Phenylethyl Glycosides from Digitalis lanata

Three new phenylethyl glycosides, 3′′′′‐O‐methylmaxoside (=2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐O‐[β‐D ‐glucopyranosyl‐(1→6)]‐4‐O‐(E)‐feruloyl‐β‐D ‐glucopyranoside; 1 ), digilanatosides A (=2‐(3,4‐dihydroxyphenyl)ethyl O‐6‐O‐(E)‐sinapoyl‐β‐D ‐glucopyranosyl‐(1→3)‐4‐O‐(E)‐caffeoyl‐β‐D ‐glucopyranoside; 2 ), and digilanatoside B (=2‐(3,4‐dihydroxyphenyl)ethyl O‐6‐O‐(E)‐p‐coumaroyl‐β‐D ‐glucopyranosyl‐(1→3)‐4‐O‐(E)‐caffeoyl‐β‐D ‐glucopyranoside; 3 ) were isolated from the aerial parts of Digitalis lanata, along with two known phenylethyl glycosides, purpureaside A and maxoside, a phenylpropanoid glucose ester, 1‐O‐(E)‐feruloyl‐β‐glucopyranose, a benzoquinolethanoid glucoside, cornoside, a cardenolide, lanatoside C, a furostane‐type steroidal saponin, purpureagitoside, and a disaccharide, sucrose. Their structures were elucidated on the basis of spectroscopic evidence (1D‐ and 2D‐NMR, and HR‐MALDI‐MS).     

Phenyl and Phenylethyl Glycosides from Picrorhiza scrophulariiflora

Three new phenyl glycosides, scrophenoside A ( 1 ), B ( 2 ), and C ( 3 ), and two new phenylethyl glycosides, scroside D ( 4 ) and scroside E ( 5 ), were isolated from the stem of Picrorhiza scrophulariiflora Pennell (Scrophularlaceae), besides five known compounds. On the basis of spectroscopic evidence, the structures of the new compounds were elucidated as 4‐acetyl‐2‐methoxyphenyl 6‐O‐[4‐(β‐D ‐glucopyranosyloxy)vanilloyl]‐β‐D ‐glucopyranoside ( 1 ), 4‐acetylphenyl 6‐O‐[(E)‐p‐coumaroyl]‐β‐D ‐glucopyranoside ( 2 ), 4‐[(1R)‐ and (1S)‐1‐hydroxyethyl]‐2‐methoxyphenyl β‐D ‐glucopyranoside ( 3a and 3b , resp.), 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐4‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 4 ), and 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐glucopyranosyl‐(1→3)‐6‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranoside ( 5 ).     

Two New Phenylethanoid Glycosides from Callicarpa longissima

Two new phenylethanoid glycosides, longissimosides A and B ( 1 and 2 , resp.), together with eight structurally related known compounds, were isolated from the EtOH extract of leaves and stems of Callicarpa longissima (Hemsl .) Merr . The structures of 1 and 2 were elucidated as 2‐(3,4‐dihydroxyphenyl)ethyl O‐(α‐L ‐rhamnopyranosyl)‐(1→3)‐O‐(2‐O‐syringoyl‐β‐D ‐xylopyranosyl)‐(1→6)‐ 4‐O‐[(E)‐caffeoyl]‐β‐D ‐glucopyranoside ( 1 ) and 2‐(3‐hydroxy‐4‐methoxyphenyl)ethyl O‐(α‐L ‐rhamnopyranosyl)‐(1→3)‐O‐(β‐D ‐apiofuranosyl)‐(1→6)‐4‐O‐[(E)‐isoferuloyl]‐β‐D ‐glucopyranoside ( 2 ) on the basis of spectroscopic data and acid hydrolysis.     

