Triterpenoid Saponins from Anemone flaccida

From the rhizome of ANEMONE FLACCIDA Fr. Schmidt, used in Chinese folk medicine, four saponins of oleanolic acid-A,B,C,D were isolated. By means of spectroscopy and chemical transformation, saponins A, B, and D were identified as 3- O-[alpha- L-rhamnopyranosyl-(1-->2)-alpha- L-arabinopyrasyl]-oleanolic acid, 3- O-[alpha- L-rhamnopyranosyl-(1-->2)-beta- D-xylopyranosyl]-oleanolic acid, and 3- O-[alpha- L-rhamnopyranosyl-(1-->2)-beta- D-glucopyranosyl]-oleanolic acid. These three saponins are known compounds but isolated from ANEMONE plants for the first time. Saponin C was elucidated as 3- O-[beta- D-glucopyranosyl-(1-->2)-beta- D-xylopyranosy1]-oleanolic acid, which has not been reported in the literature before, and is named as flaccidoside I.     

Antifungal steroid saponins from Dioscorea cayenensis

From the rhizomes of Dioscorea cayenensis Lam.-Holl (Dioscoreaceae), the new 26- O- beta- D-glucopyranosyl-22-methoxy-3 beta,26-dihydroxy-25( R)-furost-5-en-3- O- alpha- L-rhamnopyranosyl-(1-->4)- alpha- L-rhamnopyranosyl-(1-->4)-[ alpha- L-rhamnopyranosyl-(1-->2)]- beta- D-glucopyranoside ( 1) was isolated together with the known dioscin ( 2) and diosgenin 3- O- alpha- L-rhamnopyranosyl-(1-->4)- alpha- L-rhamnopyranosyl-(1-->4)-[ alpha- L-rhamnopyranosyl-(1-->2)]- beta- D-glucopyranoside ( 3). Their structures were established on the basis of spectral data. Compound 2 exhibited antifungal activity against the human pathogenic yeasts Candida albicans, C. glabrata and C. tropicalis (MICs of 12.5, 12.5 and 25 micro g/mL, respectively) whereas 3 showed weak activity and 1 was inactive.     

Two New Saponins from Phytolacca americana

Two new monodesmosidic saponins (Phytolaccosides F and D (2)) have been isolated from the roots of PHYTOLACCA AMERICANA and identified as 3- O-[alpha- L-rhamnopyranosyl(1-->2)-beta- D-glucopyranosyl (1-->2)-beta- D-xylopyranosyl]phytolaccagenic acid and 3- O-[beta- D-glucopyranosyl(1-->2)-beta- D-xylopyranosyl]phytolaccagenic acid, respectively.     

A New Triterpenoid and its Glycoside from Phytolacca esculenta

A new triterpenoid and its glycoside, designated as esculentagenic acid and esculentoside J, have been isolated and characterized from the roots of PHYTOLACCA ESCULENTA. The new compounds have been identified as 2beta,3beta,23,30-tetrahydroxyolean-12-en-28-oic acid and 3- O-[beta- D-glucopyranosyl(1-->4)-beta- D-xylopyranosyl] - 28- O-beta- D-glucopyranosyl- 2beta,3beta,23,30-tetrahydroxyolean-12-en-28-oic acid.     

A New Bidesmosidic Triterpenoidal Saponin from the Roots of Symphytum officinale

A new triterpenoidal saponin having hederagenin as the aglycone was isolated from the roots of SYMPHYTUM OFFICINALE L. The structure of this saponin was elucidated by FAB-MS, (1)H-, (13)C-NMR, 2D-NMR analyses and chemical studies as 3- O-[beta- D-glucopyranosyl-(1-->4)-alpha- L-arabinopyranosyl]-hederagenin 28- O-[beta- D-glucopyranosyl-(1-->6)-beta- D-glucopyranosyl] ester.     

Oligofurostanosides from Asparagus cochinchinensis

The aqueous extract of ASPARAGUS COCHINCHINENSIS yielded a new oligofurostanoside 3- O-[alpha- L-rhamnopyranosyl-(1-->4)-beta- D-glucopyranosyl]-26- O-(beta- D-glucopyranosyl)-(25 R)-furosta-5,20-diene,-3beta,26-diol as well as two known furostanosides, methylprotodioscin and pseudoprotodioscin.     

