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.     

Microbial deglycosylation and ketonization of ginsenosides Rg1 and Rb1 by Fusarium oxysporum

Two major ginsenosides, ginsenoside-Rg₁ (1) and ginsenoside-Rb₁ (2), were transformed by the fungus Fusarium oxysporum f. sp. Lycopersici (Z-001). 1 was converted into five metabolites, ginsenoside-F₁ (3), 6α,12β-dihydroxydammar-3-one-20(S)-O-β-d-glucopyranoside (4), 3a-oxa-3a-homo-6α,12β-dihydroxydammar-3-one-20(S)-O-β-d-glucopyranoside (5), 20(S)-protopanaxatriol (6), and 3-oxo-20(S)-protopanaxatriol (7). 2 was converted into four metabolites, ginsenoside-Rd (8), ginsenoside-F₂ (9), compound K (10), and 12β-hydroxydammar-3-one-20(S)-O-β-d-glucopyranoside (11). The structures of these metabolites were determined by the analysis of extensive spectroscopic data. Among them, 4 and 5 were two new compounds. Deglycosylation and ketonization at C-3 were recognized as the characteristic reactions of this strain.     

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.     

Two new anthraquinone glycosides from the roots of Rheum palmatum

Two new anthraquinone glycosides, named 1-methyl-8-hydroxyl-9,10-anthraquinone-3-O-β-d-(6′-O-cinnamoyl)glucopyranoside (1) and rhein-8-O-β-d-[6′-O-(3″-methoxyl malonyl)]glucopyranoside (2), have been isolated from the roots of Rheum palmatum, together with seven known compounds, rhein-8-O-β-d-glucopyranoside (3), physcion-8-O-β-d-glucopyranoside (4), chrysophanol-8-O-β-d-glucopyranoside (5), aleo-emodin-8-O-β-d-glucopyranoside (6), emodin-8-O-β-d-glucopyranoside (7), aleo-emodin-ω-O-β-d-glucopyranoside (8), and emodin-1-O-β-d-glucopyranoside (9). Their structures were elucidated on the basis of chemical and spectral analysis.     

Two new neolignan glucosides from Arctii Fructus

Two new neolignan glucosides named (7S, 8R)-4,7,9,9′-tetrahydroxy-3,3′-dimethoxyl-7′-oxo-8-4′-oxyneolignan-4-O-β-d-glucopyranoside (1) and (7′S, 8′R, 8S)-4,4′,9′-trihydroxy-3,3′-dimethoxy-7′,9-epoxylignan-7-oxo-4-O-β-d-glucopyranosyl-4′-O-β-d-glucopyranoside (2), together with two small molecular peptides named 3-benzyl-6-(1-hydroxyethyl)-2,5-piperazinedione (3) and 3-benzyl-2,5-piperazinedione (4), were isolated from the extract of Arctii Fructus. Their structures and absolute configurations were elucidated by various spectroscopic methods (IR, HR-ESI-MS, 1D and 2D NMR, and CD).     

A new pregnane glycoside and oligosaccharide from Parabarium huaitingii

Two new compounds, along with two known compounds, were isolated from the barks of Parabarium huaitingii, and their structures were determined as 5α-pregn-6-ene-3β,17α,20(S)-triol-20-O-β-d-digitoxopyranoside (1), cymaropyranurolactone 4-O-β-d-digitalopyranosyl-(1 → 4)-O-β-d-cymaropyranosyl-(1 → 4)-O-β-d-oleandropyranosyl-(1 → 4)-O-β-d-cymaropyranoside (2), 3β,17α,20(S)-trihydroxy-5α-pregn-6-ene (3), and 5α-pregn-6-ene-3β,17α,20(S)-triol-3-O-β-d-digitalopyranoside (4) by spectroscopic methods.     

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.     

Flavonoids from Camptosorus sibiricus Rupr.

Three new flavonol glycosides, kaempferol-3-O-(6-trans-caffeoyl)-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside (1), kaempferol-3-O-(6-trans-caffeoyl)-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside-7-O-β-d-glucopyranoside (2), and kaempferol-3-O-(6-trans-p-coumaroyl)-β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranoside-7-O-β-d-glucopyranoside (3), were isolated from the aerial part of Camptosorus sibiricus. Their structures were elucidated by spectroscopic methods, including 2D NMR spectral techniques.     

Aromatic glycosides from the whole plants of Iris japonica

Phytochemical investigation on the whole plants of Iris japonica led to the isolation of four new aromatic glycosides. Their structures including the absolute configurations were determined by spectroscopic and chemical methods as (?)-4-hydroxy-3-methoxy acetophenone 4-O-β-d-{6-O-[4-O-(7R,8S)-(4-hydroxy-3-methoxyphenylglycerol-8-yl)-3-methoxybenzoyl]}-glucopyranoside (1), (?)-4-hydroxy-3-methoxy acetophenone 4-O-β-d-{6-O-[4-O-(7S,8R)-(4-hydroxy-3-methoxyphenylglycerol-8-yl)-3-methoxybenzoyl]}-glucopyranoside (2), (?)-4-hydroxy-3-methoxy acetophenone 4-O-β-d-{6-O-[4-O-(7R,8R)-(4-hydroxy-3-methoxyphenylglycerol-8-yl)-3-methoxybenzoyl]}-glucopyranoside (3), (?)-4-hydroxy-3-methoxy acetophenone 4-O-β-d-{6-O-[4-O-(7S,8S)-(4-hydroxy-3-methoxyphenylglycerol-8-yl)-3-methoxybenzoyl]}-glucopyranoside (4), respectively.     

Two new furostanol saponins from Tribulus terrestris L.

