New acetylenic glucosides from Bidens bipinnata LINNE

Two new acetylenic glucosides, 8Z-decaene-4,6-diyn-1-O-beta-D-glucopyranoside named bidenoside C, and 8E-decaene-4,6-diyn-3,10-dihydroxy-1-O-beta-D-glucopyranoside named bidenoside D, have been isolated from the aerial parts of Bidens bipinnata LINNE (Asterceae). These structures have been elucidated on the basis of spectroscopic methods.     

Antiallergic agents from natural sources. 3. Structures and inhibitory effects on nitric oxide production and histamine release of five novel polyacetylene glucosides from Bidens parviflora WILLD

Five new polyacetylene glucosides, bidensyneosides A1, A2, B, C (1-4), and 3-deoxybidensyneoside B (5), have been isolated from the air-dried whole plant of Bidens parviflora WILLD. The structures were identified based on spectroscopic analysis, physicochemical properties, and application of the modified Mosher method to be 3(R),8(E)-8-decene-4,6-diyne-1,3-diol 1-O-beta-D-glucopyranoside (1), deca-3(R),8(Z) 8-decene-4,6-diyne-1,3-diol 1-O-beta-D-glucopyranoside (2), 3(R)-deca-4,6,8-triyne-1,3-diol 1-O-beta-D-glucopyranoside (3), 3(R),8(E)-8-decene-4,6-diyne-1,3,10-triol 1-O-beta-D-glucopyranoside (4), and 8(E)-8-decene-4,6-diyne-1,10-diol 1-O-beta-D-glucopyranoside (5), respectively. These compounds inhibited nitric oxide (NO) production in lipopolysaccharide and interferon-gamma activated murine macrophages (RAW264.7) and also inhibited histamine release from rat mast cells stimulated by the antigen-antibody reaction.     

Glycosides of Atractylodes lancea

Five sesquiterpenoid glycosides (two guaiane-type glycosides and three eudesmane-type glucosides) and a glucoside of an acetylene derivative were newly isolated from the water-soluble portion of the methanolic extract of Atractylodes lancea rhizome together with 26 known compounds. Their structures were characterized as atractyloside A 14-O-beta-D-fructofuranoside, (1S,4S,5S,7R,10S)-10,11,14-trihydroxyguai-3-one 11-O-beta-D-glucopyranoside, (5R,7R,10S)-isopterocarpolone beta-D-glucopyranoside, cis-atractyloside I, (2R,3R,5R,7R,10S)-atractyloside G 2-O-beta-D-glucopyranoside, and (2E,8E)-2,8-decadiene-4,6-diyne-1,10-diol 1-O-beta-D-glucopyranoside on the basis of chemical and spectroscopic investigation. The presence of six characteristic guaiane-type glucosides in both rhizomes of A. lancea and Atractylodes japonica suggested a close chemotaxonomic relationship between them.     

Polyacetylene glycosides from Gymnaster koraiensis

Two polyacetylene glycosides, gymnasterkoreasides A and B, were isolated from the roots of Gymnaster koraiensis. Their structures were elucidated to be (3R)-8-decene-4,6-diyne-1,3-diol 1-O-beta-D-glucopyraside and (3R)-8-decene-4,6-diyne-1,3-diol 1-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyraside on the basis of spectroscopic analysis including COSY, HMQC, and HMBC experiments, as well as chemical methods, which confirmed the determination of a chiral center by the modified Mosher's method.     

Chemical constituents from the colombian medicinal plant Niphogeton ternata

Two coumarins and one polyacetylene, 5-0-(3-chloro-2-hydroxy-3-methylbutyl)-8-methoxypsoralen (1), 2',3'-dihydro-jatamansin (2), and 10-chloro-1-heptadecene-4,6-diyne-3,8,9-triol (3), along with 15 known compounds (4-18), were isolated from the methanol extract of Niphogeton ternata. Their structures were elucidated by spectroscopy.     

