A novel oligosaccharide ester from Syringa pubescens

Pubescenside A (1), a novel oligosaccharide ester, has been isolated from the flowers of Syringa pubescens, together with five known compounds d-mannitol (2), meso-inositol (3), hydrostytosol (4), glucose (5), and sucrose (6). The structure of 1 was elucidated as 1-O-[β-d-glucopyranosyl-(1–6)-β-d-galactopyranosyl-(1–1)-β-d-galactopyranosyl-6]-4,4-dimethylpelargonicate by chemical and spectroscopic means. The water extract of the flowers and leaves of S. pubescens showed cytotoxicity against L2215 cell line (IC₅₀ = 78 μg/ml).     

Three new triterpenoid saponins from the seeds of Aesculus turbinata

Three new triterpenoid saponins, named isoescins VIIa (1), VIa (2), and VIIIa (3), were isolated from the seeds of Aesculus turbinata and identified by spectroscopic analysis and chemical hydrolysis. Their structures were established as 21β-O-tigloyl-28-O-acetylprotoaescigenin 3β-O-[β-d-galactopyranosyl(1 → 2)][β-d-glucopyranosyl(1 → 4)]-β-d-glucopyranosiduronic acid (Isoescin VIIa, 1), 21β-O-(2-methylbutyryl)-28-O-acetylprotoaescigenin 3β-O-[β-d-glucopyranosyl(1 → 2)] [β-d-glucopyranosyl(1 → 4)]-β-d-glucopyranosiduronic acid (Isoescin VIa, 2), and 21β-O-angeloyl-28-O-acetylbarringtogenol C 3β-O-[β-d-glucopyranosyl(1 → 2)] [β-d-glucopyranosyl(1 → 4)]-β-d-glucopyranosiduronic acid (Isoescin VIIIa, 3).     

Note: Xanthone glycosides from Swertia franchetiana

A new xanthone glycoside (1) has been isolated from Swertia franchetiana together with five known xanthone glycosides. Their structures were elucidated as 7-O-[β-d-xylopyranosyl-(1→2)-β-d-xylopyranosyl]-1,7,8-trihydroxy-3-methoxyxanthone (1), 7-O-[α-l-rhamnopyranosyl-(1→2)-β-d-xylopyranosyl]-1,7,8-trihydroxy-3-methoxyxanthone (2), 8-O-β-d-glucopyranosyl-1,3,5,8-tetrahydroxyxanthone (3), 1-O-β-d-glucopyranosyl-1-hydroxy-3,7,8-trimethoxyxanthone (4), 1-O-[β-d-xylopyranosyl-(1→6)-β-d-glucopyranosyl]-1-hydroxy-2,3,5-trimethoxyxanthone (5) and 1-O-[β-d-xylopyranosyl-(1→6)-β-d-glucopyranosyl]-1-hydroxy-3,5-dimethoxyxanthone (6) on the basis of spectroscopic evidence.     

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.     

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).     

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).     

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.     

Isolation,structural elucidation of flavonoid constituents from Leptadenia pyrotechnica and evaluation of their toxicity and antitumor activity

An investigation of Leptadenia pyrotechnica (Forsk.) Decne (Asclepiadaceace) chemical constituents led to the isolation of six flavonoids, kaempferol-3-O-α-l-rhamnopyranosyl (1′″→6″)-O-β-d-glucopyranoside (E-I.1), kaempferol-3-O-β-d-rhamnopyranosyl (1′″→6″)-O-β-d-glucopyranoside (E-I.2), texasin-7-O-β-d-glucopyranoside E-II.2, kaempferol-3-O-β-d-glucopyranoside (E-III.1), kaempferol (E-IV.1) and kaempferide-3-O-α-l-rhamnopyranosyl (1′″→6″)-O-β-d-glucopyranoside (E-I.1a). The isolation of these compounds was carried out using Sephadex LH-20 low pressure liquid chromatography (LPLC), preparative paper chromatography (PC), and high performance liquid chromatography (HPLC). The chemical structures of the isolated compounds were established by mass spectrometry (FAB- and EI- techniques), nuclear magnetic resonance NMR (¹H-, ¹³C- and COSY) spectral data and ultraviolet (UV) spectroscopic techniques. The acute toxicity of total alcoholic and total flavonoid extracts were examined by brine shrimp. The LC₅₀ values were 11.89 and 84.14 ppm for the total alcoholic and total flavonoid extracts, respectively. The mortality rates of the isolated flavonoid fractions of E-I, E-I.1, E-I.2 represent the higher percentages of mortality compared with the rest of the flavonoid fractions. The plant exhibited activity as an antitumor agent in the initial potato disc screen.     

