Isolation and characterization of a new flavone diglucoside from <Emphasis Type="Italic">Salix denticulata</Emphasis>

A new flavone diglucoside named 7,3′-dihydroxy-4′-methoxyflavone-5-O-β-D-glucopyranosyl (6″ → 1‴)-β-D-glucopyranoside (1), along with four known flavonoids, luteolin (2), isoquercetin (3), catechin (4), and diosmetin (5), has been isolated and characterized from Salix denticulata. The structure of the new flavone diglucoside was characterized by means of high field 1D and 2D NMR and MS spectral analysis.     

Identification of a new flavone glycoside from <Emphasis Type="Italic">Codonopsis nervosa</Emphasis>

A new flavone glycoside, luteolin 7-O-[(6″′-caffeoyl)-β-D-glucopyranosyl-(1 → 6)]-β-D-glucopyranoside (1), was isolated from Codonopsis nervosa, along with three other known compounds, luteolin 7-O-β-D-glucopyranoside (2), luteolin 7-O-gentiobioside (3), and tangshenoside VI (4). Their structures were determined on the basis of 1D and 2D NMR, IR, and HR-ESI-MS.     

A novel compound from <Emphasis Type="Italic">Flos carthami</Emphasis> and its bioactivity

A novel compound, 4-{1′-hydroxy-1′-mercapto-1′-[1′′-2′′(N→O)-isoquinolyl]}yl-1-benzoic acid (1), together with six known compounds, 6-hydroxykaempferol-3-O-β-D-glucopyranoside (2), rutin (3), quercetin-3-O-β-D-glucopyranoside (4), kaempferol-3-O-β-D-glucopyranoside (5), cartormin (6), hydroxysafflor yellow A (7), were isolated by chromatography from the n-BuOH fraction of 50% ethanol extraction of Flos carthami. Their structures were elucidated on the basis of spectral analysis and comparison with published data. Among them, compound 1 was shown to possess a weak protective effect against cerebral ischemic damage in rats. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 339–341, May–June, 2009.     

Separation and identification of steroidal compounds with cytotoxic activity against human gastric cancer cell lines <Emphasis Type="Italic">in vitro</Emphasis> from the rhizomes of <Emphasis Type="Italic">Paris polyphylla</Emphasis> var. <Emphasis Type="Italic">chinensis</Emphasis>

A novel steroidal saponin, along with 12 known steroidal compounds, was isolated from the rhizomes of Paris polyphylla var. chinensis. Spectral data, including two-dimensional NMR, showed that the structure of the novel saponin was 3β,21-dihydroxypregnane-5-en-20S-(22,16)-lactone-1-O-α-L-rhamnopyranosyl(1→2)-[β-D-xylopyranosyl(1→3)]-β-D-glucopyranoside. The isolated steroidal compounds were evaluated for their cytotoxic activity on human gastric cancer cell line HepG₂, SGC7901, BxPC3. Diosgenin-3-O-α-L-rhamnopyranosyl(1→2)[α-L-rabinofuranosyl(1→4)]-β-D-glucopyranoside exhibited the most potent cytotoxic activity among the isolated steroids. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 556–560, November–December, 2007.     

Two new myricetin glycosides from pine needles of <Emphasis Type="Italic">Cedrus deodara</Emphasis>

Two new myricetin glycosides, myricetin-3-O-(6″-O-E-p-coumaroyl)-α-D-glucocopyranoside (1) and 3′,5′-di-O-methylmyricetin-3-O-(6″-O-acetyl)-α-D-glucopyranoside (2), and three known flavonoids, myricetin (3), cedrin (4), and 2R,3R-dihydromyricetin (5), were isolated from the pine needles of Cedrus deodara. Their structures were elucidated on the basis of extensive spectroscopic analysis and chemical evidence.     

A new cerebrogalactoside from <Emphasis Type="Italic">Juglans mandshurica</Emphasis>

A new cerebrogalactoside, Juglans cerebroside A (1), together with five known compounds, quercetin-3-O-β-D-galactopyranoside (2), myricetin-3-O-β-D-galactopyranoside (3), 2″E-quercetin-3-O-β-D-(6″″-O-[3″(4′″-hydroxyphenyl) propylene acyl]) glucopyranoside (4), gallic acid (5), and 2-methyl-1-hexadecanol (6) were isolated from the leaves of Juglans mandshurica Maxim. The structures of these compounds were determined by 1D, 2D NMR, and MS techniques.     