Phenylethyl Glycosides from Globularia alypum Growing in Turkey

From the leaves of Globularia alypum, three new phenylethyl glycosides, namely galypumosides A (=2‐(3,4‐dihydroxyphenyl)ethyl O‐α‐rhamnopyranosyl‐(1→3)‐4‐O‐[(E)‐caffeoyl]‐6‐O‐[(E)‐p‐coumaroyl]‐β‐glucopyranoside; 1 ), B (=2‐(3,4‐dihydroxyphenyl)ethyl O‐α‐rhamnopyranosyl‐(1→3)‐4‐O‐[(E)‐caffeoyl]‐6‐O‐[(E)‐feruloyl]‐β‐glucopyranoside; 2 ), and C (=2‐(3,4‐dihydroxyphenyl)ethyl O‐α‐rhamnopyranosyl‐(1→3)‐4‐O‐[(E)‐caffeoyl]‐6‐O‐menthiafoloyl‐β‐glucopyranoside; 3 ), were isolated, together with two known phenylethyl glycosides, calceolarioside A and verbascoside. Eight iridoid glucosides, catalpol, globularicisin, globularin, globularidin, globularinin, globularimin, lytanthosalin, and alpinoside, a flavon glycoside, 6‐hydroxyluteolin 7‐O‐sophoroside, a lignan glycoside, syringaresinol 4′‐O‐β‐glucopyranoside, and a phenylpropanoid glycoside, syringin, were also obtained and characterized. The structures of the isolates were elucidated on the basis of 1D‐ and 2D‐NMR experiments as well as HR‐MALDI‐MS.     

Revised structures of avenacosides A and B and a new sulfated saponin from Avena sativa L.

The revised structures of avenacosides A and B and a new sulfated steroidal saponin isolated from grains of Avena sativa L. were elucidated. Their structures and complete NMR assignments are based on 1D and 2D NMR studies and identified as nuatigenin 3‐O‐{α‐l ‐rhamnopyranosyl‐(1→2)‐[β‐D‐glucopyranosyl‐(1→4)]‐β‐d ‐glucopyranoside}‐26‐O‐β‐d ‐glucopyranoside (1), nuatigenin 3‐O‐{α‐l ‐rhamnopyranosyl‐(1→2)‐[β‐d ‐glucopyranosyl‐(1→3)‐β‐d ‐glucopyranosyl‐(1→4)]‐β‐d ‐glucopyranoside}‐26‐O‐β‐d ‐glucopyranoside (2), and nuatigenin 3‐O‐{α‐l ‐rhamnopyranosyl‐(1→2)‐[β‐d ‐6‐O‐sulfoglucopyranosyl‐(1→4)]‐β‐d ‐glucopyranoside}‐26‐O‐β‐d ‐glucopyranoside (3). Copyright © 2012 John Wiley & Sons, Ltd.     

Highly Polar Triterpenoid Saponins from the Roots of Saponaria officinalis L.

