New Antifungal Terpenoid Glycosides from Alibertia edulis (Rubiaceae)

Phytochemical investigation from the stems of Alibertia edulis led to the isolation and identification of a new iridoid 6β‐hydroxy‐7‐epigardoside methyl ester ( 1 ) and a new saponin 3β‐O‐[α‐L ‐rhamnopyranosyl‐(1→2)‐O‐β‐D ‐glucopyranosyl‐(1→2)‐O‐β‐D ‐glucopyranosyl]‐28‐O‐β‐D ‐glucopyranoside pomolate ( 2 ), along with three known compounds, shanzhiside methyl ester ( 3 ), ixoside ( 4 ), and 3,4,5‐trimethoxyphenyl 1‐O‐β‐D ‐apiofuranosyl‐(1→6)‐O‐β‐D ‐glucopyranoside ( 5 ). The structures of 1 and 2 were established on the basis of their spectroscopic data. Iridoid 1 and saponin 2 exhibited moderate inhibitory activities against Candida albicans and C. krusei in a dilution assay.     

Iridoid Glycosides and Phenolic Compounds from the Flowers of Vitex agnus‐castus

A new and rare type of iridoid glycoside, agnusoside ( 1 ), a new caffeoylquinic acid derivative, castusic acid ( 2 ), and a new sugar ester, 1,2‐di‐(4‐hydroxybenzoyl)‐β‐glucopyranose ( 3 ), along with ten known compounds belonging to iridoid glycosides (agnuside, trans‐eurostoside), caffeoylquinic acid derivatives (chlorogenic acid and isochlorogenic acid A), flavonoids (isoorientin, isovitexin, kaempferol 3‐O‐sophoroside, luteolin 6‐C‐(2′′‐O‐trans‐caffeoyl)glucopyranoside, and simple phenolic acids (4‐hydroxybenzoic acid, 3,4‐dihydroxybenzoic acid), chemical classes were isolated from the flowers of Vitex agnus‐castus. The structures of the isolates were established by extensive 1D‐ and 2D‐NMR spectroscopic analysis as well as HR‐ESI‐MS. Agnusoside ( 1 ) represents an unusual type of iridoid glycoside with its 6‐keto C(4) nonsubstituted aglycone.     

New Iridoid and Secoiridoid Glucosides from the Roots of Gentiana manshurica

One new iridoid glucoside, 4″‐O‐β‐D ‐glucosyl‐6′‐O‐(4‐O‐β‐D ‐glucosylcaffeoyl)linearoside ( 1 ), and two new secoiridoid glucosides, 6′‐O‐acetylsweroside ( 2 ) and 6′‐O‐acetyl‐3′‐O‐[3‐(β‐D ‐glucopyranosyloxy)‐2‐hydroxybenzoyl]sweroside ( 3 ), were isolated from the dried roots of Gentiana manshurica (Gentianaceae), together with 11 known ones, including one iridoid glucoside, five secoiridoid glucosides, and five triterpenes. The structures of the new compounds were determined on the basis of detailed spectroscopic analyses and acidic hydrolysis.     

Scyphiphorins A and B,Two New Iridoid Glycosides from the Stem Bark of a Chinese Mangrove Scyphiphora hydrophyllacea

Two new iridoid glycosides, named scyphiphorins A ( 1 ) and B ( 2 ), together with four known compounds, geniposidic acid (=(1S,4aS,7aS)‐1‐(β‐D ‐glucopyranosyloxy)‐1,4a,5,7a‐tetrahydro‐7‐(hydroxymethyl)cyclopenta[c]pyran‐4‐carboxylic acid; 3 ), 4‐(4‐hydroxy‐3‐methoxybenzyl)butan‐2‐one, oleanolic acid (=(3β)‐3‐hydroxyolean‐12‐en‐28‐oic acid), and stigmasterol β‐D ‐glucoside (=(3β,22E)‐stigmasta‐5,22‐dien‐3‐yl β‐D ‐glucopyranoside), were isolated for the first time from the stem bark of a Chinese mangrove, Scyphiphora hydrophyllacea Gaertn . f. The structures of compounds 1 and 2 were determined as 10‐O‐benzoylgeniposidic acid and 10‐O‐[(2E,6R)‐8‐hydroxy‐2,6‐dimethyl‐1‐oxooct‐2‐en‐1‐yl]geniposidic acid, respectively, on the basis of spectroscopic data and chemical methods, including 2D NMR techniques.     