Two new triterpenoid saponins from Ardisia crenata

Two new triterpenoid saponins, ardisicrenoside K (1) and ardisicrenoside L (2), have been isolated from the roots of Ardisia crenata Sims. Their structures have been determined as 3β-O-{α-l-rhamnopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 4)-[β-d-glucopyranosyl-(1 → 2)]-α-l-arabinopyranosyl}-13β,28-epoxy-16-oxo-30,30-dimethoxyoleanane and 3β-O-{β-d-xylopyranosyl-(1 → 2)-β-d-glucopyranosyl-(1 → 4)-[β-d-glucopyranosyl-(1 → 2)]-α-l-arabinopyranosyl}-13β,28-epoxy-16α,20-dihydroxyoleanane by means of chemical evidences and spectral analysis. Their weak anti-fungal activity against the plant pathogenic fungus Pyricularia oryzae was evaluated in vitro.     

Triterpenoid saponins from the roots of Clematis chinensis Osbeck

A new triterpenoid saponin named clematichinenoside AR₂, along with the six known compounds, was isolated and characterized from Clematis chinensis Osbeck (Ranunculaceae), a commonly used traditional Chinese medicine with anti-inflammatory and anti-rheumatoid activities. The structure of the new saponin was elucidated as 3-O-β-[(O-α-l-rhamnopyranosyl-(1 → 6)-O-β-d-glucopyranosyl-(1 → 4)-O-β-d-glucopyranosyl-(1 → 4)-O-β-d-ribopyranosyl-(1 → 3)-O-α-l-rhamnopyranosyl-(1 → 2)-α-l-arabinopyranosyl)oxy]olean-12-en-21α-hydroxy-28-oic acid-O-α-l-rhamnopyranosyl-(1 → 4)-O-β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranosyl ester (1) by spectral analysis and chemical methods. The effects of two major saponins (clematichinenosides AR and AR₂) on the secretion of TNF-α in murine peritoneal macrophages induced by lipopolysaccharides were further investigated. The result indicated that a majority of triterpenoid saponins of this herb may be useful in the exploration of lead compounds for the treatment of some autoimmune diseases.     

Four new oleanane type Saponins from Morina nepalensis var. alba

Four new oleanane type saponins, monepalosides G–J (1–4), were isolated from the water-soluble part of the whole plant of Morina nepalensis var. alba Hand-Mazz. On the basis of chemical and spectroscopic evidence, their structures were determined as 3-O-α-L-arabinopyranosyl-(1→3)-α-L-arabinopyranosyl oleanolic acid 28-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside (monepaloside G, 1), 3-O-α-L-arabinopyranosyl-(1→3)-β-D-xylopyranosyl oleanolic acid 28-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside (monepaloside H, 2), 3-O-α-L-arabinopyranosyl-(1→3)-[β-D-glucopyranosyl-(1→2)]-α-L-arabinopyranosyl oleanolic acid 28-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside (monepaloside I, 3), 3-O-β-D-glucopyranosyl-(1→4)-β-D-glucopyranosy-(1→3)]-α-L-arabinopyranosyl oleanolic acid 28-O-β-D-glucopyranosyl-(1→6)-β-D-glucopyranoside (monepaloside J, 4), respectively. Two-dimensional NMR spectra, including H–H COSY, HMQC, 2D HMQC–TOCSY, HMBC and ROESY were utilized in the structure elucidation and complete assignments of ¹H and ¹³C NMR spectra.     

Novel furostanol saponins from the bulbs of Allium macrostemon B. and their bioactivity on [Ca2+]i increase induced by KCl

Chemical reinvestigation of the ethanol extract of the dried bulbs of Allium macrostemon B. led to the isolation of two novel furostanol saponins, named macrostemonoside M (1) and macrostemonoside N (2), together with six known saponins. The structures of new compounds were elucidated on the basis of extensive spectroscopic analysis including 1D and 2D NMR as (25R)-22-hydroxy-5β-furostane-1β,2β,3β,6α-tetraol-26-O-β-d -glucopyranoside and 22-hydroxy-5β-furost-25-(27)-ene-1β,2β,3β,6α-tetraol-26-O-β-d -glucopyranoside, respectively. The pharmacological activities of all the saponins on [Ca²⁺]_i increase induced by KCl were evaluated.     