Five new triterpenoid saponins, including 3‐O‐β‐d ‐galactopyranosyl‐(1→2)‐[β‐d ‐xylopyranosyl‐(1→3)]‐β‐d ‐glucuronopyranosyl quillaic acid 28‐O‐β‐d ‐glucopyranosyl‐(1→3)‐β‐d ‐xylopyranosyl‐(1→4)‐α‐l ‐rhamnopyranosyl‐(1→2)‐[β‐d ‐xylopyranosyl‐(1→3)‐(4‐O‐acetyl)‐β‐d ‐quinovopyranosyl‐(1→4)]‐β‐d ‐fucopyranoside ( 1 ), 3‐O‐β‐d ‐galactopyranosyl‐(1→2)‐[β‐d ‐xylopyranosyl‐(1→3)]‐β‐d ‐glucuronopyranosyl quillaic acid 28‐O‐(6‐O‐acetyl)‐β‐d ‐glucopyranosyl‐(1→3)‐[β‐d ‐xylopyranosyl‐(1→4)]‐α‐l ‐rhamnopyranosyl‐(1→2)‐[β‐d ‐xylopyranosyl‐(1→3)‐(4‐O‐acetyl)‐β‐d ‐quinovopyranosyl‐(1→4)]‐β‐d ‐fucopyranoside ( 2 ), 3‐O‐β‐d ‐galactopyranosyl‐(1→2)‐[β‐d ‐xylopyranosyl‐(1→3)]‐β‐d ‐glucuronopyranosyl quillaic acid 28‐O‐β‐d ‐xylopyranosyl‐(1→4)‐α‐l ‐rhamnopyranosyl‐(1→2)‐[β‐d ‐xylopyranosyl‐(1→3)‐(4‐O‐acetyl)‐β‐d ‐quinovopyranosyl‐(1→4)]‐β‐d ‐fucopyranoside ( 3 ), 3‐O‐β‐d ‐galactopyranosyl‐(1→2)‐[β‐d ‐xylopyranosyl‐(1→3)]‐β‐d ‐glucuronopyranosyl quillaic acid 28‐O‐β‐d ‐glucopyranosyl‐(1→3)‐β‐d ‐xylopyranosyl‐(1→4)‐α‐l ‐rhamnopyranosyl‐(1→2)‐[(4‐O‐acetyl)‐β‐d ‐quinovopyranosyl‐(1→4)]‐β‐d ‐fucopyranoside ( 4 ), 3‐O‐β‐d ‐galactopyranosyl‐(1→2)‐[β‐d ‐xylopyranosyl‐(1→3)]‐β‐d ‐glucuronopyranosyl quillaic acid 28‐O‐(6‐O‐acetyl)‐β‐d ‐glucopyranosyl‐(1→3)‐[β‐d ‐xylopyranosyl‐(1→4)]‐α‐l ‐rhamnopyranosyl‐(1→2)‐[(4‐O‐acetyl)‐β‐d ‐quinovopyranosyl‐(1→4)]‐β‐d ‐fucopyranoside ( 5 ) together with two known congeners, saponariosides A ( 6 ) and B ( 7 ) were isolated from the roots of Saponaria officinalis L. Their structures were elucidated by extensive spectroscopic methods, including 1D‐ (¹H, ¹³C) and 2D‐NMR (DQF‐COSY, TOCSY, HSQC, and HMBC) experiments, HR‐ESI‐MS, and acid hydrolysis.     

Iridoid and Phenylethyl Glycosides from Globularia sintenisii

A new iridoid glycoside, sintenoside ( 1 ) and two new phenylethyl glycosides, globusintenoside (=2‐(3,4‐dihydroxyphenyl)ethyl‐O‐6‐O‐feruloyl‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→3)‐4‐O‐caffeoyl‐β‐D ‐glucopyranoside; 2 ) and 3′′′‐O‐methylcrenatoside (=1,2‐O‐[2‐(3,4‐dihydroxyphenyl)ethan‐1,2‐diyl]‐3‐O‐α‐L ‐4‐O‐feruloyl‐rhamnopyranosyl‐β‐D ‐glucopyranose; 3 ) were isolated from the underground parts of Globularia sintenisii, along with three known iridoid glycosides, lytanthosalin, globularin, catalpol, and six known phenylethyl glycosides, verbascoside, isoverbascoside, leucoscepthoside A, plantainoside C, martynoside, and isocrenatoside. The structure elucidation of the isolated compounds was performed by spectroscopic methods (MS and 1D and 2D NMR).     

