New oleanene glycosides from the leaves of Acanthopanax japonicus

The structures of 6 new oleanene glycosides (1--6) isolated from the leaves of Acanthopanax japonicus FRANCH et. SAVART (Araliaceae) were elucidated by mass, 1D, and 2D NMR spectroscopy. The structures of 1--6 were established as 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester of 3beta,23-dihydroxy-olean-12-en-28,29-dioic acid, 3beta,30-dihydroxy-olean-12-en-23,28-dioic acid, 3beta,29-dihydroxy-olean-12-en-23,28-dioic acid (=dianic aicd), 3beta-dihydroxy-olean-12-en-23,28-dioic acid (=gypsogenic acid), 3beta,29-dihydroxy-23-oxo-olean-12-en-28-oic acid, and 3beta-hydroxy-23-oxo-olean-12-en-28,29-dioic acid, designated acanjaposide D (1), E (2), F (3), G (4), H (5), and I (6), respectively.     

Lupane glycosides from the leaves of Acanthopanax koreanum

Three new lupane-type saponins, acankoreosides F--H (1--3) were isolated from the methanol extract of the leaves of Acanthopanax koreanum NAKAI. The structures of these three saponins were established by chemical and spectroscopic analysis as 3alpha,30-dihydroxylup-20(29)-en-23,28-dioic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester (1), 3alpha,30-dihydroxylup-23-al-20(29)-en-28-oic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester (2), and (20S) 3alpha-hydroxylup-23-al-28,29-dioic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester (3), respectively. The effects of the isolates (1-3) on the lipopolysaccharide-induced production of nitric oxide and prostaglandin E2 were evaluated in RAW 264.7 macrophages.     

Sulfated lupane triterpene derivatives and a flavone C-glycoside from Gypsophila repens

A new sulfated lupane triterpene, Gypsophilin (1), and its glucosyl ester, Gypsophilinoside (2) were isolated from the roots of Gypsophila repens whereas a new flavone C-glycoside (3) was obtained from the aerial parts. Their structures were established as (3beta)-3-O-(sulfo)lup-20(29)-en-23,28-dioic acid (1), (3beta)-3-O-(sulfo)lup-20(29)-en-23,28-dioic acid -28-O-beta-D-glucopyranosyl ester (2) and luteolin-7-O-alpha-L-arabinopyranosyl-6-C-beta-glucopyranoside (3) by spectroscopic methods such as 1D and 2D NMR, HR-ESI-MS and FAB-MS.     

A new lupane glycoside from the leaves of Acanthopanax koreanum

A new lupane-type saponin, named acankoreoside E (1), was isolated from the methanol extract of the leaves of Acanthopanax koreanum, and its structure was established through chemical and spectroscopic analyses as (20S) 3alpha-hydroxy-30-oxolupan-23,28-dioic acid 28-O-[alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl] ester.     

Complete assignments of 1H and 13C NMR spectral data for three new triterpenoid saponins from Ilex hainanensis Merr

Three new oleanane-type triterpenoid saponins, ilexhainanoside C, D and E, all with 24, 28-dioic acid groups, were isolated from the leaves of Ilex hainanensis. They were 3beta-hydroxyolean-12-ene-24, 28-dioic acid-28-O-beta-D-glucopyranoside(1), 3beta, 19alpha-dihydroxyolean-12-ene-24, 28-dioic acid-28-O-beta-D-glucopyranoside(2) and 3beta, 29-dihydroxyolean-12-ene-24, 28-dioic acid-28-O-beta-D-glucopyranoside(3). The structures of these three new compounds were elucidated and complete assignments of the (1)H and (13)C NMR spectroscopic data were achieved by 1D and 2D NMR experiments [heteronuclear single quantum coherence (HSQC), HMBC and rotational nuclear Overhauser effect spectroscopy (ROESY)].     

Triterpenes from Mimusops elengi

Pentacyclic triterpenes (1) and (2) have been isolated from Mimusops elengi and assigned structures 3beta,6beta,19alpha,23-tetrahydroxy-urs-12-ene and 1beta-hydroxy-3beta-hexanoyllup-20 (29)-ene-23, 28-dioic acid, respectively, on the basis of spectroscopic studies including 2D-NMR. The compound 1 showed moderate inhibiting activity against beta-glucuronidase enzyme     

Triterpenoidal saponins from the barks of Zygophyllum fabago L

Two new triterpenoid saponins, zygophylosides O (1) and P (2), have been isolated from the barks of Zygophyllum fabago L. Their structures were elucidated as 3beta-[(2-O-sulfo-beta-D-xylopyranosyl)oxy]urs-12-ene-27,28-dioic acid and 3beta-[(2-O-sulfo-beta-D-xylopyranosyl)oxy]urs-12-ene-27,28-dioic acid 28-beta-D-glucopyranoside, respectively, by spectral and chemical evidence. Compound 1 showed weaker Nitric Oxide (NO) inhibitory activity.     