New steroidal glycosides from Hosta plantaginea (Lam.) Aschers

Four new furostanol glycosides were isolated from the flowers of Hosta plantaginea (Lam.) Aschers. On the basis of spectroscopic methods including 1D and 2D NMR experiments, their structures were elucidated as 26-O-β-d-glucopyranosyl-(25R)-22-O-methyl-5α-furostan-2α,3β,22ξ,26-tetrol 3-O-α-l-rhamnopyranosyl-(1 → 4)-O-β-d-xylopyranosyl-(1 → 3)-[O-β-d-glucopyranosyl-(1 → 2)]-O-β-d-glucopyranosyl-(1 → 4)-β-d-galactopyranoside (hostaplantagineoside A, 1), 26-O-β-d-glucopyranosyl-(25R)-5α-furostan-20(22)-ene-2α,3β,26-triol-3-O-β-d-glucopyranosyl-(1 → 2)-[O-β-d-xylopyranosyl-(1 → 3)]-O-β-d-glucopyranosyl-(1 → 4)-β-d-galactopyranoside (hostaplantagineoside B, 2), 26-O-β-d-glucopyranosyl-(25R)-5α-furostan-22(23)-ene-2α,3β,20α,26-tetraol-3-O-β-d-glucopyranosyl-(1 → 2)-[O-β-d-xylopyranosyl-(1 → 3)]-O-β-d-glucopyranosyl-(1 → 4)-O-β-d-galactopyranoside (hostaplantagineoside C, 3), 26-O-β-d-glucopyranosyl-(25R)-5α-furostan-20(22)-ene-2α,3β,26-triol-3-O-α-l-rhamnopyranosyl-(1 → 4)-O-β-d-xylopyranosyl-(1 → 3)-[O-β-d-glucopyranosyl-(1 → 2)]-O-β-d-glucopyranosyl-(1 → 4)-β-d-galactopyranoside (hostaplantagineoside D, 4).     

Four new triterpenoid glycosides from the seed residue of Hippophae rhamnoides subsp. sinensis

Four new triterpenoid saponins (1–4) were isolated from the seed residue of Hippophae rhamnoides subsp. sinensis, named 3-O-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl-(1 → 3)]-[α-l-rhamnopyranosyl-(1 → 2)]-α-l-arabinopyranosyl-13-ene-19-one-28-oic acid 28-O-β-d-glucopyranosyl ester (1), 3-O-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl-(1 → 3)]-[α-l-rhamnopyranosyl-(1 → 2)]-α-l-arabinopyranosyl-13-ene-19-one-30-hydroxyolean-28-oic acid 28-O-β-d-glucopyranosyl ester (2), 3-O-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl-(1 → 3)]-[α-l-rhamnopyranosyl-(1 → 2)]-β-d-glucopyranosyl-13-ene-19-one-28-oic acid 28-O-β-d-glucopyranosyl ester (3), and 3-O-[β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl-(1 → 3)]-[α-l-rhamnopyranosyl-(1 → 2)]-β-d-glucopyranosyl-13-ene-19-one-30-hydroxyolean-28-oic acid 28-O-β-d-glucopyranosyl ester (4), and their structures were elucidated on the basis of spectroscopic and chemical methods.     

Two new triterpenoid glycosides from Cyclocarya paliurus

Two new dammarane triterpenoid glycosides named cyclocarosides B (1) and C (2) were isolated from the leaves of Cyclocarya paliurus. Based on FAB-MS, HRESI-MS, IR, ¹H NMR, ¹³C NMR, and 2D-NMR (HMQC, HMBC, COSY, ROESY) data, the structures of cyclocarosides B (1) and C (2) were elucidated as (20S,24R)-epoxydammarane (3β,12β)-25-hydroxyl-12-O-β-d-quinovopyranosyl-3-O-β-d-quinovopyranoside (1), and (20S,24R)-epoxydammarane (3β, 12β)-25-hydroxyl-12-O-α-l-arabinopyranosyl-3-O-(5′-O-acetyl)-α-l-arabinofuranoside (2).     

Two new triterpenoid saponins from ginseng medicinal fungal substance

Two new dammarane-type triterpenoid saponins, namely ginsenosides Rb₄ (1) and Rb₅ (2), were isolated from ginseng medicinal fungal substance. The structures of 1 and 2 were established as 3β,12β,20(S)-trihydroxydammar-24(25)-ene-3-O-[α-d-glucopyranosyl-(1→4)-β-d-glucopyranosyl-(1→2)-β-d-glucopyranosyl]-20-O-β-d-glucopyranoside and 3β,12β,20(S)-trihydroxydammar-24(25)-ene-3-O-[α-d-glucopyranosyl-(1→4)-α-d-glucopyranosyl-(1→4)-β-d-glucopyranosyl-(1→2)-β-d-glucopyranosyl]-20-O-β-d-glucopyranoside on the basis of spectroscopic analysis and chemical analysis, respectively.     