Chemical Constituents from the Roots of Patrinia Rupestris

Phytochemical investigation of the roots of Patrinia rupestris afforded a new triterpenoid patrirupin A ( 1 ) and a new iridoid patrirupin B ( 2 ), as well as three known triterpenoids: 3‐oxo‐olean‐12‐en‐28‐oic acid ( 3 ), ursolic acid ( 4 ), α‐amyrin ( 5 ), three known iridoids: isovaltratum ( 6 ), 11‐ethoxyviburtinal ( 7 ), homobaldrinal ( 8 ), five known steroids: ergosterol ( 9 ), ergost‐6,22‐diene‐3β,5α,8α‐triol ( 10 ), 6‐hydroxenone ( 11 ), β‐sitosterol ( 12 ), daucosterol ( 13 ), and two known flavones: 1‐hydroxy‐5‐methoxy xanthen‐9‐one ( 14 ), 3′,4′,5,7‐tetrahydroxyflavanone ( 15 ). The new compounds were characterized by means of spectroscopic methods including UV, IR, 1D, 2D NMR and HRESIMS, and the known ones were established on the basis of comparing their NMR data with those of the corresponding compounds in the literature.     

Characterization,crystal structure and cytotoxic activity of a rare iridoid glycoside from Lonicera saccata

A new iridoid glycoside, methyl (3R,4R,4aS,7S,7aR)‐3‐hydroxy‐7‐methyl‐5‐oxooctahydrocyclopenta[c]pyran‐4‐carboxylate‐3‐O‐β‐d ‐(1′S,2′R,3′S,4′S,5′R)‐glucopyranoside, named loniceroside A, C₁₇H₂₆O₁₀, ( 1 ), was obtained from the aerial parts of Lonicera saccata. Its structure was established based on an analysis of spectroscopic data, including 1D NMR, 2D NMR and HRESIMS, and the configurations of the chiral C atoms were determined by X‐ray crystallographic analysis. The single‐crystal structure reveals that the cyclopenta[c]pyran scaffold is formed from a five‐membered ring and a chair‐like six‐membered ring connected through two bridgehead chiral C atoms. In the solid state, the glucose group of ( 1 ) plays an important role in constructing an unusual supramolecular motif. The structure analysis revealed adjacent molecules linked together through intermolecular O—H…O hydrogen bonds to generate a banded structure. Furthermore, the banded structures are linked into a three‐dimensional network by interesting hydrogen bonds. Biogenetically, compound ( 1 ) carries a glucopyranosyloxy moiety at the C‐3 position, representing a rare structural feature for naturally occurring iridoid glycosides. The growth inhibitory effects against human cervical carcinoma cells (Hela), human lung adenocarcinoma cells (A549), human acute mononuclear granulocyte leukaemia (THP‐1) and the human liver hepatocellular carcinoma cell line (HepG2) were evaluated by the MTT method.     

Two New Iridoid Glycosides from Hedyotis tenelliflora Blume

Two new iridoid glycosides, teneoside A (=(2aR,5S)‐5‐[(β‐D ‐glucopyranosyl)oxy]‐2a,4a,5,7b‐tetrahydro‐4‐{[(α‐L ‐rhamnopyranosyl)oxy]methyl}‐1H‐2,6‐dioxacyclopenta[cd]inden‐1‐one; 1 ) and teneoside B (=methyl (1S,5R)‐1‐[(β‐D ‐glucopyranosyl)oxy]‐1,4a,5,7a‐tetrahydro‐5‐hydroxy‐7‐{[(α‐L ‐rhamnopyranosyl)oxy]methyl}cyclopenta[c]pyran‐4‐carboxylate; 2 ), were isolated from the roots of Hedyotis tenelliflora Blume , along with two known compounds, deacetylasperuloside ( 3 ) and scandoside methyl ester ( 4 ). Their structures were elucidated by chemical methods (acid hydrolysis) and spectroscopic analyses.     

Eremosides A – C,New Iridoid Glucosides from Eremostachys loasifolia

Eremosides A–C ( 1 – 3 ), three new iridoid glucosides, were isolated from the AcOEt‐soluble fraction of the EtOH extract of the whole plant of Eremostachys loasifolia, along with buddlejoside B ( 4 ), 10‐O‐benzoylcatalpol ( 5 ), and pakiside A ( 6 ) reported for the first time from this species. The structures of these compounds were elucidated by spectroscopic data including 2D‐NMR, FAB‐MS, ESI‐MS, as well as by acid and basic hydrolyses.     