Flavonoids and a new polyacetylene from Bidens parviflora Willd

Fifteen flavonoids, 1-7 and 9-16, and a polyacetylene, 8, were isolated from the ethanol extract of the dried whole plant of Bidens parviflora Willd. by various chromatographic techniques. Their structures have been elucidated on the basis of spectroscopic analyses and chemical studies. Compound 8 is new and was identified as 3-(R),8(E)-decene-4,6-diyne-1,3,10-triol. All the flavonoid compounds were isolated for the first time from this plant species.     

A new acetylenic compound from the rhizomes of Atractylodes chinensis and its absolute configuration

A new acetylenic compound "atractyloyne", (3S,4E,6E,12E)-1-isovaleryloxy-tetradeca-4,6,12-triene-8,10-diyne-3,14-diol (1) was isolated from the rhizomes of Atractylodes chinensis (Compositae) together with a known compound (4E,6E,12E)-3-isovaleryloxy-tetradeca-4,6,12-triene-8,10-diyne-1,14-diol (2). These structures were determined on the basis of the spectroscopic data and chemical evidence, and the absolute configuration of 1 was established by the modified 2-methoxy-2-trifluoromethylphenylacetic acid (MTPA) method.     

New alpha-tetralonyl glucosides from the fruit of Juglans mandshurica

Five new alpha-tetralonyl glucosides, juglanosides A-E (1-5) were isolated from the fresh rejuvenated fruit of Juglans mandshurica. Their structures were elucidated as (4S)-4-hydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (1), (4S)-4,5-dihydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (2), (4S)-4,6-dihydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (3), (4S)-4,5,8-trihydroxy-alpha-tetralone 4-O-beta-D-glucopyranoside (4), and (4S)-4,5,8-trihydroxy-alpha-tetralone 5-O-beta-D-glucopyranoside (5) on the basis of spectroscopic analysis and chemical evidence.     

Steroidal glycosides and aromatic compounds from Smilax riparia

Two new steroidal glycosides named riparosides A (1) and B (2), and two aromatic compounds (3, 4), together with four known flavonoid derivatives have been isolated from the EtOH extract of the rhizomes and roots of Smilax riparia A. DC. The structure of riparoside A (1) was determined to be 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->6)]-beta-D-glucopyranosyl 3beta,20alpha-dihydroxy-5alpha-furost-22(23)-ene 26-O-beta-D-glucopyranoside. Riparoside B (2) was characterized as 3-O-alpha-L-rhamnopyranosyl-(1-->2)-[alpha-L-rhamnopyranosyl-(1-->6)]-beta-D-glucopyranosyl 3beta,16beta-dihydroxy-5alpha-pregnan-20-one 16-O-[5-O-beta-D-glucopyranosyl 5-hydroxy-4-methyl-pentanoic acid]-ester 26-O-beta-D-glucopyranoside. Compounds 3 and 4 were elucidated as a sucrosyl ferulic acid ester and 7-O-methyl-10-oxythymol gentiobioside, respectively.     

A new pentacyclic cucurbitane glucoside and a new triterpene from the fruits of Gymnopetalum integrifolium

A new pentacyclic cucurbitane glucoside, named aoibaclyin (1) and a new triterpene (2) have been isolated from the EtOH extract of the fruits of Gymnopetalum integrifolium Kurz (Cucurbitaceae), together with three known compounds, bryoamaride (3), 25-O-acetylbryoamaride (4) and beta-sitosterol 3-O-beta-D-glucopyranoside (5). The structures of these compounds were elucidated by spectroscopic analyses.     

