Cardiac glycosides from Strophanthus kombe

Twelve cardiac glycosides and aglycons were isolated from Strophanthus kombe seeds. Of these, eight were identified as cymarin, K-strophanthin-β, K-strophanthoside, periplocymarin, 17α-strophadogenin, erysimin (= helveticoside), erysimoside, and neoglucoerysimoside. Four glycosides, preliminarily designated Sk-x, Sk-y, Sk-z, and Sk-20, were new. Their chemical structures were established as 3β-O-β-D-glucopyranosyl-5β,14β,16β-trihydroxy-19-oxo-17α-card-20(22)enolide (17α-strophadogenin-3-O-β-D-glucoside), 3β-O-β-D-cymaropyranosyl-5β,14β,16β-trihydroxy-19-oxo-17α-card-20(22)enolide (17α-strophadogenin-3-O-β-D-cymaroside), 3β-O-β-D-cymaropyranosyl-4′-O-β-D-glucopyranosyl-6″-O-β-D-glucopyranosyl-5β, 14β,16β-trihydroxy-19-oxo-17α-card-20(22)enolide (17α-strophadogenin-3-O-strophanthotrioside), and 3-O-β-D-digitoxopyranosyl-4′-O-β-D-glucopyranosyl-6″-O-β-D-glucopyranosyl-5β,14β, 19-trihydroxy-card-20(22)enolide (strophanthidol-3-O-gentiobiosyldigitoxoside), respectively. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 156–159, March–April, 2006.     

New polyhydroxysteroids and steroid glycosides from the far east starfishCeramaster patagonicus

Two new polyhydroxysteroids and five new glycosides were isolated from the starfishCeramaster patagonicus and their structures were elucidated: 5α-cholestane-3β,6α,15β,16β,26-pentol, (22E)-5α-cholest-22-ene-3β,6α,8,15α,24-pentol, (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β,4β, 6α,8,15β,16β,28-heptol (ceramasteroside C₁), (22E)-28-O-[O-(2,4-di-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β, 6α,8,15β,16β,28-hexol (ceramasteroside C₂), (22E)-28-O-[O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-hydroxymethyl-5α-cholest-22-ene-3β,6α,8,15β,16β 28-hexol (eramasteroside C₃), (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-galactofuranosyl]-24-methyl-5α-cholest-22-ene-3β,4β,6α,8, 15β, 26-hexol (ceramasteroside C₄), and (22E)-28-O-[O-(2-O-methyl-β-d-xylopyranosyl)-(1→2)-β-d-xylopyranosyl]-5α-cholest-22-ene-3β,6α,8,15β,24-pentol (ceramasteroside C₅)). Three known polyhydroxysteroids (24-methylene-5α-cholestane-3β,6α,8,15β,16β,26-hexol, 5α-cholestane-3β,6α,8,15β,16β,26-hexol, and 5α-cholestane-3β,6β,15α,16β,26-pentol) were also isolated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 190–195, January, 1997.     

Study on the Association Phenomenon of Cyclodextrin to Porphyrin J-aggregates by NMR Spectroscopy

The nuclear magnetic resonance (NMR) spectroscopy demonstrated that the inclusion complexes of meso-tetrakis- (p-sulfonatophenyl) porphyrin (TPPS) with β-, Hydroxypropyl-β- and Methyl-β-cyclodextrin (β-, HP-β- and Me-β-CD) are formed, which resulted in the dissociation of TPPS J-aggregates efficiently under certain acidity. There are no significant differences in binding affinities and basic complexation mechanisms between TPPS and β-cyclodextrin (β-CD) or hydroxypropyl-β-cyclodextrin (HP-β-CD), i.e. porphyrin is included through the wide side of the cavity of β-CD or HP-β-CD. Alternatively, porphyrin is included through the narrow side of the Me-β-CD cavity.     