Synthesis of 6α-methyl-16α,17α-cyclohexano-19-norprogesterone from a 19-methyl-6-desmethyl precursor

After prolonged refluxing of 19-tosyloxy-16α,17α-cyclohexanopregn-5-en-3β-ol-20-one (3) with NaI in 2-propanol, the initially formed 19-iodo derivative (4) undergoes supraface migration of the CH₂I group from the C(10) atom to the C(6) atom, probably through involvement of a homoallyl cation. The resulting 6β-iodomethyl-16α,17α-cyclohexano-19-norpregn-5(10)-en-3β-ol (5) was transformed in three steps into 6α-methyl-16α,17α-cyclohexano-19-norprogesterone (6α-methyl-19-nor-D′ ₆-pentarane,8). The transformation of compound5 into the target product8 also gave a side product, a pentarane with aromatic ringA (10), which was isolated and characterized by spectroscopic methods. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1688–1691, September, 1997.     

Synthesis of 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (chikusetsusaponin-LT8), a glycoside from Panax japonicus

A method for preparative production of 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (1), a glycoside from Panax japonicus, chikusetsusaponin-LT₈ was developed. Chemical transformation of betulafolientriol, a component of Betula leaves extract, produced the 12-keto-20S-protopanaxadiol (3β,20S-dihydroxydammar-24-en-12-one) (2), exhaustive glycosylation of which by 2,3,4,6-tetra-O-acetyl-α-D-glucopyranosylbromide (3) under Koenigs—Knorr reaction conditions with subsequent removal of protecting groups formed 3β,20S-dihydroxydammar-24-en-12-one 3,20-di-O-β-D-glucopyranoside (1). The principal glycosylation product was 3β,20S-dihydroxydammar-24-en-12-one 3-O-β-D-glucopyranoside if equimolar amounts of (2) and (3) were used. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 44–48, January–February, 2006.     

Furostane-Type Steroidal Saponin from <Emphasis Type="Italic">Digitalis ciliata</Emphasis>

A new furostane-type steroidal glycoside and derivative of tigogenin (1) was isolated from aqueous wastes from production of the cardiac drug acetyldigitoxin from leaves of Digitalis ciliata Trautv. (Scrophulariaceae) and characterized. The structure of the glycoside was established using physical constants, chemical transformations, and spectral data as 3-O-β-D-glucopyranosyl-(1→3) [β-D-fucopyranosyl-(1→2)-β-D-glucopyranosyl-(1→4)-β-D-galactopyranosyl-(25R)-5α-furostan-3β,22α,26-triol-26-O-β-D-glucopyranoside.     

Two new triterpenoid saponins from <Emphasis Type="Italic">Lysimachia davurica</Emphasis>

Two new saponins were isolated from an ethanol extract of the whole plants of Lysimachia davuria. The new saponins were respectively characterized as 3-O-{β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-L-arabinopyranosyl}-3β,28-dihydroxyolean-12-en-30-oic acid-O-[β-D-xylopyranosyl-(1→2)-β-D-glucopyranosyl]-ester (1) and 3-O-{ β-D-glucopyranosyl-(1→2)-[β-D-glucopyranosyl-(1→4)]-α-L-arabinopyranosyl}-3β,28-dihydroxyolean-12-en-30-oic acid-O-β-D-glucopyranosyl-ester (2). Their structures were determined by 1D, 2D NMR and MS techniques. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 466–468, September–October, 2007.     

A novel chromone-substituted trimeric dihydroflavonol from <Emphasis Type="Italic">Anogeissus pendula</Emphasis>

A new chromone-substituted dihydrotriflavonol, (2S,3S)[6-{(3S) 3″,5″-dihydroxy-6″-methoxydihydrochromone}5,3′,4′,5′-tetrahydroxy-7-methoxy-3-O-8-dihydroflavone]₂ 3-O-8[6-{(3S) 3″,5″-dihydroxy-6″methoxydihydrochromone}3,5,3′,4′,5′-pentahydroxy-7-methoxydihydroflavonol] was isolated from the leaves of Anogeissus pendula. The structure was determined by UV, ¹H NMR, ¹³C NMR, HMBC, and CD data.     

