Furostane‐Type Steroidal Saponins from the Roots of Chlorophytum borivilianum

Four new furostanol steroid saponins, borivilianosides A–D ( 1 – 4 , resp.), corresponding to (3β,5α,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐22‐hydroxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐galactopyranoside ( 1 ), (3β,5α,22R,25R)‐ 26‐(β‐D ‐glucopyranosyloxy)‐22‐methoxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐galactopyranoside ( 2 ), (3β,5α,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐22‐methoxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐[β‐D ‐glucopyranosyl‐(1→2)]‐O‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 3 ), and (3β,5α,25R)‐26‐(β‐D ‐glucopyranosyloxy)furost‐20(22)‐en‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→3)‐O‐[β‐D ‐glucopyranosyl‐(1→2)]‐O‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 4 ), together with the known tribuluside A and (3β,5α,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐22‐methoxyfurostan‐3‐yl O‐β‐D ‐xylopyranosyl‐(1→2)‐O‐[β‐D ‐xylopyranosyl‐(1→3)]‐O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)]‐β‐D ‐galactopyranoside were isolated from the dried roots of Chlorophytum borivilianum Sant and Fern . Their structures were elucidated by 2D ‐NMR analyses (COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry.     

New Furostanol Glycosides from the Roots of Digitalis ciliata Trautv.

Three new furostanol glycosides, named ciliatasides A, B, and C ( 1 – 3 , resp.), have been isolated from the roots of Digitalis ciliata, along with two known furostanol glycosides. The structures of the new compounds were identified as (2α,3β,5α,14β,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐2‐hydroxyfurost‐20(22)‐en‐3‐yl β‐D ‐glucopyranosyl‐(1→2)‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranoside ( 1 ), (2α,3β,5α,14β,22R)‐26‐(β‐D ‐glucopyranosyloxy)‐2‐hydroxy‐22‐methoxyfurost‐25(27)‐en‐3‐yl β‐D ‐galactopyranosyl‐(1→2)‐[β‐D ‐xylopyranosyl‐(1→3)]‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 2 ), and (2α,3β,5α,14β,22R,25R)‐26‐(β‐D ‐glucopyranosyloxy)‐2,22‐dihydroxyfurostan‐3‐yl β‐D ‐glucopyranosyl‐(1→2)‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranoside ( 3 ).     

Structure elucidation of new oleanane‐type glycosides from three species of Acanthophyllum

From the roots of three species of Acanthophyllum (Caryophyllaceae), two new gypsogenic acid glycosides, 1 and 2, were isolated, 1 from A. sordidum and A. lilacinum, 2 from A. elatius and A. lilacinum, together with three known saponins, glandulosides B and C, and SAPO50. The structures of 1 and 2 were established mainly by 2D NMR techniques as 23‐O‐β‐D ‐galactopyranosylgypsogenic acid‐28‐O‐β‐D ‐glucopyranosyl‐(1→3)‐[β‐D ‐glucopyranosyl‐(1→6)]‐β‐D ‐galactopyranoside (1) and gypsogenic acid‐28‐O‐β‐D ‐glucopyranosyl‐(1→3)‐[β‐D ‐glucopyranosyl‐(1→6)]‐β‐D ‐galactopyranoside (2). The cytotoxicity of several of these saponins was evaluated against two human colon cancer cell lines (HT‐29 and HCT 116). Copyright © 2010 John Wiley & Sons, Ltd.     

Two New Triterpene Saponins from Acanthophyllum laxiusculum

Two new triterpene glycosides, 1 and 2 , together with three known ones, were isolated from roots of Acanthophyllum laxiusculum Schiman ‐Czeika . The structures of the new compounds were established by extensive 1D‐ and 2D‐NMR spectroscopic experiments and MS analyses as 23‐O‐β‐D ‐galactopyranosylgypsogenic acid 28‐O‐{β‐D ‐glucopyranosyl‐(1→2)‐6‐O‐[4‐carboxy‐3‐hydroxy‐3‐methyl‐1‐oxobutyl]‐β‐D ‐glucopyranosyl‐(1→6)}‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranosyl ester ( 1 ) and gypsogenic acid 28‐O‐{β‐D ‐glucopyranosyl‐(1→2)‐6‐O‐[4‐carboxy‐3‐hydroxy‐3‐methyl‐1‐oxobutyl]‐β‐D ‐glucopyranosyl‐(1→6)}‐[β‐D ‐glucopyranosyl‐(1→3)]‐β‐D ‐galactopyranosyl ester ( 2 ).     