Six new dammarane-type triterpene saponins from the leaves of Panax ginseng

Six new minor saponins, together with known ginsenosides, were isolated from the leaves of Panax ginseng. The new saponins were named as ginsenoside-Rh5, -Rh6, -Rh7 -Rh8, -Rh9 and -Rg7, and their structures were elucidated on the basis of chemical and physicochemical evidence to be as follows: ginsenoside-Rh5: 3beta,6alpha,12beta,24zeta-tetrahydroxy-dammar-20(22),25-diene 6-O-beta-D-glucopyranoside (1), -Rh6: 3beta,6alpha12beta,20(S)-tetrahydroxy-25-hydroperoxy-dammar-23-ene 20-O-beta-D-glucopyranoside (2), -Rh7: 3beta,7beta,12beta,20(S)-tetrahydroxy-dammar-5,24-diene 20-O-beta-D-glucopyranoside (3), -Rh8: 3beta,6alpha,20(S)-trihydroxy-dammar-24-ene-12-one 20-O-beta-D-glucopyranoside (4), -Rh9: 3beta,6alpha,20(S)-trihydroxy-12beta,23-epoxy-dammar-24-ene 20-O-beta-D-glucopyranoside (5) and -Rg7: 3-O-beta-D-glucopyranosyl 3beta,12beta,20(S),24(R)-tetrahydroxy-dammar-25-ene 20-O-beta-D-glucopyranoside (6).     

Glycosides of Atractylodes ovata

A new coumarin glycoside and a new glycoside of an acetylene derivative were isolated from the water-soluble portion of the methanolic extract of Atractylodes ovata rhizome together with eight known compounds. Their structures were characterized as scopoletin beta-D-xylopyranosyl-(1-->6)-beta-D-glucopyranoside and (2E)-2-decene-4,6-diyne-1,8-diol 8-O-beta-D-apiofuranosyl-(1-->6)-beta-D-glucopyranoside, respectively, based on chemical and spectroscopic investigations. A comparison of the polar constituents among Atractylodes japonica, Atractylodes lancea, and A. ovata is led to the conclusion that A. ovata is distinguishable from A. lancea and A. japonica, as also shown by phylogenetic analysis.     

ent-pimarane-type diterpenoids from Siegesbeckia orientalis L

A new ent-pimarane glucoside, named hythiemoside B (4), was isolated from the aerial part of Siegesbecikia orientalis L. (Asteraceae) together with four known ent-pimarane-type diterpenoids: darutigenol (1), darutoside (2), hythiemoside A (3), and ent-(15R),16,19-trihydroxypimar-8(14)-ene 19-O-beta-D-glucopyranoside (5). The structure of the new compound was elucidated by spectroscopic analyses and chemical transformation. The NMR data of compounds 1 (1H-) and 5 (1H- and 13C-) were also compiled in this study on the basis of 2D experiments.     

Two new glycosides from the whole plants of Glechoma hederacea L

Two new glycosides, 7S,7'S,8R,8'R-icariol A(2)-9-O-beta-D-glucopyranoside (1) and 4-allyl-2-hydroxyphenyl 1-O-beta-D-apiosyl-(1-->6)-beta-D-glucopyranoside (2), were isolated from the dried whole plants of Glechoma hederacea L. (Labiatae) together with four known compounds, cistanoside E (3), dihydrodehydrodiconiferyl alcohol 4-O-beta-D-glucopyranoside (4), apigenin 7-O-beta-D-glucuronopyranoside (5) and luteolin 7-O-beta-D-glucopyranoside (6). The structures of the new compounds were elucidated on the basis of chemical and spectral analysis.     

Phenolic derivatives from the leaves of Martinella obovata (Bignoniaceae)

A new phenolic derivative, 4-methoxyphenol 1-O-beta-D-apiofuranosyl-(1 --> 6)-O-beta-D-glucopyranoside (1), has been identified together with uncommon 3,4-dimethoxyphenol 1-O-beta-D-apiofuranosyl-(1 --> 6)-O-beta-D-glucopyranoside (2) and 3-hydroxy, 4-methoxyphenol 1-O-beta-D-apiofuranosyl-(1 --> 6)-O-beta-D-glucopyranoside (3) from the leaves of Martinella obovata (Kunth) Bureau & K. Schum., an Honduran species used in folk medicine for the treatment of eyes diseases. Verbascoside, isoverbascoside, leucoceptoside A, vitexin, isovitexin, luteolin 8-C-beta-D-glucopiranoside and spireoside were also found. All structures were elucidated on the basis of mass spectrometry and 2D NMR techniques.     

