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.     

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).     

Phenylethanoid Glycosides from the Roots of Digitalis ciliata Trautv.

Three new phenylethanoid glycosides, named digicilisides A – C ( 1  –  3 , resp.), have been isolated from the roots of Digitalis ciliata, along with five known phenylethanoid glycosides. The structures of 1  –  3 were identified as 2‐(4‐hydroxy‐3‐methoxyphenyl)ethyl β‐d ‐glucopyranosyl‐(1→3)‐[α‐l ‐rhamnopyranosyl‐(1→6)]‐4‐O‐[(E)‐feruloyl]‐β‐d ‐glucopyranoside ( 1 ), 2‐(3,4‐dihydroxyphenyl)ethyl α‐l ‐arabinopyranosyl‐(1→2)‐[β‐d ‐glucopyranosyl‐(1→3)]‐[α‐l ‐rhamnopyranosyl‐(1→6)]‐4‐O‐[(E)‐feruloyl]‐β‐d ‐glucopyranoside ( 2 ), and 2‐(3,4‐dihydroxyphenyl)ethyl β‐d ‐glucopyranosyl‐(1→3)‐{6‐O‐[(E)‐feruloyl]‐β‐d ‐glucopyranosyl‐(1→6)}‐4‐O‐[(E)‐caffeoyl]‐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.     

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 ).     

Phenolic Glycosides from the Chinese Liverwort Reboulia hemisphaerica

Four new phenolic glycosides, named rebouosides A–D ( 1 – 4 , resp.), along with three known ones 2‐(3,4‐dihydroxyphenyl)ethyl 2‐O‐α‐L ‐rhamnopyranosyl‐β‐D ‐allopyranoside ( 5 ), 2‐(3,4‐dihydroxyphenyl)ethyl β‐D ‐allopyranoside ( 6 ), 2‐(3,4‐dihydroxyphenyl)ethyl β‐D ‐glucopyranoside ( 7 ), and a nucleoside, inosine ( 8 ), were isolated from Chinese liverwort Reboulia hemisphaerica. Their structures were elucidated by acidic hydrolysis and extensive spectroscopic methods, including 2D‐NMR techniques.     

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.     

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.     

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).     

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.     

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.     

Glycosidic Constituents of Celastrus orbiculatus

Three new, 1 – 3 , and seven known phenolic and terpenic glycosides were isolated from the BuOH‐soluble fraction of 95% EtOH extract of the roots and rhizomes of Celastrus orbiculatus. The structures of the new compounds were elucidated as carvacrol 2‐O‐α‐L ‐rhamnopyranosyl‐(1→6)‐β‐D ‐glucopyranoside ( 1 ), 5‐methoxycarvacrol 2‐O‐α‐L ‐rhamnopyranosyl‐(1→6)‐β‐D ‐glucopyranoside ( 2 ), and 15‐hydroxytorreyol 10‐O‐β‐D ‐apiofuranosyl‐(1→6)‐β‐D ‐glucopyranoside ( 3 ) on the basis of spectroscopic analysis and chemical methods.     

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 ).     

New Triterpenoid and Ergostane Glycosides from the Leaves of Hydrocotyle umbellata L.

Two new triterpenoid glycosides, together with two new ergostane glycosides, umbellatosides A–D ( 1 – 4 , resp.), have been isolated from the leaves of Hydrocotyle umbellata L. Their structures were established by 2D‐NMR spectroscopic techniques (¹H,¹H‐COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry as 3β,22β‐dihydroxy‐3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]olean‐12‐en‐28‐oic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 1 ), 3‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucuronopyranosyl]oleanolic acid 28‐O‐β‐D ‐glucopyranosyl ester ( 2 ), (3β,11α,26)‐ergosta‐5,24(28)‐diene‐3,11,26‐triol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 3 ), and (3β,11α,21,26)‐ergosta‐5,24(28)‐diene‐3,11,21,26‐tetrol 3‐O‐(β‐D ‐glucopyranosyl)‐11‐O‐(α‐L ‐rhamnopyranosyl)‐26‐O‐β‐D ‐glucopyranoside ( 4 ).     

Ypsilactosides A and B,Two New C22‐Steroidal Lactone Glycosides from Ypsilandra thibetica

Two new C₂₂‐steroidal lactone glycosides, ypsilactosides A ( 1 ) and B ( 2 ), were isolated from the EtOH extract of the whole plant of Ypsilandra thibetica. Their structures were established as (3β,5α,16β,20S)‐3,16‐dihydroxy‐6‐oxopregnane‐20‐carboxylic acid γ‐lactone 3‐(β‐D ‐glucopyranoside) ( 1 ) and (3β,16β)‐3,16‐dihydroxypregna‐5,20‐diene‐20‐carboxylic acid γ‐lactone 3‐{O‐α‐L ‐rhamnopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐glucopyranoside} ( 2 ) on the basis of extensive spectroscopic analyses and chemical degradations.     

New Glycosides from Salvia moorcroftiana (Lamiaceae)

From the MeOH extract of Salvia moorcroftiana Wall. (Lamiaceae), four new compounds, the two flavonoid glycosides genkwanin 4′‐[O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐galactopyranoside] ( 1 ) and genkwanin 4′‐[O‐α‐L ‐arabinopyranosyl‐(1→3)‐α‐L ‐rhamnopyranoside] ( 2 ), and the two benzene derivatives 4‐hydroxy‐2‐isopropyl‐5‐methylphenyl O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐glucopyranoside ( 3 ) and nonyl 4‐hydroxybenzoate ( 4 ), were isolated in addition to two known compounds. The structures of all new compounds were determined by 1D and 2D homonuclear and heteronuclear NMR spectroscopy and by comparison with published data.     