New Steroidal Saponins from the Leaves of Yucca elephantipes

Two new spirostanol saponins, namely elephanosides G and H ( 1 and 2 , resp.) were isolated from the leaves of Yucca elephantipes (Agavaceae), together with the two known furostanol saponins 3 and 4 and the six known flavonoid O‐ and C‐glycosides 5 – 10 . The new structures were elucidated as (3β,25S)‐spirost‐5‐en‐3‐yl O‐β‐D ‐glucopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside ( 1 ) and (3β,5β,25R)‐3‐[(2‐O‐β‐D ‐glucopyranosyl‐β‐D ‐galactopyranosyl)oxy]spirostan‐12‐one ( 2 ) on the basis of detailed spectroscopic analysis and acidic hydrolysis.     

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 ).     

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 Cytotoxic Nonsulfated Pentasaccharide Holostane (=20‐Hydroxylanostan‐18‐oic Acid γ‐Lactone) Glycosides from the Sea Cucumber Holothuria grisea

Two new lanostane‐type nonsulfated pentasaccharide triterpene glycosides, 17‐dehydroxyholothurinoside A ( 1 ) and griseaside A ( 2 ), were isolated from the sea cucumber Holothuria grisea. Their structures were elucidated by spectroscopic methods, including 2D‐NMR and MS experiments, as well as chemical evidence. Compounds 1 and 2 possess the same pentasaccharide moieties but differ slightly in their side chains of the holostane‐type triterpene aglycone. The structures of the two new glycosides were established as (3β,12α)‐22,25‐epoxy‐3‐{(O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[O‐3‐O‐methyl‐β‐D ‐glucopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐6‐deoxy‐β‐D ‐glucopyranosyl‐(1→2)]‐β‐D ‐xylopyranosyl)oxy}‐12,20‐dihydroxylanost‐9(11)‐en‐18‐oic acid γ‐lactone ( 1 ) and (3β,12α)‐3‐{(O‐β‐D ‐glucopyranosyl‐(1→4)‐O‐[O‐3‐O‐methyl‐β‐D ‐glucopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranosyl‐(1→4)‐6‐deoxy‐β‐D ‐glucopyranosyl‐(1→2)]‐β‐D ‐xylopyranosyl)oxy}‐12,20,22‐trihydroxylanost‐9(11)‐en‐18‐oic acid γ‐lactone ( 2 ). The 17‐dehydroxyholothurinoside A ( 1 ) and griseaside A ( 2 ) exhibited significant cytotoxicity against HL‐60, BEL‐7402, Molt‐4, and A‐549 cancer cell lines.     

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.     

Two New Dammarane‐Type Bisdesmosides from the Fruit Pedicels of Panax notoginseng

Two new dammarane‐type triterpenoidal saponins, notoginsenosides FP₁ ( 1 ) and FP₂ ( 2 ), were isolated from the fruit pedicels of Panax notoginseng, along with 22 known compounds. Their structures were elucidated on the basis of spectroscopic evidences and chemical methods. The known compounds were identified as ginsenosides Rg₁ ( 3 ), Re ( 4 ), Rb₃ ( 5 ), Rc ( 6 ), Rd ( 7 ), Rb₂ ( 8 ), Rb₁ ( 9 ), F₂ ( 10 ), and F₁ ( 11 ); as notoginsenosides R₁ ( 12 ), Fa ( 13 ), and Fc ( 14 ); as vina‐ginsenoside R₇ ( 15 ); as gypenosides IX ( 16 ), XVII ( 17 ), and XIII ( 18 ), and as chikusetsusaponin‐L₅ ( 19 ), quercetin 3‐O‐β‐D ‐glucopyranosyl‐(1→2)‐β‐D ‐galactopyranoside ( 20 ), kaempferol 3‐O‐β‐D ‐glucopyranosyl‐(1→2)‐β‐D ‐galactopyranoside ( 21 ), benzyl‐β‐primeveroside ( 22 ), (S)‐tryptophan ( 23 ), and icariside B₆ ( 24 ). Compounds 15, 19 and 22 – 24 are reported for the first time from the title plant.     