Two new furostanol saponins, tribufurosides B (1) and C (2), were isolated from the fruits of Tribulus terrestris L. With the help of chemical and spectral analyses (IR, MS, 1D NMR and 2D NMR), the structures of two new furostanol saponins were established as 26-O-β-d-glucopyranosyl-(25S)-5α-furost-20(22)-en-2α,3β,26-triol-3-O-β-d-galactopyranosyl(1 → 2)-β-d-glucopyranosyl(1 → 2)-β-d-galactopyranoside (1) and (25S)-5α-furost-20(22)-en-12-one-3β, 26-diol-26-O-β-d-glucopyranoside (2).     

Two new dammarane-type triterpene saponins from red American ginseng

Two new dammarane-type triterpene saponins were isolated from the red American ginseng. The new saponins were named as pseudoginsenoside G₁ (1) and pseudoginsenoside G₂ (2). Their structures were elucidated by the combined analysis of NMR and mass spectrometry as 3-O-[β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl]-dammar-12-one-20S,24R-epoxy-3β,25-diol (pseudoginsenoside G₁) (1) and 3-O-[β-d-glucopyranosyl-(1 → 2)-β-d-glucopyranosyl]-dammar-12-one-20S,24S-epoxy-3β,25-diol (pseudoginsenoside G₂) (2).     

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).     

Two new dihydrobenzofuran lignans from Rabdosia lophanthoides (Buch.-Ham.ex D.Don) Hara

Two new dihydrobenzofuran lignanosides, (7R,8S)-4,3′,9′-trihydroxyl-3-methoxyl-7,8-dihydrobenzofuran-1′-propylneolignan-9-O-(6-O-syringoyl)-β-d-glucopyranoside, named lophanthoside B (1) and (7R,8S)-4,9,9′-trihydroxyl-3-methoxyl-7,8-dihydrobenzofuran-1′-propylneolignan-3′-O-β-d-glucopyranoside (2), an enantiomer of umbroside, along with four known dihydrobenzofuran lignans (3–6), were isolated from 50% acetone extract of Rabdosia lophanthoides (Buch.-Ham.ex D.Don) Hara. Their structures were elucidated by NMR and MS experiments.     

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.     

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.     

Two new steroidal saponins from Tribulus terrestris L.

Two new steroidal saponins were isolated from the fruits of Tribulus terrestris L. Their structures were elucidated by spectroscopic and chemical analysis as (23S,24R,25R)-5α-spirostane-3β,23,24-triol-3-O-{α-l-rhamnopyranosyl-(1 → 2)-[β-d-glucopyranosyl-(1 → 4)]-β-d-galactopyranoside} (1) and (23S,24R,25S)-5α-spirostane-3β,23,24-triol-3-O-{α-l-rhamnopyranosyl-(1 → 2)-[β-d-glucopyranosyl-(1 → 4)]-β-d-galactopyranoside} (2).     

Phytolacacinoside A,a new triterpenoid saponin from Phytolacca acinosa Roxb

Phytolacacinoside A (1), a novel triterpenoid saponin, together with the seven known compounds, was isolated from 75% ethanol extract of the root of Phytolacca acinosa Roxb (Phytolaccaceae). Their structures were elucidated on the basis of analysis of spectroscopic data and physicochemical properties as 3-O-β-[(β-d-glucopyranosyl-(1 → 4)-O-β-d-xylopyranosyl)]-11β-methoxy-jaligonic acid 30-methyl ester 28-O-β-d-glucopyranoside (1), 3-O-β-[(β-d-glucopyranosyl-(1 → 4)-O-β-d-xylopyranosyl)]-jaligonic acid 30-methyl ester 28-O-β-d-glucopyranoside (2, esculentoside G), 3-O-β-[(β-d-glucopyranosyl-(1 → 4)-O-β-d-xylopyranosyl)]-jaligonic acid 30-methyl ester (3, phytolaccoside E), 3-O-β-d-xylopyranosyl-jaligonic acid 30-methyl ester (4, phytolaccoside B), hypaphorine (5), palmitic acid monoglyceride (6), β-sitosterol (7), and daucosterol (8).     

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.     

Two new steroidal saponins from Tribulus terrestris

Two new steroidal saponins and two known flavonoid glycosides were isolated from the fruits of Tribulus terrestris. Their structures were assigned by spectroscopic analysis and chemical reaction as 26-O-β-d-glucopyranosyl-(25R)-5α-furostan-12-one-3β,22α,26-triol-3-O-β-d-glucopyranosyl (1 → 2)-β-d-glucopyranosyl(1 → 4)-β-d-galactopyranoside (1), 26-O-β-d-glucopyranosyl-(25S)-5α-furostan-22-methoxy-2α,3β,26-triol-3-O-β-d-glucopyranosyl(1 → 2)-β-d-glucopyranosyl(1 → 4)-β-d-galactopyranoside (2), kaempferol-3-gentiobioside (3), and isorhamnetin-3-gentiobioside (4).     

Two new chlorophenyl glycosides from the bulbs of Lilium brownii var. viridulum

Two rare new chlorophenyl glycosides, 2,4,6-trichlorol-3-methyl-5-methoxy-phenol 1-O-β-d-glucopyranosyl-(1 → 6)-β-d-glucopyranoside (1) and 4-chlorol-5-hydroxyl-3-methyl-phenol 1-O-α-l-rhamnopyranosyl-(1 → 6)-β-d-glucopyranoside (2), along with three known compounds (3–5) were isolated from the bulbs of Lilium brownii var. viridulum. The structures of the new compounds were elucidated on the basis of spectroscopic and chemical methods. All the compounds exhibited weak inhibition of NO production in LPS-stimulated RAW 264.7 cells.