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.     

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.     

Lupane-triterpene carboxylic acids from the leaves of Acanthopanax trifoliatus

Two new lupane-triterpene carboxylic acids, called acantrifoic acid A (1) and acantrifoside C (2) have been isolated from the leaves of Acanthopanax trifoliatus. Based on extensive 1D and 2D NMR spectroscopic data, their chemical structures were determined as 3 alpha-acetoxy-30-hydroxylup-20(29)-ene-23,28-dioic acid and 3 alpha-acetoxy-30-hydroxylup-20(29)-ene-23,28-dioic acid 28-O-alpha-L-rhamnopyranosyl-(1-->4)-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester.     

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.     

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.     

Two oleananes from Ammannia auriculata Willd

Two new compounds: 3-β,15-α,23,28-tetrahydroxyolean-12-en-3-O-arabinopyaranoside and 3-β,23,28-trihydroxy-olean-12-en-3-O-β-D-glucopyranoside were isolated from the aerial parts of Ammania auriculata along with the known compounds kaempferol, β-sitosterol-3-O-β- D-glucoside, 2-α,3-β,23-trihydroxyolean-12-en-28-oic acid-28-O-β-D-glucopyranoside, quercetin, kaempferol-3-O-α-L-arabinofuranoside, kaempferol-3-O-β-D-xylopyranoside and ellagic acid. Structures of these compounds were elucidated on the basis of their spectroscopic data (NMR, UV, MS and IR spectra). The antioxidant activities of the total extract, the fractions CH(2)Cl(2), EtOAc and the remaining aqueous together with the compounds 1, 6 and 9 were comparable with that of the standard antioxidant, ascorbic acid.     

Two new triterpenoid saponins isolated from Polygala japonica

Bioassay guided investigation of whole parts of Polygala japonica afforded two new triterpenoid saponins, characterized as 3-O-beta-D-glucopyranosyl medicagenic acid 28-O-{beta-D-xylopyranosyl(1-->4)-[beta-D-apiofuranosyl(1-->3)]-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl} ester (1), 3-O-beta-D-glucopyranosyl 2-oxo-olean-12-en-23, 28-dioic acid 28-O-{beta-D-xylopyranosyl(1-->4)-[beta-D-apiofuranosyl(1-->3)]-alpha-L-rhamnopyranosyl(1-->2)-beta-D-glucopyranosyl} ester (2), together with four known triterpenoid saponins (3-6). Their structures were elucidated by spectroscopic and chemical methods. Saponins 3, 4 and 5 showed significant anti-inflammation effects on carrageenan-induced acute paw edema in mouse.     

19-nor-11-Oxooleanan-12-ene and 18,19-seco-19-oxours-11,13(18)-diene triterpenes from Diospyros decandra bark

Four new triterpenes, 2α,3β-dihydroxy-19-nor-11-oxo-20-dimethylurs-12-en-24,28-dioic acid (equivalent to 2α,3β-dihydroxy-19-nor-11-oxoolean-12-en-24,28-dioic acid), 2α,3β-dihydroxy-18,19-seco-19-oxours-11,13(18)-dien-24,28-dioic acid, 2α,3β,19α-trihydroxy-11-oxours-12-en-24,28-dioic acid and 2α,3β,19α-trihydroxy-28-1′-β-d-[glucopyranosyl-(1″→6′)-glucopyranosyl]-urs-12-en-24,28-dioic acid were isolated from the methanol extract of the bark of Diospyros decandra as their acetate-methyl ester derivatives. The first two compounds represent the biosynthetic transformation products of 2α,3β,19-trihydroxyurs-24,28-dioic acid via oxidative rearrangement of ring E.     

New triterpenoid saponins from Stelmatocrypton khasianum

Four new triterpenoid saponins, designated as stelmatotriterpenosides E-H (1-4), together with three known compounds, asterbatanoside B (5), 2alpha,3beta,19alpha,23-tetrahydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (6) and 2alpha,3beta,19alpha,23-tetrahydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl ester (7), were isolated from the stems of Stelmatocrypton khasianum. On the basis of chemical and spectral evidence, the structures of 1-4 were established as 2alpha,3beta,23-trihydroxy-olean-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (1), 2alpha,3beta,23-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester (2), 2alpha,3beta,19alpha-trihydroxy-urs-12-en-28-oic acid-3-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl-(1-->2)-beta-D-glucopyranosyl ester (3), and 2beta,3beta,19alpha-trihydroxy-urs-12-en-24,28-dioic acid-24-O-beta-D-glucopyranosyl-28-O-beta-D-glucopyranosyl diester (4).     