Seven New Acyl Glycosides from Erycibe obtusifolia

Seven new acyl glycosides, benzyl 5‐O‐vanilloyl‐β‐d ‐apiofuranosyl‐(1→6)‐β‐d ‐glucopyranoside ( 1 ), 4‐hydroxy‐3‐methoxyphenyl 5‐O‐syringoyl‐β‐d ‐apiofuranosyl‐(1→6)‐β‐d ‐glucopyranoside ( 2 ), isopentyl 5‐O‐syringoyl‐β‐d ‐apiofuranosyl‐(1→6)‐β‐d ‐glucopyranoside ( 3 ), 3,4,5‐trimethoxyphenyl 5‐O‐sinapoyl‐β‐d ‐apiofuranosyl‐(1→6)‐β‐d ‐glucopyranoside ( 4 ), 6‐methoxy‐7‐[(6‐O‐sinapoyl‐β‐d ‐glucopyranosyl)oxy]coumarin ( 5 ), 6‐methoxy‐7‐[(2‐O‐sinapoyl‐β‐d ‐glucopyranosyl)oxy]coumarin ( 6 ), and isopentyl β‐d ‐apiofuranosyl‐(1→6)‐[5‐O‐syringoyl‐β‐d ‐apiofuranosyl‐(1→2)]‐β‐d ‐glucopyranoside ( 7 ), were isolated from Chinese folk herb Erycibe obtusifolia. Their structures were elucidated on the basis of extensive spectroscopic analysis, including UV, IR, MS, and 1D‐ and 2D‐NMR techniques. Further, these compounds were evaluated against HCT‐8 (human colon carcinoma), Bel‐7402 (human liver carcinoma), BGC‐823 (human stomach carcinoma), A549 (human lung carcinoma), and A2780 (human ovarian carcinoma) cell lines, however, none of them exhibited a significant bioactivity (IC₅₀ > 10 μm ).     

New Triterpenoidal Saponins Acylated with Monoterpenic Acid from Albizia adianthifolia

Four new triterpenoidal saponins acylated with monoterpenic acid, i.e., adianthifoliosides C, D, E, and F ( 1 – 4 ), besides the two known julibroside III and the monodesmonoterpenyl elliptoside A, were isolated from the roots of Albizia adianthifolia. Their structures were elucidated on the basis of extensive 1D‐ and 2D‐NMR studies and mass spectrometry as 3‐O‐{O‐α‐L ‐arabinopyranosyl‐(1→2)‐O‐β‐d‐ fucopyranosyl‐(1→6)‐O‐[β‐d‐ glucopyranosyl‐(1→2)]‐β‐d‐ glucopyranosyl}‐21‐O‐{(2E,6S)‐6‐{{4‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐(β‐D ‐quinovopyranosyloxy)octa‐2,7‐dienoyl]‐β‐d‐ quinovopyranosyl}oxy}‐2‐(hydroxymethyl)‐6‐methylocta‐2,7‐dienoyl}acacic acid 28‐{O‐α‐L ‐arabinofuranosyl‐(1→4)‐O‐[β‐d‐ glucopyranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐d‐ glucopyranosyl} ester ( 1 ), 21‐O‐{(2E,6S)‐6‐{{4‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐(β‐d‐ quinovopyranosyloxy)octa‐2,7‐dienoyl]‐β‐d‐ quinovopyranosyl}oxy}‐2‐(hydroxymethyl)‐6‐methylocta‐2,7‐dienoyl}‐3‐O‐{O‐β‐D ‐xylopyranosyl‐(1→2)‐O‐β‐d‐ fucopyranosyl‐(1→6)‐2‐(acetylamino)‐2‐deoxy‐β‐d‐ glucopyranosyl}acacic acid 28‐{O‐α‐L ‐arabinofuranosyl‐(1→4)‐O‐[β‐d‐ glucopyranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐d‐ glucopyranosyl} ester ( 2 ), 21‐O‐{(2E,6S)‐6‐{{3‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐(β‐d‐ quinovopyranosyloxy)octa‐2,7‐dienoyl]‐β‐d‐ quinovopyranosyl}oxy}‐2,6‐dimethylocta‐2,7‐dienoyl}‐3‐O‐{O‐β‐D ‐xylopyranosyl‐(1→2)‐O‐β‐d‐ fucopyranosyl‐(1→6)‐2‐(acetylamino)‐2‐deoxy‐β‐d‐ glucopyranosyl}acacic acid 28‐{O‐α‐L ‐arabinofuranosyl‐(1→4)‐O‐[β‐d‐ glucopyranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐d‐ glucopyranosyl} ester ( 3 ), and 3‐O‐{O‐α‐L ‐arabinopyranosyl‐(1→2)‐O‐β‐d‐ fucopyranosyl‐(1→6)‐O‐[β‐d‐ glucopyranosyl‐(1→2)]‐β‐d‐ glucopyranosyl}‐21‐O‐{(2E,6S)‐2,6‐dimethyl‐6‐(β‐d‐ quinovopyranosyloxy)octa‐2,7‐dienoyl}acacic acid 28‐{O‐α‐L ‐arabinofuranosyl‐(1→4)‐O‐[β‐d‐ glucopyranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐d‐ glucopyranosyl} ester ( 4 ).     

