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).     

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.     

Two new furostanol glycosides from the fibrous root of Ophiopogon japonicus (Thunb.) Ker-Gawl

Two new furostanol glycosides, ophiopogonins H (1) and I (2), were isolated from the fibrous root of Ophiopogon japonicus. The structures of 1 and 2 were established as (25R)-26-[(O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl)]-22α-hydroxyfurost-5-ene-3-O-[α-l-rhamnopyranosyl-(1 → 2)]-β-d-glucopyranoside and (25R)-26-[(O-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl)]-20α-hydroxyfurost-5,22-diene-3-O-[α-l-rhamnopyranosyl-(1 → 2)]-β-d-glucopyranoside on the basis of spectroscopic means including HR-ESI-MS, 1D and 2D NMR experiments.     

Two new furostanol saponins from the seeds of Trigonella foenum-graecum

Two new furostanol saponins, together with two known steroidal saponins, were isolated from the seeds of Trigonella foenum-graecum L. The structures of the new compounds were determined by detailed analysis of 1D NMR, 2D NMR, MS spectra and chemical evidences as 26-O-β-d-glucopyranosyl-(25S)-5-en-furost-3β,22α,26-triol 3-O-α-l-rhamnopyranosyl-(1 → 2)-[β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranosyl-(1 → 3)-β-d-glucopyranosyl-(1 → 4)]-β-d-glucopyranoside (1) and 26-O-β-d-glucopyranosyl-(25R)-5-en-furost-3β,22α,26-triol 3-O-α-l-rhamnopyranosyl-(1 → 2)-[β-d-glucopyranosyl-(1 → 6)]-β-d-glucopyranosyl-(1 → 3)-β-d-glucopyranosyl-(1 → 4)]-β-d-glucopyranoside (2).     

Pregnane glycosides from Solanum nigrum

Two new pregnane saponins, solanigroside A (1) and solanigroside B (2), along with two known compounds (3 and 4), were isolated from 60% ethanolic extract of the dried herb of Solanum nigrum L. The structures of 1 and 2 were elucidated as 5α-pregn-16-en-3β-ol-20-one 3-O-β-d-xylopyranosyl-(1 → 3)-O-[α-l-arabinopyranosyl-(1 → 2)]-O-β-d-glucopyranosyl-(1 → 4)-O-[α-l-rhamnopyranosyl-(1 → 2)]-O-β-d-galactopyranoside (1) and 5α-pregn-16-en-3β-ol-20-one 3-O-β-d-glucopyranosyl-(1 → 2)-O-[β-d-glucopyranosyl-(1 → 3)]-O-β-d-glucopyranosyl-(1 → 4)-O-β-d-galactopyranoside (2), respectively, on the basis of extensive spectroscopic analysis as well as comparison with reported spectroscopic data of related compounds. This paper deals with the isolation and structural characterisation of pregnane glycosides from S. nigrum L.     

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.     

Two new furostanol saponins from the fibrous root of Ophiopogon japonicus

Two new furostanol saponins ophiopogonins J (1) and K (2) were isolated from the fibrous roots of Ophiopogon japonicus. The structures of 1 and 2 were established as (25R)-26-O-[(β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl)]-14-hydroxy-furost-5,20(22)-diene 3-O-[α-l-rhamnopyranosyl-(1 → 2)]-β-d-glucopyranoside (1), and (25R)-26-O-[(β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl)]-furost-5,20(22)-diene 3-O-α-l-rhamnopyranosyl-(1 → 2)[(β-d-xylopyranosyl-(1 → 4)-β-d-glucopyranoside)] (2) on the basis of spectroscopic means including HRESIMS, 1D, and 2D NMR experiments.     

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.     

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.     

A novel triterpenoid saponin from Polygala tenuifolia Willd.