Isoflavone glycosides from the bark of Amorpha fruticosa

Four known isoflavone glucosides have been isolated from the bark of Amorpha fruticosa, which is a traditional remedy plant, for the first time. They were elucidated as 3′-hydroxy-4′-methoxyisoflavone-7-O-β-D-glucopyranoside (1), 4′,6-dimethoxyisoflavone-7-O-β-D-glucopyranoside (2), 4′-methoxyisoflavone-7-O-β-D-glucopyranoside (3), and 3′,5-dihydroxy-4′-methoxyisoflavone-7-O-β-D-glucopyranoside (4), based on the UV, FT-IR, EIMS, FABMS, HREIMS, and NMR (¹H and ¹³C, DEPT, COSY, NOESY, HMQC, and HMBC) data. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 336–338, July–August, 2006.     

Ellagic acid derivatives from the stem bark of <Emphasis Type="Italic">Dipentodon sinicus</Emphasis>

Ellagic acid derivatives were isolated from Dipentodon sinicus and their structures were identified as 3,3′,4′-tri-O-methylellagic acid (1), 3,3′-di-O-methylellagic acid (2), 4,4′-di-O-methylellagic acid (3), 3,3′-di-O-methylellagic acid-4′-O-α-L-rhamnopyranoside (4), 3,3′,4′-tri-O-methylellagic acid-4′-O-β-D-glucopyranoside (5), 3,3′-di-O-methylellagic acid-4′-O-β-D-glucopyranoside (6), and ellagic acid (7). All the compounds were isolated for the first time from the title plant. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 106–107, March–April, 2007.     

New glycosidic and other constituents from hulls of <Emphasis Type="Italic">Oryza sativa</Emphasis>

Three new compounds, 4-hydroxymethylene-7-(9,9,13-trimethylcyclohexyl)-heptanyl-3′,7′,7′-trimethylcyclohexa-2′,4′-dien-1′-oate (1), 1-(n-hexadec-7-enoxy)-6-(n-octadecanoxy)-β-D-glucopyranoside (2), and (Z)-12-hydroxy-9-octadecenoic acid-12-β-D-glucopyranoside (3), along with the known compound hexacosanoic acid (4), were isolated and identified from the rice hulls of Oryza sativa. Their structures were elucidated by 1D and 2D NMR spectroscopic techniques (¹H-¹H COSY, ¹H-¹³C HETCOR, DEPT) aided by EIMS, FABMS, HRFABMS, and IR spectra. Published in Khimiya Prirodnykh Soedinenii, No. 4, pp. 344–347, July–August, 2007.     

Triterpene Glycosides from <Emphasis Type="Italic">Cussonia paniculata</Emphasis>. II. Acetylated Glycosides from Leaves

Structures of 13 new acetylated triterpene glycosides from leaves of Cussonia paniculata (Araliaceae) were established as 28-O-(2-O-acetyl- and 3-O-acetyl-α-L-rhamnopyranosyl)-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β -D-glucopyranosides of 23-hydroxybetulinic acid (1a and 1b) and hederagenin (2a and 2b), 3-O-α-L-arabinopyranosyl-28-O-(2-O-acetyl- and 3-O-acetyl-a-L-rhamnopyranosyl)-(1→ 4)-O-β-D-glucopyranosyl-(1→6)-O-β-D-glycopyranosides of oleanic (3a and 3b) and ursolic (3c and 3d) acids, 3-O-α-L-arabinopyranosyl-28-O-(4-O-acetyl-, 2-O-acetyl-, and 3-O-acetyl-α-L-rhamnopyranosyl)-(1→4)-O-β-D-glucopyranosyl-(1→ 6)-O-β-D-glucopyranosides of hederagenin (4, d5a and 5b), and 3-O-β-D-glucopyranosyl-(1→2)-O-α-L-arabinopyranosyl-28-O-(2-O-acetyl- and 3-O-acetyl-α-L-rhamnopyranosyl)-(1→4)-O-β-D-glucopyranosyl-(1→6)-O-β-D- glucopyranosides of oleanic acid (6a and 6b). The structures of the compounds were established using chemical methods and NMR spectroscopy. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 351–356, July–August, 2005.     