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.     

Steroidal Saponins from Disporopsis pernyi

Four new steroidal saponins, named disporosides A–D ( 1 – 4 ), corresponding to (3β,25R)‐3‐[(β‐D ‐glucopyranosyl‐(1→2)‐[β‐D ‐glucopyranosyl‐(1→6)]‐β‐D ‐glucopyranosyl)oxy]‐5β‐spirostan ( 1 ), (3β,25R)‐3‐[(β‐D ‐glucopyranosyl‐(1→2)‐[6‐O‐hexadecanoyl‐β‐D ‐glucopyranosyl‐(1→6)]‐β‐D ‐glucopyranosyl)oxy]‐5β‐spirostan ( 2 ), (3β,22R,25R)‐26‐[(β‐D ‐glucopyranosyl)oxy]‐3‐[(β‐D ‐glucopyranosyl‐(1→2)‐β‐D ‐glucopyranosyl)oxy]‐5β‐furostan ( 3 ), and (3β,22R,25R)‐26‐[(β‐D ‐glucopyranosyl)oxy]‐3‐[(β‐D ‐glucopyranosyl‐(1→2)‐[β‐D ‐glucopyranosyl‐(1→6)]‐β‐D ‐glucopyranosyl)oxy]‐5β‐furostan ( 4 ), have been isolated from the fresh rhizomes of Disporopsis pernyi, together with the three known compounds Ys‐I, agavoside B, and (3β,25R)‐3‐[(β‐D ‐xylopyranosyl‐(1→3)‐β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranosyl)oxy]‐5α‐spirostan‐12‐one. Their structures were elucidated by spectroscopic analyses, chemical transformations (acid hydrolysis), and comparison with literature data.     

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 Cycloartane and Flavonol Glycosides from Corchorus depressus

Two new monodesmosidic cycloartane triterpene glycosides, depressosides E and F, and two new flavonol glycosides, depressonol A and B, were isolated from the butanol‐soluble part of the EtOH extract of Corchorus depressus L . The structures of the new compounds were elucidated as (22R,24S)‐22,25‐epoxy‐9,19‐cyclolanostane‐3β,16β,24‐triol 3‐[α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranoside] ( 1 ), (22R,24S)‐22,25‐epoxy‐9,19‐cyclolanostane‐3β,16β,24‐triol 3‐[α‐D ‐glucopyranosyl‐(1→3)‐β‐D ‐glucopyranoside] ( 2 ), kaempferol 3‐[β‐D ‐glucopyranosyl‐(1→4)‐β‐D ‐galactopyranoside] 7‐[α‐L ‐arabinofuranoside] ( 4 ), and kaempferol 3‐[β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐galactopyranoside] 7‐[α‐L ‐arabinofuranoside] ( 5 ) on the basis of chemical evidence and detailed spectroscopic studies.     

Oleanane Saponins from Rhizome of Anemone raddeana

Two new oleanolic acid‐type triterpenoid saponins, raddeanosides R₂₂ and R₂₃ ( 1 and 2 , resp.), together with four known saponins were isolated from the rhizome of Anemone raddeana Regel. The structures of the new compounds were elucidated as oleanolic acid 3‐O‐β‐D ‐glucopyranosyl(1→2)[β‐D ‐glucopyranosyl(1→4)]‐α‐L ‐arabinopyranoside ( 1 ) and oleanolic acid 3‐O‐α‐L ‐arabinopyranosyl(1→3)‐α‐L ‐rhamnopyranosyl(1→2)[β‐D ‐glucopyranosyl(1→4)]‐α‐L ‐arabinopyranoside ( 2 ). The four known compounds were identified as oleanolic acid 3‐O‐α‐L ‐arabinopyranoside ( 3 ), oleanolic acid 3‐O‐β‐D ‐glucopyranosyl(1→4)‐α‐L ‐arabinopyranoside ( 4 ), hederasaponin B ( 5 ), and hederacholchiside E ( 6 ) on the basis of chemical and spectral evidences. Compound 4 is reported for the first time from the Anemone genus, while the other three known compounds have been already found in this plant.     