Chemical composition and antioxidant activity of Campanula alliariifolia

In this study, the chemical constituents of Campanula alliariifolia Willd. (Campanulaceae) are being investigated for the first time with the aid of this article. Five known compounds, which were quercetin-3-O-glucoside, quercetin-3-O-rutinoside, kaempferol-3-O-glucoside, lobetyolin (9-O-beta-D-glucopyranosyl-2,10-tetradecadien-4,6-diyne-8,14-diol) and lobetyol (2,10-tetradecadien-4,6-diyne-8,9,14-triol), were isolated from the methanol extract. The antioxidant activity of the methanol extract and the purified compounds of the plant was investigated with DPPH (1,1-diphenyl-picrilyhydrazyl) (free radical scavenging activity) and reducing power methods. The methanol extract has antioxidant capacity according to the mentioned methods. Lobetyol and lobetyolin showed significant antioxidant activity more than both methanol extract and other purified compounds.     

Novel extended tetrathiafulvalenes based on acetylenic spacers: synthesis and electronic properties

A selection of mono- and diacetylenic dithiafulvalenes was synthesized and employed for the construction of extended tetrathiafulvalenes (TTFs) with hexa-2,4-diyne-1,6-diylidene or deca-2,4,6,8-tetrayne-1,10-diylidene spacers between the two 1,3-dithiole rings. By stepwise acetylenic scaffolding using (E)-1,2-diethynylethene (DEE) building blocks, an extended TTF containing a total of 18 C(sp) and C(sp(2)) atoms in the spacer was prepared. The versatility of the acetylenic dithiafulvene modules was also established by the efficient synthesis of a thiophene-spaced TTF, employing a palladium-catalyzed cross-coupling reaction. The developed synthetic protocols allow functionalization of the extended TTFs in three general ways: with 1) peripheral substituents on the fulvalene cores, 2) alkynyl moieties laterally appended to the spacer, and 3) cobalt clusters involving acetylenic moieties. Strong chromophoric properties of the extended TTFs were revealed by linear and nonlinear optical spectroscopies. Extensive electrochemical studies and calculations on these compounds are also reported, as well as X-ray crystallographic analyses.     

A novel cycloartane triterpene glycoside from the seeds of Cassia sophera L

A new cycloartane triterpene glycoside (1), named Cyclosophoside A, was isolated from the seeds of Cassia sophera L. The structure of 1 has been determined as 29-O-beta-D-glucopyranoside of 1alpha, 3beta, 24xi, 25-tetrahydroxy-9, 19-cycloartan-29-oic acid by means of physicochemical properties and spectroscopic methods (1D and 2D NMR, MS).     

Rossicasins A, B and rosicaside F, three new phenylpropanoid glycosides from Boschniakia rossica

Three phenylpropanoid glycosides have been isolated, together with the known phenylpropanoid glycosides rossicaside A (4), B (5), E (6), and trans-p-coumaryl alcohol 1-O-beta-D-glucopyranosyl(1-->4)-alpha-L-rhamnopyranosyl(1-->3)-beta-D-glucopyranoside (7), and an acylated oligosaccharide beta-D-glucopyranosyl(1-->4)-alpha-L-rhamnopyranosyl-(1-->3)-(4-O-trans-caffeoyl)-D-glucopyranose) (8), from the aqueous extract of Boschniakia rossica (CHAM. et SCHLECH.) FEDTSCH. et FLEROV. Spectroscopic evidence led to the assignments of their structures as trans-p-coumaryl-(6'-O-beta-D-xylopyranosyl)-O-beta-D-glucopyranoside (1), trans-p-coumaryl-(6'-O-alpha-L-arabinopyranosyl)-O-beta-D-glucopyranoside (2) and 2-(3,4-dihydroxyphenyl)-R,S-2-ethoxy-ethyl-O-beta-D-glucopyranosyl(1-->4)-alpha-L-rhamnopyranosyl(1-->3)(4-O-trans-caffeoyl)-beta-D-glucopyranoside (3), designated as rossicasin A, rossicasin B, and rossicaside F, respectively. Compound 7 was identified from the degradation reaction and this is the first isolation from a natural source.