Six New Triterpenoid Glycosides from Gynostemma pentaphyllum

Six new triterpenoid glycosides, gynosaponins I–VI ( 1 – 6 , resp.), together with three known compounds, ginseng Rb₁ ( 7 ), gypenoside XLIX ( 8 ), and gylongiposide I ( 9 ), were isolated from the aerial parts of Gynostemma pentaphyllum. Based on ESI‐MS, IR, 1D‐ and 2D‐NMR data (HMQC, HMBC, COSY, and TOCSY), the structures of the new compounds were determined as (3β,12β,20S)‐trihydroxydammar‐24‐ene 20‐O‐[α‐rhamnopyranosyl‐(1→2)]‐β‐glucopyranoside ( 1 ), (3β,12β,20S)‐trihydroxydammar‐24‐ene 20‐O‐[α‐rhamnopyranosyl‐(1→2)] [α‐rhamnopyranosyl‐(1→3)]‐β‐glucopyranoside ( 2 ), (3β,12β,20S)‐trihydroxydammar‐24‐ene 3‐O‐β‐glucopyranosyl‐20‐O‐[α‐rhamnopyranosyl‐(1→2)]‐β‐glucopyranoside ( 3 ), (3β,12β,20S)‐trihydroxydammar‐24‐ene 3‐O‐β‐glucopyranosyl‐20‐O‐[α‐rhamnopyranosyl‐(1→2)] [α‐rhamnopyranosyl‐(1→3)]‐β‐glucopyranoside ( 4 ), (3β,12β,20S)‐trihydroxydammar‐24‐ene 3‐O‐{[β‐glucopyranosyl‐(1→2)]‐β‐glucopyranosyl}‐20‐O‐[α‐rhamnopyranosyl‐(1→2)]‐β‐glucopyranoside ( 5 ), and (3β,12β,20S)‐trihydroxydammar‐24‐ene 3‐O‐{[β‐glucopyranosyl‐(1→2)]‐β‐glucopyranosyl}‐20‐O‐[α‐rhamnopyranosyl‐(1→2)] [α‐rhamnopyranosyl‐(1→3)]‐β‐glucopyranoside ( 6 ).     

Clintoniosides A – C,New Polyhydroxylated Spirostanol Glycosides from the Rhizomes of Clintonia udensis

Phytochemical analyses were carried out on the rhizomes of Clintonia udensis (Liliaceae) with particular attention paid to the steroidal glycoside constituents, resulting in the isolation of three new polyhydroxylated spirostanol glycosides, named clintonioside A ( 1 ), B ( 2 ), and C ( 3 ). On the basis of their spectroscopic data, including 2D‐NMR spectroscopy, in combination with acetylation and hydrolytic cleavage, the structures of 1 – 3 were determined to be (1β,3β,23S,24S,25R)‐1,23,24‐trihydroxyspirost‐5‐en‐3‐yl O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐glucopyranoside ( 1 ), (1β,3β,23S,24S)‐3,21,23,24‐tetrahydroxyspirosta‐5,25(27)‐dien‐1‐yl O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[β‐D ‐xylopyranosyl‐(1→3)]‐β‐D ‐glucopyranoside ( 2 ), and (1β,3β,23S,24S)‐21‐(acetyloxy)‐24‐[(6‐deoxy‐β‐D ‐gulopyranosyl)oxy]‐3,23‐dihydroxyspirosta‐5,25(27)‐dien‐1‐yl O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[β‐D ‐xylopyranosyl‐(1→3)]‐β‐D ‐glucopyranoside ( 3 ).     