Lupane triterpenoids from Acacia mellifera with cytotoxic activity

Three new pentacyclic triterpenoids: (20R)-3-oxolupan-30-al (1), (20S)-3-oxolupan-30-al (2) and (20R)-28-hydroxylupen-30-al-3-one (3), along with (20S)-3beta-hydroxylupan-30-al (4), the latter previously described as a constituent of an epimeric mixture, were isolated from Acacia mellifera. In addition, the known metabolites 30-hydroxylup-20-(29)-en-3-one (5), 30-hydroxylup-20-(29)-en-3beta-ol (6), atranorin, methyl 2,4-dihydroxy-3,6 dimethyl benzoate, sitosterol-3beta-O-glucoside and linoleic acid were found in the analyzed plant species for the first time. The structures of the new metabolites were elucidated by extensive spectroscopic analyses and their relative stereochemistry was determined by NOESY experiments. The new metabolite 3 exhibited significant cytotoxic activity against the NSCLC-N6 cell line, derived from a human non-small-cell bronchopulmonary carcinoma.     

A New Esterification Reaction in Synthesis of Gibberellins

Esterification is an important reaction in organic synthesis. In the synthesis of gibberellin derivative, a new es terification reaction was found. Ent-16-oxo-20-norgibberella-9-ene-7, 19-dioic acid 7-(methyl ester) (Ⅰ) is a key material in synthesis of GA73. [1] Ⅰ is dissolved in acetone, and treated with ICl and anhydrous K2CO3 at room temperature for 2 h to produce a new ester, ent-16-oxo-20-norgibberella-9-ene-7, 19-dioic acid 7-(methyl ester), 19-(oxopropyl ester ) (Ⅱ). The yield is above 90%. The structure of Ⅱ is confirmed by NMR and MS.     

Chemical constituents of the aerial parts of Kalidium foliatum

Studies on the chemical constituents of the aerial parts of Kalidium foliatum have led to the isolation of three new and one known compounds. The structures of new constituents have been elucidated through spectral studies including 2D-NMR experiments (HMQC, HMBC, COSY, NOESY and J-resolved) and MS/MS fragmentation using Q-TOF mass spectrometer equipped with an ESI source as kalidiumoside C (=3beta-hydroxy-29-methylmalonoxy-olean-12-en-23,28-dioic acid-23-methyl-28-beta-D-glucopyranosyl ester; 1), kalidiunin (=3beta,23,29-trihydroxy-olean-12-en-28-methyl-oate; 2) and kalidiumoside D (=3beta,23,29-trihydroxyolean-12-en-28-oic acid-beta-D-glucopyranosyl ester; 3). The known compound was identified as 3beta,23,29-trihydroxy-olean-12-en-28-oic acid 4) through comparison of its spectral data with those reported in literature. Acid hydrolysis of both 2 and 3 yielded the known compound 4 providing a conclusive evidence of the proposed structures.     

Fargosides A-E, triterpenoid saponins from Holboellia fargesii

Five new triterpenoid saponins, fargosides A, B, C, D, and E, were isolated from the roots of Holboellia fargesii. The structures of fargosides A-E were elucidated on the basis of chemical and physicochemical evidence and found to be 3beta,20alpha-dihydroxy-29-norolean-12-en-28-oic acid 3-O-beta-D-xylopyranosyl-(1-->2)-beta-D-glucopyranoside (1), 3beta,20alpha,24-trihydroxy-29-norolean-12-en-28-oic acid 23-O-beta-D-fucopyranosyl-(1-->2)-[alpha-L-arabinopyranosyl-(1-->3)]-beta-D-glucopyranoside (2), 3beta,23-dihydroxy-30-norolean-2,20(29)-dien-28-oic acid 3-O-alpha-L-arabinopyranosyl-(1-->2)-[beta-D-glucopyranosyluronic acid-(1-->3)]-alpha-L-arabinopyranoside (3), 3beta,23-dihydroxy-30-norolean-12,20(29)-dien-28-oic acid 3-O-methyl beta-D-glucopyranosyluronate-(1-->3)-alpha-L-arabinopyranoside (4), and 3beta,23-dihydroxy-olean-12-en-28-oic acid 3-O-methyl beta-D-glucopyranosyluronate-(1-->3)-alpha-L-arabinopyranoside (5), respectively.     