Triterpenoid saponins from the rhizome of Polygonatum sibiricum

Three new triterpenoid saponins, polygonoides C (1), D (2), and E (3), were obtained from the ethanolic extract of the rhizome of Polygonatum sibiricum Redoute. On the basis of NMR and ESI-MS spectra, and chemical evidence, the structures of the three new compounds were elucidated as 3-O-α-L-rhamnopyranosyl-(1 → 2)-β-D-glucopyranosyl-(1 → 4)-β-D-glucopyranosyl-3β,7β,22β-trihydroxy-oleanolic acid (1), 3-O-α-L-rhamnopyranosyl-(1 → 2)-β-D-glucopyranosyl-(1 → 4)-β-D-glucopyranosyl-3β,7β,22β-trihydroxy-oleanolic acid methyl ester (2), and 3-O-β-D-glucopyranosyl-(1 → 3)-β-D-glucopyranosyl-(1 → 4)-[α-L-rhamno-pyranosyl-(1 → 2)]-β-D-glucopyranosyl-3β,21β-dihydroxy-oleanolic acid 28-O-β-D-glucopyranosyl-(1 → 3)-β-D-glucopyranosyl-(1 → 3)-β-D-glucopyranoside (3).     

Cuneatoside,a new megastigmane diglycoside from Erythroxylum cuneatum Blume

A new megastigmane diglycoside, inamoside 6′-O-l-α-arabinofuranoside (cuneatoside), was isolated from the leaves and branches of Erythroxylum cuneatum together with seven known compounds, (+)-catechin, quercetin 3-O-α-l-rhamnoside, apocynol B, (6S,9R)-roseoside, vomifoliol 9-O-α-l-arabinofuranosyl (1 → 6)-β-d-glucopyranoside, inamoside, and citroside A The structural elucidations were based on analyses of physical and spectroscopic data.     

Furostanol oligoglycosides from Asparagus cochinchinensis

Three new furostanol oligoglycosides, named aspacochioside A (1), B (2) and C (3), together with the known compound 3-O-[{α-l-rhamnopyranosyl-(1→4)}{β-d-glucopyranosyl}]-26-O-[β-d-glucopyranosyl]-(25S)-5β-spirostane-3β-ol were isolated from the roots of Asparagus cochinchinensis. Their structures were elucidated by spectroscopic techniques (IR, HR-ESIMS, ESIMS/MS, 1D and 2D NMR) and chemical methods as 3-O-[{α-l-rhamnopyranosyl-(1→4)}{β-d-glucopyranosyl}]-26-O-[β-d-glucopyranosyl]-(25S)-5β-furostane-3β,22α,26-triol (1), 3-O-[{α-l-rhamnopyranosyl-(1→4)}{β-d-glucopyranosyl}]-26-O-[β-d-glucopyranosyl]-22α-methoxy-(25S)-5β-furostane-3β,26-diol (2), and 3-O-[{α-l-rhamnopyranosyl-(1→4)}{β-d-glucopyranosyl}]-26-O-[β-d-glucopyranosyl]-(25S)-5β-furost-20(22)-en-3β,26-diol (3).     

New oleanane-type triterpenoid saponins isolated from the seeds of Celosia argentea

Three new oleanane-type triterpenoid saponins named celosins H (1), I (2), and J (3) were isolated from the seeds of Celosia argentea L. Their structures were characterized as 3-O-β-d-xylopyranosyl-(1 → 3)-β-d-glucuronopyranosyl-polygalagenin 28-O-β-d-glucopyranosyl ester, 3-O-β-d-glucuronopyranosyl-medicagenic acid 28-O-β-d-xylcopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-β-d-fucopyranosyl ester, and 3-O-β-d-glucuronopyranosyl-medicagenic acid 28-O-α-l-arabinopyranosyl-(1 → 3)-[β-d-xylcopyranosyl-(1 → 4)]-α-l-rhamnopyranosyl-(1 → 2)-β-d-fucopyranosyl ester by NMR, MS, and chemical evidences, respectively. In our opinion, celosins H–J could be used as chemical markers for the quality control of C. argentea seeds.