Water‐Soluble Constituents from the Liverwort Marchantia polymorpha

Four new glycosides, the bibenzyl glycoside α,β‐dihydrostilbene‐2,4′,5‐triol 2,5‐di‐(β‐D ‐glucopyranoside) ( 1 ), the shikimic acid glycoside shikimic acid 4‐(β‐D ‐xylopyranoside) ( 2 ), and two phenylethanoid glycosides 2‐(3,4‐dihydroxyphenyl)ethyl O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐allopyranoside ( 3 ) and 2‐(3,4‐dihydroxyphenyl)ethyl O‐β‐D ‐xylopyranosyl‐(1→6)‐β‐D ‐allopyranoside ( 4 ), together with three known aromatic glycosides were isolated from the H₂O‐soluble fraction of the EtOH extract of the liverwort Marchantia polymorpha. Their structures were elucidated on the basis of chemical and spectroscopic evidences.     

Acylated Triterpene Saponins from Atroxima liberica Stapf

The four new acylated triterpene saponins 1 – 4 , isolated as two pairs of isomers and named libericosides A₁/A₂ and B₁/B₂, one pair of isomers 5 / 6 , the (Z)‐isomer libericoside C₂ ( 5 ) being new, one new sucrose ester, atroximoside ( 7 ), and eight known compounds were isolated from the roots of Atroxima liberica by repeated MPLC and VLC on normal and reversed‐phase silica gel. Their structures were elucidated on the basis of extensive 1D‐ and 2D‐NMR studies (¹H‐ and ¹³C‐NMR, DEPT, COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry as 3‐O‐β‐D ‐glucopyranosylpresenegenin 28‐{O‐α‐L ‐arabinopyranosyl‐(1→3)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐4‐O‐[(E)‐3,4‐dimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 1 ) and its (Z)‐isomer 2 , 3‐O‐β‐D ‐glucopyranosylpresenegenin 28‐{O‐α‐L ‐arabinopyranosyl‐(1→4)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[O‐β‐D ‐xylopyranosyl‐(1→3)‐β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐[(E)‐3,4‐dimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 3 ) and its (Z)‐isomer 4 , 3‐O‐β‐D ‐glucopyranosylpresenegenin 28‐{O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[6‐O‐acetyl‐β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐[(Z)‐3,4‐dimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 5 ), and 3‐O‐[(Z)‐feruloyl]‐β‐D ‐fructofuranosyl α‐D ‐glucopyranoside ( 7 ). Compounds 1 – 6 and the known saponins 8 / 9 were evaluated against the human colon cancer cells HCT 116 and HT‐29 and showed moderate to weak cytotoxicity.     

Bidesmosidic Oleanane Saponins from Xerospermum noronhianum

Three new oleanane‐type triterpenoid saponins, 3‐O‐(α‐L ‐rhamnopyranosyl(1→2)‐β‐D ‐fucopyranosyl)‐28‐O‐{[α‐L ‐rhamnopyranosyl(1→2)] [β‐D ‐fucopyranosyl(1→6)]‐β‐D ‐glucopyranosyl} oleanolic acid ( 1 ), 3‐O‐[α‐L ‐rhamnopyranosyl(1→3)‐β‐D ‐fucopyranosyl]‐28‐O‐[α‐L ‐rhamnopyranosyl(1→4)‐β‐D ‐glucopyranosyl] oleanolic acid ( 2 ), and 3‐O‐{α‐L ‐rhamnopyranosyl(1→2)‐[3′,4′‐diacetoxy‐β‐D ‐fucopyranosyl]}‐28‐O‐[α‐L ‐rhamnopyranosyl(1→2)‐β‐D ‐glucopyranosyl] oleanolic acid ( 3 ) have been isolated from the stems of Xerospermum noronhianum. The structures of the saponins were determined as a series of bidesmosidic oleanane saponins based on spectral evidence. The anticholinesterase activity of the saponins 1 – 3 was also evaluated.     