Triterpenoid saponins from Androsace umbellata and their anti-proliferative activities in human hepatoma cells

Two new triterpenoid saponins, along with five known ones, were isolated from the EtOH extract of the whole plants of Androsace umbellata. The structures of the new triterpenoid saponins were identified as 3- O-[ beta- D-xylopyranosyl-(1-->2)- beta- D-glucopyranosyl-(1-->4)-[ beta- D-glucopyranosyl-(1-->2)]- alpha- L-arabinopyranosyl]-3 beta-hydroxy-13 beta,28-epoxy-16-oxo-oleanan-30-al ( 1) and 3- O- beta- D-xylopyranosyl-(1-->2)- beta- D-glucopyranosyl-(1-->4)- alpha- L-arabinopyranosyl-3 beta-hydroxy-13 beta,28-epoxy-16-oxo-oleanan-30-al ( 2) on the basis of their spectral and chemical properties. All these compounds showed significant cytotoxic activities in human hepatoma cells.     

Antifungal saponins from Paris polyphylla Smith

Three steroidal saponins, including one new and two known compounds, were isolated from the rhizomes of Paris polyphylla Smith. One- and two-dimensional NMR, LC-MS, and interpretation of hydrolytic cleavage experiments led to the identification of the structure of the new saponin as ( 25R)-spirost-5-ene-3 beta,17 alpha-diol (pennogenin) 3- O-{ O- alpha- L-rhamnopyranosyl-(1-->2)- O-[ O- beta-xylopyranosyl-(1-->5)- alpha- L-arabinofuranosyl-(1-->4)]- beta- D-glucopyranoside}. The isolated saponins were evaluated for their antifungal activity against Cladosporium cladosporioides and Candida species and showed comparable activity to chemicals used in some commercial products.     

Triterpenoid saponins with anti-inflammatory activity from Codonopsis lanceolata

Six triterpenoid saponins, including a new compound named codonolaside III, were isolated from the roots of Codonopsis lanceolata. The spectral and chemical data revealed the structure of codonolaside III to be 3- O-[ beta- D-xylopyranosyl -(1-->3)- beta- D-glucuronopyranosyl]-3 beta,16 alpha-dihydroxyolean-12-ene-28-oic acid 28- O-[ beta- D-xylopyranosyl-(1-->4)- alpha- L-rhamnpyranosyl-(1-->2)][ beta- D-glucopyranosyl -(1-->4)]- alpha- L-arabinopyranosyl ester. The xylene-induced mouse ear edema inhibitory effect assay disclosed codonolaside and codonolasides I - III as the major anti-inflammatory constituents in this crude drug.     

Triterpenoid Glycosides from the Roots of Patrinia scabiosaefolia

Four saponins were isolated from the roots of PATRINIA SCABIOSAEFOLIA (Valerianaceae) and identified as 3- O-alpha- L-arabinopyranosylhederagenin 28- O-beta- D-glucopyranosyl(1-->6)-beta- D-glucopyranoside ( 2) and its 2'-acetate ( 1) and 3- O-beta- D-glucopyranosyl(1-->3)-alpha- L-rhamnopyranosyl(1-->2)-alpha- L-arabinopyranosyloleanolic acid ( 3) and its 28- O-beta D-glucopyranosyl(1-->6)-beta- D-glucopyranoside ( 4).     

New Flavonoids from Boldoa purpurascens Cav

Phytochemical analysis of the leaves of BOLDOA PURPURASCENS Cav. led to isolation of four flavone glycosides, three of which are new compounds. Their structures have been determined by mass spectrometry and by 1 D and 2 D NMR analysis, i. e., 4',5-dihydroxy-6,7-methylenedioxyflavonol 3- O-alpha- L-rhamnopyranosyl-(1-->2)-beta- D-xylopyranoside ( 1), 4',5-dihydroxy-6,7-methylenedioxyflavonol 3- O-beta- D-xylopyranoside ( 2), and 4',5-dihydroxy-6,7-methylenedioxyflavonol 3- O-alpha- L-rhamnopyranosyl-(1-->2)-beta- D-glucopyranoside ( 3). The known compound was 4',5-dihydroxy-6,7-methylenedioxyflavonol 3- O-beta- D-glucopyranoside ( 4). The aglycone 4',5-dihydroxy-6,7-methylenedioxyflavonol is known as gomphrenol. Compounds 1 and 2 failed to show antifungal activity when tested against three different strains of fungi, i. e., FUSARIUM CULMORUM, BOTRYTIS CINEREA, and ASPERGILLUS FLAVUS.     

Microbial metabolism of pseudoprotodioscin

Microbial transformation of the furostanol saponin pseudoprotodioscin ( 1) using Aspergillus fumigatus resulted in the isolation of two new steroidal metabolites, 3- O-[bis- alpha- L-rhamnopyranosyl-(1-->2 and 1-->4)- beta- D-glucopyranosyl]-22 R,25 R-spirost-5-ene-3 beta,20 alpha-diol ( 2) and 3- O-[bis- alpha- L-rhamnopyranosyl-(1-->2 and 1-->4)- beta- D-glucopyranosyl]-25 R-furost-5-ene-3 beta,22 alpha,26-triol ( 3), in addition to the previously reported steroidal saponins: dioscin ( 4) and progenin II ( 5). The structure elucidation of these metabolites was based primarily on 1D and 2D NMR analyses. Metabolites 2 - 5 showed significant cytotoxicity against cancer cell lines A375, L929, and HeLa with IC (50) values ranging from 1.18 microM to 17.88 microM.     