Cytotoxic effect of some pentacyclic triterpenes and hemisynthetic derivatives of stigmasterol

Two different oxidation reactions (PCC and KMnO₄) of stigmasterol gave three products, stigmasta-4,22-dien-3-one (1a), stigmasta-4,22-diene-3,6-dione (1b), and 3-O-acetyl-5β,6β-epoxystigmast-22-ene-3-ol (1c). The cytotoxic activities of hemisynthetic compounds, stigmasterol, and four pentacyclic triterpens 2–5 previously isolated from cultivated and wild Triumfetta cordifolia and identified were investigated against human fibrosarcoma cell line (HT1080). Most of the drugs showed moderate cytotoxic activity. It was also notice that the triterpene skeleton had a range of number of OH functions in which activity was observed. Spectroscopic analyses (¹H and ¹³ C NMR) and mass were used to elucidate the structure of hemisynthetic compounds.     

Steroids from the marine bryozoan <Emphasis Type="Italic">Bugula neritina</Emphasis>

One new compound, 3β-hydroxy-25-methoxy-(23E)-cholesta-5,23-diene (1), together with five known steroids, cholesteryl myristate (2), cholest-4-en-3-one (3), cholesterol (4), 3β,5α,9α-trihydroxy-(22E,24R)-ergosta7,22-dien-6-one (5), and 3β,5α,6β-trihydroxy-(22E,24R)-ergosta-7,22-diene (6), were isolated and identified from the marine bryozoan Bugula neritina.     

Furostanol Glycosides from leaves of the Chinese plant <Emphasis Type="Italic">Tribulus terrestris</Emphasis>

The structures of five furostanol glycosides (1–5), of which the 26-O-β-D-glucopyranosyl-(25S),5α-furost20(22)-en-12-one-2α,3β,26-triol-3-O-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside (1) was new, from the leaves of Tribulus terrestris L. were established using chemical and NMR spectroscopic methods.     

Phenolic constituents from the stems of <Emphasis Type="Italic">Acanthopanax senticosus</Emphasis>

A new phenolic glycoside was isolated from the stems of Acanthopanax senticosus together with sixteen known compounds. The structure of the new compound was determined to be 2,6-dimethoxy-4-[(1E)-3,3-dimethoxy-1-propenyl]phenyl β-D-glucopyranoside (1) by means of physical, chemical, and spectroscopic methods. Of the known compounds, salvadoraside (7), (7R,8S)-dihydrodehydrodiconiferyl alcohol 4,9′-di-O-β-D-glucopyranoside (8), 3-(4-O-β-D-glucopyranosylferuloyl)quinic acid (15), rel-5-(1R,5S-dimethyl-3R,4R,8S-trihydroxy-7-oxa-6-oxobicyclo[3,2,1]oct-8-yl)-3-methyl-2Z,4E-pentadienoic acid (16), and lycoperodine-l (17) were first reported from the title plant. The inhibitory activities of the isolated compounds against α-glucosidase from rat intestine were also reported.     

A new furostanol glycoside with fatty acid synthase inhibitory activity from <Emphasis Type="Italic">Ophiopogon japonicusa</Emphasis>

A new furostanol glycoside, named ophiopogonin J (1), was isolated from the fibrous root of Ophiopogon japonicas. The structure of the compound was established as (25R)-26-[(O-β-D-glucopyranosyl-(1 → 2)-β-D-glucopyranosyl)]-20α -hydroxyfurost-5, 22-diene-3-O-α-L-rhamnopyranosyl-(1 → 2)-[β-D-xylopyranosyl(1 → 4)]-β-D-glucopyranoside on the basis of spectroscopic methods, including HR-ESI-MS and 1D and 2D NMR experiments.