Polar steroidal compounds from the Far-Eastern starfish <Emphasis Type="Italic">Lethasterias fusca</Emphasis>

Nine steroidal compounds including three new steroidal glycosides, viz., sodium (24S)-3,24-di-O-(β-D-xylopyranosyl)-5α-cholestane-3β,6β,8,15α,24-pentol 15-sulfate (fuscaside A), (24S)-3,24-di-O-(β-D-xylopyranosyl)-5α-cholestane-3β,6β,8,15α,24-pentol (fuscaside B), and (22E,24R)-24-O-(β-D-xylopyranosyl)-5α-cholest-22-ene-3β,6α,8,15β,24-pentol (desulfated minutoside A); three previously known glycosides, viz., distolasterosides D₁ and D₂ and pycno-podioside A; two previously known polyhydroxysteroids, viz., 5α-cholestane-3β,6α,8,15β,16β,26-hexaol and 5α-cholestan-3β,4β,6α,7⇇8,15β,16β,26-octol; and the known sodium 24,25-dihydro-marthasterone 3-sulfate were isolated from the Far-Eastern starfish Lethasterias fusca. The structures of these compounds were elucidated by NMR spectroscopy and mass spectrometry. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 196–200, January, 2008.     

A new hexahydroxysteroid from the Far Eastern starfishLuidiaster dawsoni

A new polyhydroxysteroid was isolated from the starfishLuidiaster dawsoni; the structure of the product was established as (24S,25R)-24-methylcholestane-3β, 5α, 6β, 15α, 16β, 26-hexaol. A mixture of methyl-α- and β-d-glucopyranosides was also isolated from the extract of this starfish. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2088–2090, October, 1998.     

Reactions of functionalized alkyl halides withN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxide salts

Some characteristic features of reactions ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxide salts with various α- and β-functionalized alkyl halides were established. Some α-and β-functionalizedN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides and e ethylenebis[N-(β-hydroxyalkyl)-N′-oxydiazeneN-oxides] were synthesized for the first time. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 123–129, January, 1999.     

Two new coumarin biosides from Angelica dahurica

Two new coumarin biosides, tert-O-β-D-apiofuranosyl-(1→6)-O-β-D-glucopyranosyl-byakangelicin (1) and 2′-O-β-D-apiofuranosyl-(1→6)-β-D-glucopyranosyl-peucedanol (2), were isolated from the fresh roots of Angelica dahurica. The structures of the new compounds were elucidated on the basis of spectral analysis. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 561–563, November–December, 2008.     

A new stilbene glycoside from the <Emphasis Type="Italic">n</Emphasis>-butanol fraction of <Emphasis Type="Italic">Veratrum dahuricum</Emphasis>

A new stilbene glycoside, 5-methylresveratrol-3,4′-O-β-D-diglucopyranoside (1), was isolated from the n-butanol fraction of the rhizomes of Veratrum dahuricum, together with five known stilbenoids: resveratrol-3-O-β-D-glycoside (2), 4′-methylresveratrol-3-O-β-D-glycoside (3), oxyresveratrol-4′-O-β-D-glycoside (4), oxyresveratrol-3-O-β-D-glycoside (5), and oxyresveratrol-3,4′-O-β-D-diglycoside (6), and found for the first time in the investigated plant. The structures of six isolates were identified on the basis of 1D and 2D NMR data. Compounds 1–6 showed platelet aggregation inhibition, and compound 1 had an IC₅₀ value of 383.6 μM against platelet aggregation induced by AA. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 279–282, May–June, 2009.     

Triterpene glycosides from Kalopanax septemlobum. VI. Glycosides from leaves of Kalopanax septemlobum var. typicum introduced to crimea

Thirteen known glycosides of hederagenin and oleanolic acid and the three new triterpene glycosides of oleanolic acid-28-O-α-L-rhamnopyranosyl-(1→4)-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester 3-O-β-D-glucopyranosyl-(1→4)-O-β-D-xylopyranosyl-(1→ 3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside of oleanolic acid and the 28-O-α-L-rhamnopyranosyl-(1→4)-O-6-O-acetyl-β-D-glucopyranosyl-(1→ 6)-O-β-D-glucopyranosyl esters 3-O-β-D-xylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside of oleanolic acid and 3-O-β-D-glucopyranosyl-(1→4)-O-β-Dxylopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→ 2)-O-α-L-arabinopyranoside of oleanolic acid were isolated from leaves of Kalopanax septemlobum var. typicum introduced to Crimea. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 40–43, January–February, 2006.     