Phenylpropane glycosides from Juniperus phoenicea

Juniperoside, a new 9-O[beta- D-glucopyranoside]-3,4,5-trimethoxycinnamyl alcohol has been isolated along with the 9- O-[alpha-L-arabinofuranosyl-(1-->6)-beta- D-glucopyranoside]cinnamyl alcohol (rosarin) and coumarin 7- O-beta- D-glucopyranoside (skimmin) from the acetone extract of the aerial parts of Juniperus phoenicea L. The structure elucidation of these natural products was achieved mainly by mass and NMR spectroscopy.     

Triterpenoid Saponins from Primula denticulata

Two triterpene glycosides denticin ( 1) and denticulatin ( 2) have been isolated from the whole plant of PRIMULA DENTICULATA Sm. and their structures were established by spectral and chemical studies as 3beta-{ O-beta- D-glucopyranosyl-(1-->4)-[ O-beta- D-xylopyranosyl-(1-->2)]- O-(beta- D-glucopyranosyl-(1-->4)-[ O-beta- D-glucopyranosyl-(1-->2)]-alpha- L-arabinopyranosyloxy}-16alpha-hydroxy-13beta, 28-epoxyolean-30-al and 3beta-{ O-beta- D-glucopyranosyl-(1-->2)- O-beta- D-glucopyranosyl-(1-->4)-[ O-beta- D-xylopyranosyl-(1-->2)]- O-beta- D-glucopyranosyl-(1-->4)-[ O-beta- D-glucopyranosyl-(1-->2)]-alpha-L-arabinopyranosyloxy}-16alpha-hydroxy-13beta,28-epoxyolean-30-al, respectively.     

太白楤木根皮的齐墩果酸皂甙

从太白楤木(Aralia taibaiensis Z.Z.Wang et H.C.Zheng)根皮中首次分离到5个齐墩果酸皂甙,根据理化性质和光谱数据,分别鉴定为木皂甙A(1),3-O-[α-L-呋喃阿拉伯糖(1→4)-β-D-吡喃葡萄糖醛酸丁酯]-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(2),3-O-[α-L-呋喃阿拉伯糖(1→4)-β-D-吡喃葡萄糖醛酸乙酯]-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(3),屏边三七甙R₂(4)和3-O-｛β-D-吡喃葡萄糖(1→3)[α-L-呋喃阿拉伯糖(1→4)]-β-D-吡喃葡萄糖醛酸乙酯｝-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(5)。2,3和5为新化合物,分别命名为太白楤木皂甙I(taibaienoside I)、太白楤木皂甙II(taibaienoside II)和太白楤木皂甙III(taibaienoside III)。     

Cussonosides A and B, two Triterpene-saponins from Cussonia barteri.

Two major saponins have been isolated from the stem bark of CUSSONIA BARTERI Seem (Araliaceae). Structural elucidation employing mainly (1)H- and (13)C-NMR, FAB-MS and GC-MS spectroscopic methods revealed a new hederagenin 28- O-[alpha- L-rhamnopyranosyl (1 --> 4)-beta- D-glucopyranosyl (1 --> 6)]-beta- D-glucopyranosyl ester (Cussonoside A), and the corresponding oleanolic acid analogue (Cussonoside B). Cussonoside A exhibits a pronounced sedative effect.     

Anti-complement activity of norlignans and terpenes from the stem bark of Styrax japonica

A new norlignan, styraxlignolide A (1), and two new terpenes, styraxosides A (2) and B (3), were isolated from the MeOH-soluble fraction of Styrax japonica Sieb. et Zucc. (Styracaceae) stem bark, together with two known compounds, egonol (4) and masutakeside I (5). The new compounds were determined as 5-(3'-hydroxypropyl)-7-methoxy-2-(3',4'-dimethoxyphenyl)-benzofuran 3'- O-[beta-D-xylopyranoside-(1-->6)-beta- D-glucopyranoside] (1), 3beta,7beta-dihydroxy-4alpha,4beta,8beta,10beta,14alpha-pentamethyl-5alpha-gon-16-en-2-one 3-O-[beta-D-glucopyranoside-(1-->2)-beta-D-glucopyranoside] (2), and 3beta,17beta-dihydroxy-28-norolean-12-en-16-one 3-O-[alpha-L-rhamopyranoside-(1-->2)-beta-D-glucuronopyranoside] (3) by spectroscopic means including 2D-NMR. The five compounds were tested in vitro for anti-complement activity against the complement system. Compounds 1, 3, 4, and 5 displayed inhibitory activity in the anti-complement assay, with IC50 values of 123, 65, 33, and 166 microM, respectively. Compound 1a and camellenodiol (3a), obtained from acid hydrolysis of 1 and 3, respectively, did not affect the hemolytic activity of human serum against sensitized erythrocytes. This shows that a sugar seems to play a role of enhancing significantly anti-complement activity.     