Three new triterpenoid saponins from Dianthus superbus

Three new triterpenoid saponins (1-3) were isolated from the dried aerial parts of Dianthus superbus L. (Caryophyllaceae). Their structures were established as 3-O-β-D-glucopyranosyl gypsogenic acid 28-O-[β-D-6-O-((3S)-3-hydroxyl-3-methylglutaryl)glucopyranosyl(1→6)]-β-D-glucopyranoside (1), 3-O-β-D-glucopyranosyl gypsogenic acid 28-O-[β-D-glucopyranosyl(1→3)][β-D-6-O-((3S)-hydroxyl-3-methylglutaryl)glucopyranosyl(1→6)]-β-D-glucopyranoside (2), 3-O-α-L-arabinopyranosyl-3β,16α-dihydroxyolean-12-en-23,28-dioic acid 28-O-[β-D-glucopyranosyl-(1→6)]-β-D-glucopyranoside (3), on the basis of various spectroscopic analyses and chemical degradations.     

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.     

Two new bioactive oleanane triterpene glycosides from Terminalia arjuna

Two new oleanane-type triterpene glycosides designated as Termiarjunoside I and Termiarjunoside II were isolated from stem bark of Terminalia arjuna (Combretaceae) and characterized as olean-1alpha,3beta,9alpha,22alpha-tetraol-12-en-28-oic acid-3beta-D-glucopyranoside (1) and olean-3alpha,5alpha,25-triol-12-en-23,28-dioic acid-3alpha-D-glucopyranoside (2) based on chemical and spectral data evidences. Both compounds 1 and 2 potently suppressed the release of nitric oxide and superoxide from macrophages and also inhibited aggregation of platelets.     

New triterpenoids from Corchorus trilocularis

Two new tetracyclic triterpenoid trilocularol A and trilocularol A 3-glucoside and one pentacyclic triterpenoid tirlocularoside A were isolated from Corchorus trilocularis L., their structure were elucidated as 3beta,6alpha,16alpha,20(S),27-pentahydroxydammar-24(Z)-ene (1), 3beta-D-glucopyranosyloxy-6alpha,16alpha,20(S),27-tetrahydroxydammar-24(Z)-ene (2) and 2alpha,3beta,19alpha,30-tetrahydroxyurs-12-en-24,28-dioic acid 28-O-beta-D-glucopyranosyl ester (3). respectively, on the basis of detailed spectroscopic studies.     

New triterpene glucosides from the roots of Rosa laevigata Michx

Two new ursane-type triterpene glucosides, 2alpha,3alpha,24-trihydroxyurs-12,18-dien-28-oic acid beta-D-glucopyranosyl ester (1) and 2alpha,3alpha,23-trihydroxyurs-12,19(29)-dien-28-oic acid beta-D-glucopyranosyl ester (2), were isolated from the roots of Rosa laevigata, together with three known compounds: 2alpha,3beta,19alpha-trihydroxyurs-12-en-28-oic acid beta-Dglucopyranosyl ester (3), 2alpha,3alpha,19alpha-trihydroxyurs-12-en-28-oic acid beta-D-glucopyranosyl ester (4) and 2alpha,3beta,19alpha,23-tetrahydroxyurs-12-en-28-oic acid beta-D-glucopyranosyl ester (5). The structures of new compounds were established on the basis of detailed 1D and 2D NMR spectroscopic analyses. Compounds 2 and 5 exhibited modest in vitro antifungal activities against Candida albicans and C. krusei.     