New Acylated Presenegenin Saponins from Two Species of Muraltia

Six new acylated bisdesmosidic triterpene glycosides 1 – 6 were isolated from the roots of Muraltia heisteria (L.) DC., as three inseparable mixtures 1 / 2, 3 / 4 , and 5 / 6 of the (E)‐ and (Z)‐3,4,5‐trimethoxycinnamoyl derivatives. The compound pair 1 / 2 along with four known saponins were also isolated from the roots of Muraltia satureioides DC. Their structures were elucidated mainly by spectroscopic experiments including 2D‐NMR techniques 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‐[6‐O‐acetyl‐β‐D ‐galactopyranosyl‐(1→3)]‐4‐O‐[(E)‐3,4,5‐trimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 1 ) and its (Z)‐isomer 2 , 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐6‐O‐acetyl‐β‐D ‐galactopyranosyl‐(1→3)‐O‐[3‐O‐acetyl‐α‐L ‐rhamnopyranosyl‐(1→2)]‐4‐O‐[(E)‐3,4,5‐trimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 3 ) and its (Z)‐isomer 4 , and 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐3‐O‐acetyl‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[β‐D ‐xylopyranosyl‐(1→3)]‐4‐O‐[(E)‐3,4,5‐trimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 5 ) and its (Z)‐isomer 6 , respectively.     

Presenegenin Glycosides from Securidaca welwitschii

The five new presenegenin glycosides 1 – 5 were isolated from Securidaca welwitschii, together with one known sucrose diester. Compounds 1 – 4 were obtained as pairs of inseparable (E)/(Z)‐isomers of a 3,4‐dimethoxycinnamoyl derivative, i.e., 1 / 2 and 3 / 4 . Their structures were elucidated mainly by 2D‐NMR techniques and mass spectrometry as 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐[(E)‐3,4‐dimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 1 ) and its (Z)‐isomer 2 , 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐{O‐β‐D ‐galactopyranosyl‐(1→4)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐3‐O‐acetyl‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐[(E)‐3,4‐dimethoxycinnamoyl]‐β‐D ‐fucopyranosyl} ester ( 3 ) and its (Z)‐isomer 4 , and 3‐O‐(β‐D ‐glucopyranosyl)presenegenin 28‐[O‐β‐D ‐galactopyranosyl‐(1→3)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐fucopyranosyl] ester ( 5 ) (presenegenin=(2β,3β,4α)‐2,3,27‐trihydroxyolean‐12‐ene‐23,28‐dioic acid).     

Tetrapterosides A and B,two new oleanane‐type saponins from Tetrapleura tetraptera

From the stem bark of Tetrapleura tetraptera, two new oleanane‐type saponins, tetrapteroside A 3‐O‐{6‐O‐[(2E,6S)‐2,6‐dimethyl‐6‐hydroxyocta‐2,7‐dienoyl]‐β‐D ‐glucopyranosyl‐(1 → 2)‐β‐D ‐glucopyranosyl‐(1 → 3)‐β‐D ‐glucopyranosyl‐(1 → 4)‐[β‐D ‐glucopyranosyl‐(1 → 2)]‐β‐D ‐glucopyranosyl}‐3,27‐dihydroxyoleanolic acid (1), and tetrapteroside B 3‐O‐{ β‐D ‐glucopyranosyl‐(1 → 2)‐6‐O‐[(E)‐feruloyl]‐β‐D ‐glucopyranosyl‐(1 → 3)‐β‐D ‐glucopyranosyl‐(1 → 4)‐[β‐D ‐glucopyranosyl‐(1 → 2)]‐β‐D ‐glucopyranosyl}‐3,27‐dihydroxyoleanolic acid (2), were isolated. Further extractions from the roots led to the isolation of four known oleanane‐type saponins. Their structures were elucidated by the combination of mass spectrometry (MS), one and two‐dimensional NMR experiments. Copyright © 2009 John Wiley & Sons, Ltd.     