New Chemical Constituents from Borreria verticillata (Rubiaceae)

A phytochemical study on Borreria verticillata has led to the isolation of two novel simple indole alkaloids, 6‐methoxy‐4‐(3‐methylbut‐2‐en‐1‐yl)‐1H‐indole, named verticillatine A ( 1 ), and 1‐(1H‐indol‐6‐yl)‐3‐methylbutan‐1‐one, named verticillatine B ( 2 ), one new iridoid, 6′‐O‐(2‐glyceryl)scandoside methyl ester ( 3 ), with the glycerol unit linked to a glucose unit, and two known ones, asperuloside ( 4 ) and scandoside methyl ester ( 5 ). The structures of these compounds were elucidated on the basis of spectroscopic‐data analyses, mainly ¹H‐ and ¹³C‐NMR, including 2D experiments (¹H,¹H‐COSY, NOESY, HMBC, and HMQC), and HR‐ESI‐MS.     

New Anthraquinone and Iridoid Glycosides from the Stems of Hedyotis hedyotidea

Five new anthraquinone glycosides, hedanthrosides A–E ( 1 – 5 , resp.) and two new iridoid glycosides, hediridosides A and B ( 6 and 7 , resp.), along with two known anthraquinones and four known iridoids, were isolated from the stems of Hedyotis hedyotidea (DC.) Merr . The structures of the new compounds were elucidated on the basis of 1D‐ and 2D‐NMR, and HR‐MS analysis and chemical methods.     

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).     

Monoterpenoid glucoindole alkaloids and iridoids from Pterocephalus pinardii

A new secondary metabolite, pterocephaline, along with the known cantleyoside, 7α‐morroniside, 3β,5α‐tetrahydrodesoxycordifoline lactam, 5S‐5‐carboxyvincoside, sweroside, and loganin have been isolated from the aerial parts of P. pinardii (Dipsacaceae). Moreover, cantleyoside‐methyl‐hemiacetal and cantleyoside‐dimethyl‐acetal were obtained as seco‐iridoid artifacts. The structures were elucidated by extensive spectroscopic methods including 1D‐(¹H, ¹³C and TOCSY) and 2D‐NMR (DQF‐COSY, HSQC and HMBC). Monoterpenoid glucoindole alkaloids were encountered for the first time in Dipsacaceae family. Copyright © 2010 John Wiley & Sons, Ltd.     

Two New Iridoid Esters from the Root and Rhizome of Valeriana jatamansi Jones

Two new iridoid esters, named valerjatadoids A and B ( 1 and 2 , resp.), together with three known iridoid esters, jatamanin O ( 3 ), jatamanvaltrate P ( 4 ), and jatamanvaltrate Q ( 5 ), have been isolated from the root and rhizome of Valeriana jatamansi Jones . The structures of the two new compounds were elucidated by spectroscopic analyses, including 2D‐NMR techniques.     

Terpenoids from the Flower of Cacalia Tangutica

A thorough investigation of Cacalia tangutica (Franch.) Hand‐Mazz afforded two new epimeric eremophilane sesquiterpenoids, 7β‐ H‐3α‐angeloyloxy‐9‐ene‐11,12‐epoxy‐8‐oxoeremophilane ( 1 ) and 7α‐H‐3α‐angeloyloxy‐9‐ene‐11,12‐epoxy‐8‐oxoeremophilane ( 2 ), as well as four known sesquiterpenes, petasol ( 3 ), oplopanone ( 4 ), 4,5‐epoxy‐β‐caryophyllene ( 5 ), 4(15)‐eudesmene‐1β,6α‐diol ( 6 ), and three known monoterpenes, 1β,2α‐dihydroxy‐p‐menth‐5‐ene ( 7 ), 5α‐hydroxy‐2‐oxo‐p‐menth‐6(1)‐ene ( 8 ), 5β‐hydroxy‐2‐oxo‐p‐menth‐6(1)‐ene ( 9 ), and two known triterpenes, maniladiol 3‐O‐palmitate ( 10 ), taraxasteryl palmitate ( 11 ). The new compounds were characterized by means of spectroscopic methods including 1D, 2D NMR and HRESIMS, and the known ones were established on the basis of comparing their NMR data with those of the corresponding compounds in the literature. In addition, cytotoxicity against selected cancer cells (HL‐60, HO‐8910 and A‐549) of compounds 1 ‐ 4 , 6 , 7 , 10 were measured in vitro.     

New Iridoid Triesters from Valeriana jatamansi

Two new iridoid triesters, valeriotriates A ( 1 ) and B ( 2 ), were isolated from the roots of Valeriana jatamansi Jones . Their structures were elucidated by HR‐ESI‐MS and 1D‐ and 2D‐NMR spectroscopy.     