A new triterpenoid saponin, tenuifoside A, was isolated together with three known triterpenoid saponins 2, 3, and 4 from the roots of Polygala tenuifolia Willd. With the help of chemical and spectral analyses (IR, MS, 1D-NMR, and 2D-NMR), the structure of the new saponin was elucidated as 3-O-β-d-glucopyranosyl presenegenin 28-O-β-d-xylopyranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)-[β-d-apiofuranosyl-(1 → 3)]-α-l-rhamnopyranosyl-(1 → 2)-[4-O-p-methoxycinnamoyl]-[α-l-rhamnopyranosyl-(1 → 3)]-β-d-fucopyranosyl ester (1). Three known triterpenoid saponins (2–4) were identified on the basis of spectroscopic data.     

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.     

New acylated triterpene saponins from Polygala tenuifolia willd

Two new acylated presenegenin glycosides E-onjisaponin H (5) and Z-onjisaponin (6) together with seven known saponins were isolated from the roots of Polygala tenuifolia Willd. Compounds 5 and 6 were obtained as a pair of isomers due to trans and cis-p-methoxycinnamoyl. Their structures were elucidated mainly by 2D-NMR techniques including ¹H–¹HCOSY, TOCSY, HSQC, HMBC as 3-O-(β-d-glucopyranosyl) presenegenin 28-{O-β-d-apiofuranosyl-(1 → 3)-O-[β-d-xylopyranosyl-(1 → 4)]-O-α-l-rhamnopyranosyl-(1 → 2)-O-[α-l-rhamnopyranosyl-(1 → 3)]-4-O-[(E)-p-methoxycinnamoyl]-β-d-fucopyranosyl} ester (5) and its (Z)-isomer (6).     

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).     

A new triterpenoid saponin from Ardisia gigantifolia

A new triterpenoid saponin, named 3-O-β-d-glucopyranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 2)-[α-l-rhamnopyranosyl-(1 → 3)]-β-d-glucopyranosyl-(1 → 4)-[β-d-glucopyranosyl-(1 → 2)]-α-l-arabinopyranosyl-3β,16α,28,30-tetrahydroxy-olean-12-ene (1), along with four known triterpenoids (2–5), was isolated from the rhizomes of Ardisia gigantifolia. Their structures were elucidated by spectroscopic methods. Compounds 1–4 showed cytotoxic activity against Hela, EJ, BCG, and HepG-2 cell lines. The percentage of early apoptotic cells after treatment with 1 was significantly increased compared with control cells (p < 0.05).     

Two new triterpenoid saponins from Sarcandra glabra

Two new triterpenoid saponins, named sarcandroside A and B, have been isolated from Sarcandra glabra (Thunb) Nakai. Their structures have been established as 3β,19α,20β-trihydroxyurs-11,13 (18)-diene-28,20β-lactone-3-O-β-d-glucopyranosyl (1 → 3)-[α-l-rhamnopyranosyl(1 → 2)]-β-d-xylopyranoside (1) and 3-O-β-d-glucopyranosyl (1 → 3)-[α-l-rhamnopyranosyl(1 → 2)]-β-d-xylopyranosyl-pomolic acid 28-O-β-d-glucopyranosyl ester (2) by means of spectral and chemical methods.     

Triterpene constituents from the seedling of Aronia melanocarpa

Two new triterpene saponins, 16-O-acetyl-21-O-angeloyltheasapogenol A 3-O-[β-d-galactopyranosyl(1 → 2)][β-d-xylopyranosyl(1 → 2)-α-l-arabinopyranosyl (1 → 3)]-β-d-glucopyranosiduronic acid (1) and 16,28-O-diacetyl-21-O-tigloyltheasapogenol A 3-O-[β-d-galactopyranosyl(1 → 2)][β-d-xylopyranosyl(1 → 2)-α-l-arabinopyranosyl (1 → 3)]-β-d-glucopyranosiduronic acid (2), together with four known triterpenenes, have been isolated from the dried seedling of Aronia melanocarpa, and their structures established by spectroscopic and chemical evidence.     

