-xylopyranosyl-(1 → 4)-α-L-rhamnopyranosyl-(1 → 2)-[α-L-rhamnopyranosyl-(1 → 6)]-β-D-glucopyranosyl ester (1), gymnocladus saponin E (2), and gymnocladus saponin F₂ (3).     

Two new phenols from Lysimachia patungensis

Two new phenols, methyl 3-(2-O-β-d-glucopyranosyl-3-hydroxy-5-methoxyphenyl) propionate (1) and myricetin-3,3′,5′-tri-O-α-l-rhamnopyranoside (2), together with six known phenols compounds (3–8), were isolated from the whole plant of Lysimachia patungensis Hand.-Mazz. Their structures were elucidated on the basis of the interpretation of spectroscopic data, viz., ESI-MS, HR-TOF-MS, UV, IR, and NMR. All the known phenols were isolated from the genus Lysimachia for the first time. A preliminary bioassay revealed that compounds 3 and 7 exhibited significant protective effects against hydrogen peroxide-induced damage in human retinal endothelial cells (HRECs) with the concentration of 10 μM, respectively. Compound 1 showed moderate activity against the HRECs damage at 100 μM.     

A pair of isomeric saponins with cytotoxicity from Albizzia julibrissin

Two new saponins have been isolated from the stem barks of Albizzia julibrissin Durazz, and their structures identified as 3-O-[β-d-xylopyranosyl-(1 → 2)-β-d-fucopyranosyl-(1 → 6)-β-d-2-deoxy-2-acetoamidoglucopyranosyl]-21-O-{(6S)-2- trans -2-hydroxymethyl-6-methyl-6-O-[4-O-((6S )-2- trans -2-hydroxymethyl-6-hydroxy-6-methyl-2,7-octadienoyl)-β-d-quinovopyranosyl]-2,7-octadienoyl}-acacic acid-28-O-β-d-glucopyranosyl-(1 → 3)-[α-l-arabinofuranosyl-(1 → 4)]-α-l-rhamnopyranosyl-(1 → 2)-β-d-glucopyranosyl ester (1) and 3-O-[β-d-xylopyranosyl-(1 → 2)-β-d-fucopyranosyl-(1 → 6)-β-d-2-deoxy-2-acetoamidoglucopyranosyl]-21-O-{(6S)-2-trans-2-hydroxymethyl-6-methyl-6-O-[3-O-((6S)-2-trans-2-hydroxymethyl-6-hydroxy-6-methyl-2,7-octadienoyl)-β-d-quinovopyranosyl]-2,7-octadienoyl}acacic acid 28-O-β-d-glucopyranosyl-(1 → 3)-[α-l-arabinofuranosyl-(1 → 4)]-α-l-rhamnopyranosyl-(1 → 2)-β-d-glucopyranosyl ester (2), based on chemical and spectral evidences, named as julibroside J₁₉ and julibroside J₁₈, respectively. Both compounds show significant inhibition action against HeLa, Bel-7402 and MDA-MB-435 cancer cell lines in vitro.     

Two new 8-O-4′-type lignans from the stem of Schima superba and their cell growth inhibitory activities against human cancer cell lines

Two new lignans (1 and 2) were isolated from the EtOH extracts of the stem of Schima superba, and elucidated as (7R,8S)-1-(3,4-dimethoxyphenyl)-2-O-(2-methoxy-4-omegahydroxypropylphenyl)propane-1,3-diol (1) and threo-1-(4-hydroxy-3-methoxyphenyl)-1-methoxy-2-{4-[1-formyl-(E)-vinyl]-2-methoxyphenoxy}-3-propanol (2) by spectral analysis. Compounds 1 and 2 showed cell growth inhibitory activity against HeLa, CNE, HepG-2, and HEp-2 cell lines. Compound 1 exhibited significant cytotoxicities with IC₅₀ values of less than 4 μg/ml against all the tested cell lines.     

A novel spinosin derivative from Semen Ziziphi Spinosae

A novel spinosin derivative, 6?-(4?′-O-β-d-glucopyranosyl)-vanilloyl spinosin (1) was isolated from the methanol extract of Semen Ziziphi Spinosae, together with five known flavonoids, swertish (2), spinosin (3), 6?-feruloylspinosin (4), isospinosin (5) and kaempferol 3-O-α-l-rhamnopyranosyl-(1 → 2)-O-[O-α-l-rhamnopyranosyl-(1 → 6)]-β-d-glucopyranoside (6), and two alkanoids, zizyphusine (7) and 6-(2′,3′-dihydroxyl-4′-hydroxymethyl-tetrahydro-furan-1′-yl)-cyclopentene[c]pyrrole-1,3-diol (8). The structure of compound 1 was elucidated by spectroscopic methods including UV, IR, ESI-TOF-MS, 1D, and 2D NMR techniques.     

Triterpenoid glycosides from Stauntonia chinensis

A new bidesmoside triterpenoid saponin, named stauntoside C1 (1), along with three known saponins (2–4) was isolated from Stauntonia chinensis DC. (Lardizabalaceae). Their structures were established by means of spectral and chemical methods as 3-O-β-d-xylopyranosyl-(1 → 2)-O-β-d-xylopyranosyl-(1 → 3)-O-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl oleanolic acid 28-O-α-l-rhamnopyranosyl-(1 → 4)-β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranosyl ester (1), scabiosaponin E (2), sieboldianoside B (3), and kizutasaponin K₁₂ (4).     

Three new steroidal saponins from Fritillaria pallidiflora

Three new steroidal saponins, pallidiflosides A (1), B (2), and C (3), have been isolated from the dry bulbs of Fritillaria pallidiflora Schrenk. Their structures were elucidated as 26-O-β-d-glucopyranosyl-(25R)-furost-5,20(22)-dien-3β,26-diol-3-O-β-d-xylopyranosyl(1 → 4)-[α-l-rhamnopyranosyl(1 → 2)]-β-d-glucopyranoside (1); 26-O-β-d-glucopyranosyl-3β,26-dihydroxyl-20,22-seco-25(R)-furost-5-en-20,22-dione-3-O-α-l-rhamnopyranosyl(1 → 2)-β-d-glucopyranoside (2); and (25R)-spirost-5-ene-3β,17α-diol-3-O-β-d-glucopyranosyl(1 → 4)-β-d-galactopyranoside (3) by spectroscopic techniques and chemical means.     

Two natural compounds – a benzofuran and a phenylpropane – from Artemisia dracunculus

The structure elucidation of three metabolites herniarin (7-methoxy-2H-chromen-2-one, 1), phytoalexin (5-acetyl-6-hydroxy-2-(1-hydroxy-1-methylethyl)benzofuran, 2), and prestragol (3-(4′-methoxyphenyl)-prop-1,2-diol, 3) isolated from Artemisia dracunculus was determined on the basis of 1D, 2D NMR methods and by an X-ray crystallographic determination.