Guaiacin A and B from the Leaves of Guaiacum officinale

Guaiacin A and B, two new saponins, have been isolated from the leaves of G. OFFICINALE and were characterised on the basis of (13)C-NMR and FAD mass spectroscopy as 3- O-(beta- D-glucopyranosyl (1-->3)-alpha- L-arabinopyranosyl]-30-nor-olean-12,20(29)-dien-28- O-beta- D-glucopyranosyl ester ( 1) and 3- O-[ D-glucopyranosyl-(1-->3)-alpha- L-arabinopyranosyl] oleanolic acid-28- O-beta- D-glucopyranosyl ester ( 2).     

Constituents with DNA topoisomerases I and II inhibitory activity and cytotoxicity from the roots of Rubia cordifolia

Activity-directed isolation of the ethyl acetate fraction from the roots of Rubia cordifolia resulted in the identification of a new anthraquinone, 1,3,6-trihydroxy-2-hydroxymethyl-9,10-anthraquinone-3- O- α- L-rhamnopyranosyl-(1?→?2)- β-D-(6'-O-acetyl)-glucopyranoside (1), two new dihydronaphtoquinones, 1,4-dihydroxy-2-carbomethoxy-3-prenylnaphthalene-1-O- β-D-glucopyranoside (2) and mollugin-1-O- β- D-glucopyranoside (3), and a new monoterpenoid, 3 R,3a S,4 R,6a R-3,4,6-tris(hydroxymethyl)-3,3a,4,6a-tetrahydro-2 H-cyclopenta[ B]furan-2-one (4), together with nine known compounds (5-13). The structures of these compounds were elucidated on the basis of spectroscopic evidence. In addition, their DNA topoisomerases I and II inhibitory activity and cytotoxicity were measured.     

Inhibiting activities of the secondary metabolites of Phlomis brunneogaleata against parasitic protozoa and plasmodial enoyl-ACP Reductase, a crucial enzyme in fatty acid biosynthesis

Anti-plasmodial activity-guided fractionation of Phlomis brunneogaleata (Lamiaceae) led to the isolation of two new metabolites, the iridoid glycoside, brunneogaleatoside and a new pyrrolidinium derivative (2 S,4 R)-2-carboxy-4-( E)- p-coumaroyloxy-1,1-dimethylpyrrolidinium inner salt [(2 S,4 R)-1,1-dimethyl-4-( E)- p-coumaroyloxyproline inner salt]. Moreover, a known iridoid glycoside, ipolamiide, six known phenylethanoid glycosides, verbascoside, isoverbascoside, forsythoside B, echinacoside, glucopyranosyl-(1-->G (i)-6)-martynoside and integrifolioside B, two flavone glycosides, luteolin 7- O-beta- D-glucopyranoside ( 10) and chrysoeriol 7- O-beta- D-glucopyranoside ( 11), a lignan glycoside liriodendrin, an acetophenone glycoside 4-hydroxyacetophenone 4- O-(6'- O-beta- D-apiofuranosyl)-beta- D-glucopyranoside and three caffeic acid esters, chlorogenic acid, 3-O-caffeoylquinic acid methyl ester and 5- O-caffeoylshikimic acid were isolated. The structures of the pure compounds were elucidated by means of spectroscopic methods (UV, IR, MS, 1D and 2D NMR, [alpha] (D)) and X-ray crystallography. Compounds 10 and 11 were determined to be the major anti-malarial principles of the crude extract (IC (50) values of 2.4 and 5.9 micrograms/mL, respectively). They also exhibited significant leishmanicidal activity (IC (50) = 1.1 and 4.1 micrograms/mL, respectively). The inhibitory potential of the pure metabolites against plasmodial enoyl-ACP reductase (FabI), which is the key regulator of type II fatty acid synthases (FAS-II) in P. falciparum, was also assessed. Compound 10 showed promising FabI inhibiting effect (IC (50) = 10 micrograms/mL) and appears to be the first anti-malarial natural product targeting FabI of P. falciparum.