Three diterpenoids (excoecarins V1-V3) and a flavanone glycoside from the fresh stem of Excoecaria agallocha

Three new diterpenoids, excoecarins V1-V3 (1-3) and a new flavanone glycoside (7) were isolated from the fresh stem of Excoecaria agallocha L. Their structures were elucidated as: 2alpha,3alpha,18-trihydroxy-3beta,20-epoxybeyer-15-ene (1), ent-2,3-secokaur-16-en-2,3-dioic acid (2), ent-3,4-seco-16alpha-hydroxyatis-4(19)-en-3-oic acid (3), and 3,5,7,3',5'-pentahydroxy-2R,3R-flavanonol 3-O-alpha-L-rhamnopyranoside (7) on the basis of spectroscopic data, chemical evidence, and/or X-ray analysis.     

Lupane-triterpenes from Bupleurum flavum

Two new triterpenoids, lup-20(29)-en-3 alpha, 28-diol (1) and lup-20(29)-en-3 alpha, 28,30-triol (2), have been isolated from aerial parts of Bupleurum flavum, a native plant of the Eastern Mediterranean area (Bulgaria, Greece, and Turkey). Their structures were elucidated by spectral analysis. The known compounds betulin, betulinic acid, jasminol, together with the lignan nemerosin and eight flavonoids (kaempferol, isokaempferide, gossipetin, quercetin, luteolin, isorhamnetin 3-O-beta-D-glucopyranoside, isorhamnetin 3-rutinoside, and rutin) were also characterized.     

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.     

Triterpene glycosides from the stems of Akebia quinata

The stems of Akebia quinata have been analyzed for their triterpene glycoside constituents, resulting in the isolation of six new triterpene glycosides, along with 19 known ones. On the basis of extensive spectroscopic analysis, including 2D NMR data, and chemical evidence, the structures of the new compounds were deter-mined to be 3beta-[(O-beta-D-glucuronopyranosyl-(1-->3)-alpha-L-arabinopyranosyl)oxy]olean-12-en-28-oic acid O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3beta-[(O-beta-D-glucuronopyranosyl-(1-->3)-O-[alpha-L-rhamnopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl)oxy]olean-12-en-28-oic acid O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3beta-[(O-beta-D-glucuronopyranosyl-(1-->3)-alpha-L-arabinopyranosyl)oxy]-23-hydroxyolean-12-en-28-oic acid O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3beta-[(O-beta-D-glucuronopyranosyl-(1-->3)-O-[alpha-L-rhamnopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl)oxy]-23-hydroxyolean-12-en-28-oic acid O-alpha-L-rhamnopyranosyl-(1-->4)-O-beta-D-glucopyranosyl-(1-->6)-beta-D-glucopyranosyl ester, 3beta-[(O-beta-D-glucopyranosyl-(1-->3)-O-[alpha-L-rhamnopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl)oxy]-29-hydroxyolean-12-en-28-oic acid, and 3beta-[(O-beta-D-glucopyranosyl-(1-->3)-O-[alpha-L-rhamnopyranosyl-(1-->2)]-alpha-L-arabinopyranosyl)oxy]-23,29-dihydroxyolean-12-en-28-oic acid, respectively. The main triterpene glycosides contained in the stems of A. quinata were found to have two sugar units at C-3 and C-28 of the aglycone in this study, whereas those of Akebia trifoliate were reported to possess one sugar unit at C-28 of the aglycone. It may be possible to distinguish between A. quinata and A. trifoliate chemically by comparing their triterpene glycoside constituents.     

Two minor diterpene glycosides from the leaves of Stevia rebaudiana

Two new new diterpene glycosides, 13-[(2-O-(6-O-beta-D-glucopyranosyl)-beta-D-glucopyranosyl-beta-D-glucopyranosyl)oxy] kaur-16-en-18-oic acid beta-D-glucopyranosyl ester (1) and 13-[(2-O-beta-D-glucopyranosyl-3-O-beta-D-fructofuranosyl-beta-D-glucopyranosyl)oxy] kaur-16-en-18-oic acid beta-D-glucopyranosyl ester (2) were isolated from the leaves of Stevia rebaudiana, along with the known steviol glycosides stevioside, rebaudiosides A-F and dulcoside A. The structures of the two new compounds were established on the basis of extensive 2D NMR (COSY, HSQC, and HMBC), MS and chemical studies.