New Triterpenes from the Heartwood of Melaleuca leucadendron L.

Fourteen chemical constituents were isolated from the CHCl₃ soluble portion of the heartwood of Melaleuca leucadendron L. These compounds include β-sitosterol (1) , β-sitostenone (2) , 6-hydroxy-4,6-dimethyl-3-hepten-2-one (3) , naphthalene (4) , squalene (5) , 2α3β-dihydroxyurs-12-en-28-oic acid (6) , 3β-hydroxylup-20(29)-en-27,28-dioic acid (7) , 2α,3β-dihydroxyolean-12-en-28-oic acid (8) , 3β,23-dihydroxyolean-12-en-28-oic acid (9) , 2α,3β,23-trihydroxyolean-12-en-28-oic acid (10) , 3β-trans-p-coumaroyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (11) , and three novel oleanane derivatives 23-trans-p-coumaroyloxy-2α,3β-dihydroxyotean-12-en-28-oic acid (12), 3β-trans-caffeoyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (13) , and its isomer 3β-cis-caffeoyloxy-2α,23-dihydroxyolean-12-en-28-oic acid (14) , The three novel compounds were characterized as the two and three O-methylated derivatives, respectively.     

Two new triterpenoid saponins from Platycodon grandiflorum.

Two new triterpenoid saponins, platycoside D [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl-(1-->6)-beta-D- glucopyranosyl-2 beta, 3 beta, 16 alpha, 23-tetrahydroxyolean-12-ene-28-oic acid 28-O-beta-D- apiofuranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alpha-L-rhamnop yranosyl- (1-->2)-alpha-L-arabinopyranoside] and platycoside E [3-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl- (1-->6)-beta-D-glucopyranosyl-2 beta,3 beta,16 alpha,23,24-pentahydroxyolean-12-ene-28-oic acid 28-O-beta-D-apiofuranosyl-(1-->3)-beta-D-xylopyranosyl-(1-->4)-alp ha-L- rhamnopyranosyl-(1-->2)-alpha-L-arabinopyranoside] were isolated from the roots of Platycodon grandiflorum. Structural determination is based on spectral and chemical evidence.     

Constituents of Ilex Species I. On the Leaves of Ilex Cornuta Lindl

Phytochemical examination on the leaves of Ilex cornuta Lindl. (Aquifoliaceae) resulted in the isolation and identification of lupeol (I), 3β-hydroxylup-20(29)-en-30-al (II), oleanolic acid (III), and β-sitosterol-β-D-glucoside (IV).     

New triterpenoids from the leaves of Abrus precatorius

Three new (1-3) triterpenoids and one known (4) triterpenoid were isolated from an acid hydrolyzed methanol-soluble extract of the leaves of Abrus precatorius. Their structures were identified as (20S,22S)-3beta,22-dihydroxycucurbita-5(10),24-diene-26,29-dioic acid delta-lactone (1), 3-O-[6'-methyl-beta-D-glucuronopyranosyl]-3beta,22beta-dihydroxyolean-12-en-29-oic acid methyl ester (2), 3-O-beta-D-glucuronopyranosylsophoradiol methyl ester (3), and sophoradiol (4) by spectroscopic techniques including 2D NMR.     

The Terpenoids of Maytenus boaria MOL. (Celastraceae)

The known triterpenoids β-amyrin (= olean-12-en-3β-ol; 22 ), lupeol (= lup-20(29)-en-3β-ol; 17 ), betulin (= lup-20(29)-ene-3β,28-diol; 18 ), lup-20(29)-ene-3β,30-diol ( 20 ), oleanolic acid (= 3β-hydroxyolean-12-en-28-oic acid; 21 ), and betulonic acid (= 3-oxolup-20(29)-en-28-oic acid; 19 ), together with epicatechol (= cis-2-(3,4-dihydroxyphenyl)-3,4-dihydro-2H-1-benzopyran-3,5,7-triol; 23 ), 5′-O-methylgallocatechol (= trans-2-(3,4-dihydroxy-5-methoxyphenyl)-3,4-dihydro-2H-1-benzopyran-3,5,7-triol; 24 ), and 4-hydroxybenzaldehyde were isolated from the aerial parts of Maytenus boaria (MOL. ). Additonally, the eight 4,C⁴-dihydro-β-agarofuran sesquiterpenoids 1–8 , one of them a diol with a (4R)-configuration, and compound 9 were present in the extract. The structures of these compounds were established by spectroscopic and chemical means.     