New saponins from Sechium mexicanum

The chemical study of Sechium mexicanum roots led to the isolation of the two new saponins {3‐O‐β‐D ‐glucopyranosyl (1 → 3)‐β‐D ‐glucopyranosyl‐2β,3β,16α,23‐tetrahydroxyolean‐12‐en‐28‐oic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1 → 3)‐β‐D ‐xylopyranosyl‐(1 → 4)‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐α‐L ‐arabinopyranoside} (1) and {3‐O‐β‐D ‐glucopyranosyl (1 → 3)‐β‐D ‐glucopyranosyl‐2β,3β,16α,23‐tetrahydroxyolean‐12‐en‐28‐oic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1 → 3)‐β‐D ‐xylopyranosyl‐(1 → 4)‐[β‐D ‐apiosyl‐(1 → 3)]‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐α‐L ‐arabinopyranoside} (2), together with the known compounds {3‐O‐β‐D ‐glucopyranosyl‐(1 → 3)‐β‐D ‐glucopyranosyl‐2β,3β,6β,16α,23‐pentahydroxyolean‐12‐en‐28‐oic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1 → 3)‐β‐D ‐xylopyranosyl‐(1 → 4)‐α‐L ‐rhamnopyranosyl‐(1 → 2)‐α‐L ‐arabinopyranoside} (3), tacacosides A₁ (4) and B₃ (5). The structures of saponins 1 and 2 were elucidated using a combination of ¹H and ¹³C 1D‐NMR, COSY, TOCSY, gHMBC and gHSQC 2D‐NMR, and FABMS of the natural compounds and their peracetylated derivates, as well as by chemical degradation. Compounds 1–3 are the first examples of saponins containing polygalacic and 16‐hydroxyprotobasic acids found in the genus Sechium, while 4 and 5, which had been characterized partially by NMR, are now characterized in detail. Copyright © 2009 John Wiley & Sons, Ltd.     

Two New Spirostanol Glycosides from Cestrum parqui

Two new steroidal glycosides, parquisoside A ( 1 ) and B ( 2 ) were isolated from the aerial parts of Cestrum parqui (family Solanaceae). Their common aglycone is a new steroid of the spirostane series, which we name parquigenin. It has the structure (3β,24S,25S)‐spirost‐5‐ene‐3,24‐diol, i.e. a (24S,25S)‐24‐hydroxydiosgenin. The structures of parquisosides A and B were elucidated as (3β,24S,25S)‐spirost‐5‐ene‐3,24‐diol 3‐O‐{[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→4)}‐β‐D ‐glucopyranoside ( 1 ) and (3β,24S,25S)‐spirost‐5‐ene‐3,24‐diol 3‐O‐{[α‐L ‐rhamnopyranosyl)‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐glucopyranosyl‐(1→4)‐α‐L ‐rhamnopyranosyl‐(1→4)}‐β‐D ‐glucopyranoside ( 2 ), respectively, on the basis of detailed spectroscopic studies and chemical analysis. The crude extract of Cestrum parqui showed inhibition of carrageenin‐induced edema.     

Unusual Nortriterpenoid Saponins from Stauntonia chinensis

Four new saponins, yemuosides YM₁₇–YM₂₀ ( 1 – 4 , resp.), were isolated from the rattan of Stauntonia chinensis DC. (Lardizabalaceae) along with a known saponin, nipponoside D ( 5 ). Their structures were elucidated by spectroscopic analysis and chemical evidence as 20,30‐dihydroxy‐29‐noroleanolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 1 ), 20,29‐dihydroxy‐30‐noroleanolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 2 ), 29‐hydroxy‐30‐norolean‐20(21)‐enolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 3 ), 29‐hydroxyoleanolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 4 ), and 23,29‐dihydroxyoleanolic acid 28‐O‐α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 5 ). Yemuoside YM₁₇–YM₁₉ ( 1 – 3 , resp.) contain novel unusual nortriterpene aglycones.     

New Triterpenoid Glycosides from Centella asiatica

Four new triterpenoid glycosides named asiaticoside C ( 1 ), D ( 2 ), E ( 3 ), and F ( 4 ) were isolated from the BuOH fraction of the EtOH extract of whole plants of Centella asiatica, together with three known compounds, asiaticoside ( 5 ), madecassoside ( 6 ), and scheffuroside B ( 7 ). Based on FAB‐MS, IR, ¹H‐ and ¹³C‐NMR, and 2D‐NMR data (HMQC, HMBC, COSY), the structures of the new compounds were determined as (2α,3β,4α)‐23‐(acetyloxy)‐2,3‐dihydroxyurs‐12‐en‐28‐oic acid O‐α‐L ‐rhamnopyranosyl‐(1→4)‐O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 1 ), (2α,3β)‐2,3‐dihydroxyurs‐12‐en‐28‐oic acid O‐α‐L ‐rhamnopyranosyl‐(1→4)‐O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 2 ), asiatic acid 6‐O‐β‐D ‐glycopyranosyl‐β‐D ‐glucopyranosyl ester ( 3 ), (3β,4α)‐3,23‐dihydroxyurs‐12‐en‐28‐oic acid O‐α‐L ‐rhamnopyranosyl‐(1→4)‐O‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl ester ( 4 ).