Tensioactive Compounds from the Aquatic Plant Ranunculus fluitans L. (Ranunculaceae)

In the search for the cause for the formation of persistent foam in the Rhine River below the Rhine Fall at Schaffhausen, an investigation of the tensioactive principles from the aquatic plant Ranunculus fluitans L. (Ranunculaceae) was carried out. Two new (see 1 and 2 ) and four known bisdesmosidic triterpene saponins (see 4 – 6 ) were isolated along with the two known diacylglycerol galactosides 7 and 8 . The saponin structures were established by the identification of the aglycon and sugar moieties by HPLC and chiral capillary zone electrophoresis (CZE), ion‐spray LC/MS and extensive 1‐ and 2D homo‐ and heteronuclear NMR spectroscopy. The structures of the new oleanane‐type saponins were identified as 3‐O‐[β‐D ‐glucopyranosyl‐(1→3)‐α‐L ‐arabinopyranosyl]‐28‐O‐[α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl]hederagenin ( 1 ) and 3‐O‐[β‐D ‐glucopyranosyl‐(1→3)‐β‐D ‐glucopyranosyl]oleanolic acid [α‐L ‐rhamnopyranosyl‐(1→4)‐β‐D ‐glucopyranosyl‐(1→6)‐β‐D ‐glucopyranosyl] ester ( 2 ). LC/MS Studies of tensioactive fractions revealed the presence of additional glycoglycerolipids.     

New Flavonoids from Lysimachia christinae Hance

A chemical investigation of Lysimachia christinae, a traditional Chinese medicine used as an effective conservative treatment for gall stones, hepatolithiasis, and urinary calculi, resulted in the isolation of two new flavonoids, myricetin 3,3′‐di‐α‐L ‐rhamnopyranoside ( 1 ) and quercetin 3,3′‐di‐α‐L ‐rhamnopyranoside ( 2 ), along with the five known flavonoids quercetin 3‐[O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐galactopyranoside], amentoflavone, hyperin, quercetin 3‐β‐D ‐glucopyranoside, and kaempferol 3‐α‐L ‐rhamnopyranoside. Amentoflavone was reported for the first time from the genus Lysimachia, and quercetin 3‐[O‐α‐L ‐rhamopyranosyl‐(1→2)‐β‐D ‐galactopyranoside] was isolated from this plant for the first time. The structures of the new compounds were elucidated on the basis of their chemical reactions and extensive spectroscopic analyses, including UV, mass, and NMR spectra.     

New Acylated Preatroxigenin Saponins from Atroxima congolana

Eight new acylated preatroxigenin saponins 1 – 8 were isolated as four inseparable mixtures of the trans‐ and cis‐4‐methoxycinnamoyl derivatives, atroximasaponins A₁/A₂ ( 1 / 2 ), B₁/B₂ ( 3 / 4 ), C₁/C₂ ( 5 / 6 ) and D₁/D₂ ( 7 / 8 ) from the roots of Atroxima congolana. These compounds are the first examples of triterpene saponins containing preatroxigenin (=(2β,3β,4α,22β)‐2,3,22,27‐tetrahydroxyolean‐12‐ene‐23,28‐dioic acid as aglycone. Their structures were elucidated on the basis of extensive 1D‐ and 2D‐NMR studies and FAB‐MS as 3‐O(β‐D ‐glucopyranosyl)preatroxigenin 28‐{O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[O‐β‐D ‐glucopyranosyl‐(1→3)‐β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐(trans‐4‐methoxycinnamoyl)‐β‐D ‐fucopyranoyl} ester ( 1 ) and its cis‐isomer 2 , 3‐O‐(β‐D ‐glucopyranosyl)preatroxigenin 28‐{O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→ 2)‐O‐[O‐6‐O‐acetyl‐β‐D ‐glucopyranosyl‐(1→3)‐β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐(trans‐ 4‐methoxycinnamoyl)‐β‐D ‐fucopyranosyl} ester ( 3 ) and its cis‐isomer 4 , 3‐O‐(β‐D ‐glucopyranosyl)preatroxigenin 28‐{O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐[β‐D ‐apiofuranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[O‐6‐ O‐acetyl‐β‐D ‐glucopyranosyl‐(1→3)‐β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐(trans‐4‐methoxycinnamoyl)‐β‐D ‐fucopyranoyl} ester ( 5 ) and its cis‐isomer 6 , 3‐O‐(β‐D ‐glucopyranosyl)preatroxigenin 28‐{O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐[β‐D ‐apiofuranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐O‐[O‐β‐D ‐xylopyranosyl‐(1→3)‐β‐D ‐glucopyranosyl‐(1→3)]‐4‐O‐(trans‐4‐methoxycinnamoyl)‐β‐D ‐fucopyranosyl ester ( 7 ) and its cis‐isomer 8 .     