Triterpenes and saponins from Ilex psammophila

Two new saponins were isolated from the leaves of Ilex psammophila. Their structure was established by chemical and spectroscopic methods as 28-O-beta-D-glucopyranosylester of 20(S)-ilexgenin A ([structure: see text]) and 28-O-beta-D-glucopyranosylester of 20(S)-3beta,19alpha,24-trihydroxyurs-12-ene-23, 28-dioic acid ([structure: see text]).     

Trypanocidal constituents in plants 6. 1) Minor withanolides from the aerial parts of Physalis angulata

Further study of the methanol extract of the aerial parts of Physalis angulata (Solanaceae) resulted in the isolation of new withanolides, designated physagulins L, M and N, together with known withanolide, physagulin D and flavonol glycoside, quercetin 3-O-rhamnosyl-(1-->6)-galactoside. The chemical structures of these new withanolides were elucidated by detailed spectroscopic analyses to be (20R,22R)-15alpha-acetoxy-5alpha,6beta,14beta,17beta,27-pentahydroxy-1-oxo-witha-2, 24-dienolide, (20S,22S)-15alpha-acetoxy-5alpha,6beta,14alpha,23beta-tetrahydroxy-1-oxo-witha-2,16,24-trienolide and (20S,22R)-15alpha-acetoxy-5beta,6beta-epoxy-14alpha-hydoxy-3beta-methoxy-1-oxo-witha-16,24-dienolide, respectively. All these compounds showed weak trypanocidal activity against trypomastigotes, an infectious form of Trypanosoma cruzi, the etiologic agent for Chagas' disease. Withanolides obtained in the previous paper showed considerable trypanocidal activity, suggesting the structure-activity relationships.     

Three new pentacyclic triterpenes and some flavonoids from the fruits of an Indian Ayurvedic plant Dendrophthoe falcata and their estrogen receptor binding activity

Extensive chromatographic screening of extracts of the fruits of the Indian Ayurvedic plant, Dendrophthoe falcata, resulted in the isolation of three new triterpenes, 3beta-acetoxy-1beta-(2-hydroxy-2-propoxy)-11alpha-hydroxy-olean-12-ene (1), 3beta-acetoxy-11alpha-ethoxy-1beta-hydroxy-olean-12-ene (2) and 3beta-acetoxy-1beta-hydroxy-11alpha-methoxy-olean-12-ene (3) along with nine known compounds, 3beta-acetoxy-1beta,11alpha-dihydroxy-olean-12-ene (4), 3beta-acetoxy-1beta,11alpha-dihydroxy-urs-12-ene (5), 3beta-acetoxy-urs-12-ene-11-one (6), 3beta-acetoxy-lup-20(29)-ene (7), 30-nor-lup-3beta-acetoxy-20-one (8), (20S)-3beta-acetoxy-lupan-29-oic acid (9), kaempferol-3-O-alpha-L-rhamnopyranoside (10), quercetin-3-O-alpha-L-rhamnopyranoside (11), and gallic acid (12). The structures of these compounds were determined using 1D and 2D NMR and high resolution electrospray mass spectrometry. These compounds were assayed for binding to estrogen receptors-alpha and beta and kaempferol-3-O-alpha-L-rhamnopyranoside (10) was found to be a ligand for both receptors with greater affinity for beta. The triterpenes (1-9) are reported for the first time in the genus Dendrophthoe and assumes taxonomic significance.     

Chemical constituents of two sages with free radical scavenging activity

From the aerial parts of Salvia trichoclada Bentham and S. verticillata L. one new and two known phenolic acids, 3-(3',4'-dihydroxyphenyl)-2-hydroxymethyl propionic acid (1), 3-(3',4'-dihydroxyphenyl) lactic acid (2), and rosmarinic acid (3); two flavonoids, apigenin 4'-methyl ether 7-O-glucuronide (4), and luteolin 7-O-beta glucuronide (5); two lupan type triterpene aglycones, lupeol (6), and 30-hydroxylup-20 (29)-en-3-on (7); an oleanane-type triterpene acid, oleanolic acid (8); and an ursan-type triterpene acid, ursolic acid (9) were isolated. The structures of the compounds were elucidated by spectroscopic analysis. Different extracts of the plants were examined for their free radical scavenging activities by DPPH (2,2-Diphenyl-1-picrylhydrazyl) assay. Some of the polar extracts showed high free radical scavenging activity.