Chemical Components of Seriphidium Santolium Poljak

A new biflavonoid glucoside, apigenin‐7‐O‐β‐D‐glucopyranoside‐(3′‐O‐7″)‐quercetin‐3″‐methyl ether ( 1 ) together with twenty known compounds, apigenin ( 2 ), luteolin ( 3 ), chrysoeriol ( 4 ), tricin ( 5 ), hispidulin ( 6 ), pectolinarigenin ( 7 ), eupatilin ( 8 ), 5,7‐dihydroxy‐6,3′,4′,5′‐tetramethoxyflavone ( 9 ), 5,7,4′‐trihydroxy‐6,3′,5′‐trimethoxyflavone ( 10 ), 3,6‐O‐dimethylquercetagetin‐7‐O‐β‐D‐glucoside ( 11 ), 6‐hydroxy‐5,7‐dimethoxy‐coumarin ( 12 ), taraxerol ( 13 ), taraxeryl acetate ( 14 ), a mixture of β‐sitosterol ( 15 ) and stigmasterol ( 16 ), a mixture of the n‐alkyl trans‐p‐coumarates ( 17 ), a mixture of the n‐alkyl trans‐ferulates ( 18 ), 2‐hydroxy‐4,6‐dimethoxyacetophenone ( 19 ), 4‐hydroxy‐2,6‐dimethoxyphenol‐1‐O‐β‐D‐glucopyranoside ( 20 ), and 2‐hydroxycinnamoyl‐β‐D‐glucopyranoside ( 21 ), were isolated from the whole plant of Seriphidium santolium Poljak. The structures of these compounds were determined by means of spectral and chemical studies.     

Two New Iridoids from the Stem of Catalpa ovata

Two new iridoids, 6‐O‐[(E)‐feruloyl]jioglutin D ( 1 ) and 6‐O‐(4‐hydroxybenzoyl)jioglutin D ( 2 ), and six known compounds, minecoside ( 3 ), specioside ( 4 ), picroside II ( 5 ), picroside III ( 6 ), 4‐hydroxybenzoic acid ( 7 ), and martynoside ( 8 ), were isolated from the stem of Catalpa ovata. The structures of the new compounds were established on the basis of spectroscopic techniques, including 1D‐ and 2D‐NMR.     

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.     

Chemical Components of Anaphalis Sinica Hance

Twenty components (including a new flavanone) were isolated and identified from the whole plant of Anaphalis sinica Hance. Their structures were determined on the basis of spectral analysis and chemical transformation. These components are 6‐[(5‐methyl‐6‐ethyl‐4‐hydroxy‐pyrone‐3‐yl)‐methylene]glabranine ( 1 ), kaempferol ( 2 ), tiliroside ( 3 ), quercetin ( 4 ), quercetin‐3‐O‐β‐D‐glucoside ( 5 ), scutellarin ( 6 ), 5,7‐dihydroxy‐8‐methoxyflavone ( 7 ), 5,7‐dihydroxy‐4′‐methoxy‐flavone‐7‐O‐α‐L‐rhamnopyranosyl(1→6)‐β‐D‐glucopyranoside ( 8 ), helipyrone ( 9 ), 4′‐hydroxydehydrokawain ( 10 ), panamin ( 11 ), ursolic acid ( 12 ), pomolic acid ( 13 ), 3‐acetyloleanolic acid ( 14 ), a mixture of N‐(2‐hydroxy‐acyl)‐4‐hydroxy‐8(E)‐ene‐sphingenine ( 15 ), O‐methyl‐D‐inositol ( 16 ), a mixture of β‐sitosterol ( 17 ) and stigmasterol ( 18 ) and a mixture of daucosterol ( 19 ) and stigmasterol‐β‐D‐glucoside ( 20 ). Among them, 6‐[(5‐methyl‐6‐ethyl‐4‐hydroxy‐pyrone‐3‐yl)‐methylene]glabranine ( 1 ) is a new compound, and ¹³C NMR data of panamin ( 11 ) is reported for the first time.     

New Iridoid Glycosides from Lamium eriocephalum subsp. eriocephalum

Two new iridoid glycosides, eriobioside ( 1 ) and lamerioside ( 2 ), were isolated from the aerial parts of Lamium eriocephalum subsp. eriocephalum, along with the two known compounds lamiide ( 3 ) and ipolamiide ( 4 ). Their structures were elucidated by spectroscopic methods (UV, 1D‐ and 2D‐NMR) and by mass spectrometry (HR‐ESI‐MS).