New Triterpenoid Saponins from Achyrantes aspera Linn.

Two new bisdesmosidic triterpenoid saponins, i.e. 1 and 2 , were isolated, besides the three known saponins 3 – 5 , from the MeOH extract of the aerial parts of Achyranthes aspera Linn. (Amaranthaceae). Their structures were elucidated as β‐D ‐glucopyranosyl 3β‐[O‐α‐L ‐rhamnopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranuronosyloxy]machaerinate ( 1 ) and β‐D ‐glucopyranosyl 3β‐[O‐β‐D ‐galactopyranosyl‐(1→2)‐O‐α‐D ‐glucopyranuronosyloxy]machaerinate ( 2 ) by NMR spectroscopy, including 2D‐NMR experiments (machaerinic acid=3β,21β‐dihydroxyolean‐12‐en‐28‐oic acid). The other saponins were identified as β‐D ‐glucopyranosyl 3β[O‐α‐L ‐rhamnopyranosyl‐(1→3)‐O‐β‐D ‐glucopyranuronosyloxy]oleanolate ( 3 ), β‐D ‐glucopyranosyl 3‐β‐[O‐β‐D ‐galactopyranosyl‐(1→2)‐O‐β‐D ‐glucopyranuronosyloxy]oleanolate ( 4 ), and β‐D ‐glucopyranosyl 3β‐[O‐β‐D ‐glucopyranuronosyloxy]oleanolate ( 5 ) (oleanolic acid=3β‐hydroxyolean‐12‐en‐28‐oic acid).     

Three New Medicagenic Acid Saponins from Polygala micrantha Guill. & Perr.

Three new medicagenic acid saponins, micranthosides A–C ( 1 – 3 ), were isolated from the roots of Polygala micrantha Guill . & Perr ., along with six known presenegenin saponins. Their structures were elucidated on the basis of extensive 1D‐ and 2D‐NMR experiments (¹H, ¹³C, DEPT, COSY, TOCSY, NOESY, HSQC, and HMBC) and mass spectrometry as 3‐O‐β‐D ‐glucopyranosylmedicagenic acid 28‐[O‐β‐D ‐galactopyranosyl‐(1→4)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐fucopyranosyl] ester ( 1 ), 3‐O‐β‐D ‐glucopyranosylmedicagenic acid 28‐[O‐6‐O‐acetyl‐β‐D ‐galactopyranosyl‐(1→4)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐fucopyranosyl] ester ( 2 ), and 3‐O‐{O‐β‐D ‐glucopyranosyl‐(1→3)‐O‐[β‐D ‐glucopyranosyl‐(1→6)]‐β‐D ‐glucopyranosyl}medicagenic acid 28‐{O‐β‐D ‐apiofuranosyl‐(1→3)‐O‐β‐D ‐xylopyranosyl‐(1→4)‐O‐[β‐D ‐apiofuranosyl‐(1→3)]‐O‐α‐L ‐rhamnopyranosyl‐(1→2)‐β‐D ‐fucopyranosyl} ester ( 3 ). Compounds 1 – 3 were evaluated against HCT 116 and HT‐29 human colon cancer cells, but they did not show any cytotoxicity.