Cytotoxic triterpenoid saponins from Vaccaria segetalis

By the guidance of bioassay, one new cytotoxic triterpenoid saponin, 3-O-[β-d-galactopyranosyl-(1 → 2)-β-d-glucuronopyranosyl] quillaic acid 28-O-β-d-glucopyranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)-α-l-rhamnopyranosyl-(1 → 2)-[β-d-fucopyranosyl-(1 → 4)]-β-d-fucopyranoside (1), and five known cytotoxic triterpenoid saponins, vaccaroside E (2), vaccaroside G (3), vaccaroside B (4), segetoside H (5) and segetoside I (6), were isolated from Vaccaria segetalis. Their structures were established on the basis of ESI-MS, IR, extensive NMR (¹H NMR, ¹³C NMR, TOCSY, ¹H–¹H COSY, DEPT, HMQC, HMBC and ROESY) analyses, chemical degradation, and by comparing with previously reported data. Compounds 1–6 showed moderate cytotoxic activities against LNcap, P-388 and A-549 cell lines with IC₅₀ values in the range 0.1–12.9 μM.     

Three new C-flavonoids from Corallodiscus flabellata

Three new C-glycosylflavones, named 5,7,4′-trihydroxy-6-methoxy-8-C-[β-d-xylopyranosyl- (1 → 2)]-β-d-glucopyranosyl flavonoside (1), 5,7,4′-trihydroxy-8-methoxy-6-C-[β-d-xylopyranosyl-(1 → 2)]-β-d-glucopyranosyl flavonoside (2), and 5,3′,4′-trihydroxy-7,8-dimethoxy-6-C-[β-d-xylopyranosyl-(1 → 2)]-β-d-glucopyranosyl flavonoside (3), along with two known compounds 5,4′-dihydroxy-7-methoxy-6-C-glucopyranosyl-flavonoside (4), 3-methoxy-4-hydroxymethyl benzoate (5) were isolated from 70% acetone extract of Corallodiscus flabellata. Their structures were identified on the basis of spectroscopic techniques and chemical methods.     

Two new bioactive triterpene glycosides from the sea cucumber Pseudocolochirus violaceus

By activity-guided fractionation, two new triterpene glycosides, violaceusides A (1) and B (2), were isolated from the sea cucumber Pseudocolochirus violaceus as active compounds causing morphological abnormality of Pyricularia oryzae mycelia. By extensive 2D NMR techniques and chemical evidence, the structures of the two new glycosides were established as 16β-acetoxy-3-O-[3-O-methyl-β-d-glucopyranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)-β-d-quinovopyranosyl-(1 → 2)-4-O-sodiumsulphate-β-d-xylopyranosyl]-holosta-7,24-diene-3β-ol (1) and 16β-acetoxy-3-O-[3-O-methyl-β-d-glucopyranosyl-(1 → 3)-β-d-xylopyranosyl-(1 → 4)-β-d-glucopyranosyl-(1 → 2)-4-O-sodiumsulphate-β-d-xylopyranosyl]-holosta-7,24-diene-3β-ol (2), respectively. The two glycosides also exhibited significant cytotoxicity against HL-60 and BEL-7402 cancer cell lines.     

Two new triterpenoid saponins from Symplocos Chinensis

Two new triterpenoid saponins, symplocososides X (1) and Y (2) have been isolated from the roots of Symplocos chinensis, and their structures elucidated as 21β-O- cinnamoyl-22α-O-(2-methylbutanoyl)-15α, 16α, 28-trihydroxyolean-12-ene-3β-O-[β-d-glucopyranosyl (1 → 2)]-α-l-arabinofuranosyl (1 → 4)-β-d-glucuronopyranoside (1) and 21β-O-cinnamoyl-22α-O-(2-methylbutanoyl)-15α, 16α, 28-trihydroxyolean-12-ene-3β-O-(3-O-acetyl)-[β-d-glucopyranosyl (1 → 2)]-α-l-arabinofuranosyl (1 → 4)-β-d-glucuronopyranoside (2) by spectral and chemical methods. Their antitumor activities have also been tested.