Isoflavonoid Glycosides from the Rhizomes of Iris germanica

Five new di‐ and triglycosides, irigenin 7‐[O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranoside] ( 1 ), 6‐hydroxygenistein 4′‐[O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranoside] ( 2 ), nigricin 4′‐[O‐β‐D ‐glucopyanosyl‐(1→6)‐β‐D ‐glucopyranoside] ( 3 ), nigricin 4′‐[O‐β‐D ‐glucopyanosyl‐(1→2)‐O‐[α‐L ‐rhamnopyranosyl‐(1→6)]‐β‐D ‐glucopyranoside] ( 4 ), and 7‐{4′‐{[2″‐O‐(4′′′′‐acetyl‐2′′′′‐methoxyphenyl)‐β‐D ‐glucopyranosyl]oxy}‐3′‐(β‐D ‐glucopyranosyloxy)phenyl]‐9‐methoxy‐8H‐1,3‐dioxolo[4,5‐g]‐[1 benzopyran‐8‐one‐] ( 5 ), along with a known compound, nigricin 4′‐(β‐D ‐glucopyranoside) ( 6 ), were isolated from the rhizomes of Iris germanica. The structures of these compounds were established by spectroscopic methods, including 2D NMR spectroscopic techniques.     

Five New Medicagenic Acid Saponins from Muraltia ononidifolia

Five new triterpene saponins 1 – 5 were isolated from the roots of Muraltia ononidifolia E. Mey along with the two known saponins 3‐O‐[O‐β‐D ‐glucopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl]medicagenic acid 28‐[O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl] ester and 3‐O‐(β‐D ‐glucopyranosyl)medicagenic acid 28‐[O‐α‐L ‐rhamnopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl] ester (medicagenic acid=(4α,2β,3β)‐2,3‐dihydroxyolean‐12‐ene‐23,28‐dioic acid). Their structures were elucidated mainly by spectroscopic experiments, including 2D‐NMR techniques, as 3‐O‐(β‐D ‐glucopyranosyl)medicagenic acid 28‐[O‐β‐ D ‐apiofuranosyl‐(1→3)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl] ester ( 1 ), 3‐O‐(β‐D ‐glucopyranosyl)medicagenic acid 28‐{[O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐[β‐D ‐apiofuranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl} ester ( 2 ), 3‐O‐[O‐β‐D ‐glucopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl]medicagenic acid 28‐{O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐[β‐D ‐apiofuranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl} ester ( 3 ), 3‐O‐[O‐β‐D ‐glucopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl]medicagenic acid 28‐[O‐α‐L ‐rhamnopyranosyl‐(1→2)‐α‐L ‐arabinopyranosyl] ester ( 4 ), and 3‐O‐[O‐β‐D ‐glucopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl]medicagenic acid ( 5 ).     

Two New Homo‐aro‐cholestane Glycosides and a New Cholestane Glycoside from the Roots and Rhizomes of Paris polyphylla var. pseudothibetica

Two new homo‐aro‐cholestane glycosides and a new cholestane glycoside, along with three known saponins, were isolated from the 95% EtOH extract of the roots and rhizomes of Paris polyphylla var. pseudothibetica. The structures of the new compounds were elucidated as 3β‐O‐{α‐L ‐rhamnopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→4)‐[α‐L ‐rhamnopyranosyl‐(1→2)]}‐β‐D ‐glucopyranosylhomo‐aro‐cholest‐5‐ene‐26‐O‐β‐D ‐glucopyranoside (parispseudoside A, 1 ), 3β‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucopyranosylhomo‐aro‐cholest‐5‐ene‐26‐O‐β‐D ‐glucopyranoside (parispseudoside B, 2 ), and (25R)‐3β‐O‐{α‐L ‐rhamnopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→4)‐[α‐L ‐rhamnopyranosyl‐(1→2)]}‐β‐D ‐glucopyranosyl‐cholesta‐5,17(20)‐diene‐16,22‐dione‐26‐O‐β‐D ‐glucopyranoside (parispseudoside C, 3 ) by spectroscopic methods, including 1D‐ and 2D‐NMR, and MS experiments, as well as chemical evidences.