Asterosaponin P2 from the Far-Eastern starfishpatiria (asterina) pectinifera

A new polyhydroxylated steroidal glycoside, asterosaponin P₂, was isolated from the Far-Eastern starfishPatiria (Asterina) pectinifera. The glycoside was identified as the 24R)-29-O-[2-O-sulfo-α-L-arabinofuranosyl]-24-ethyl-5α-cholestane-3β, 6α,8β,15α,16β,29-hexol Na salt. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1818–1820, October. 2000     

Study on the Inclusion Compounds of Eugenol with α-, β-, γ- and Heptakis (2,6-di-O-methyl)-β-cyclodextrins

Several host–guest inclusion compounds of eugenol as a guest molecule and cyclodextrins (α-,β-,γ-CD) and heptakis (2,6-di-O-methyl)-β-cyclodextrin (DMβ-CD) as hosts were investigated in the solid state and in aqueous solution. The one-to-one solid inclusion compounds of eugenol and β-CD or γ-CD were prepared, but those of eugenol with α- or DMβ-CD were not obtained under the same condition. However, the UV-visible absorption spectroscopy data indicated that the liquid guest could form a 1:1 inclusion compound with all four hosts respectively in aqueous solution. The two solid inclusion compounds were characterized by powder X-ray diffraction (XRD), infrared spectroscopy (IR), thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR). The association constants (K), calculated from the modified Benesi–Hidebrand equation, of eugenol with α-, β-, γ- and DMβ-CD is 4.95 × 10⁴, 3.96 × 10⁵, 1.47 × 10⁵ and 9.33 × 10⁴ mol⁻¹ dm³, respectively.     

Glutinane triterpenes from the stem bark of <Emphasis Type="Italic">Euonymus hamiltonianus</Emphasis>

Three new glutinane-type triterpenes, 19α-glutin-5-en-19-ol (1), 2β,15α,21β-glutin-11-ene-2,15,21-triol (2), and 2β,19α-glutin-7,21-diene-2,19-diol (3), were isolated from the stem bark of Euonymus hamiltonianus. Their structures were determined by 1D and 2D NMR along with MS and IR. Published in Khimiya Prirodnykh Soedinenii, No. 3, pp. 321–323, May–June, 2009.     

Gangliosides from the starfishEvasterias echinosoma: identification of a disialoganglioside containing 8-O-methyl-N-acetylneuraminic acid andN-formylgalactosamine

Gangliosides were isolated from the starfishEvasterias echinosoma and their structures were elucidated by chemical and physicochemical methods. Two major gangliosides were found to be disialogangliosides, whose carbohydrate chain is based on the trisaccharide β-N-acylgalactosaminyl-(l→3)-β-galactosyl-(l→4)-β-glucose (acyl is formyl or acetyl), both residue at of 8-O-methyl-N-acetylneuraminic acid being attached to theN-acylgalactosamine residue at positions 3 and 6. The minor components are disialogangliosides with linear carbohydrate chains in which the terminal sialic acid residue is attached to the penultimateN-acetylneuraminic acid residue at positions 4, 8, or 9. The lipid part of the gangliosides consists of sphingenine and unsubstituted fatty acids (mainly, palmitic and stearic acids). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 156–161, January, 2000.     

Gangliosides from the starfishEvasterias echinosoma: identification of a disialoganglioside containing 8-O-methyl-N-acetylneuraminic acid andN-formylgalactosamine

Gangliosides were isolated from the starfishEvasterias echinosoma and their structures were elucidated by chemical and physicochemical methods. Two major gangliosides were found to be disialogangliosides, whose carbohydrate chain is based on the trisaccharide β-N-acylgalactosaminyl-(l→3)-β-galactosyl-(l→4)-β-glucose (acyl is formyl or acetyl), both residue at of 8-O-methyl-N-acetylneuraminic acid being attached to theN-acylgalactosamine residue at positions 3 and 6. The minor components are disialogangliosides with linear carbohydrate chains in which the terminal sialic acid residue is attached to the penultimateN-acetylneuraminic acid residue at positions 4, 8, or 9. The lipid part of the gangliosides consists of sphingenine and unsubstituted fatty acids (mainly, palmitic and stearic acids). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 156–161, January, 2000.     

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.     

Separation and Determination of Eremophilenolides from Ligulariopsis shichuana by Capillary Zone Electrophoresis

A new method of capillary zone electrophoresis (CZE) was established by simultaneous assay of four eremophilenolides, 3β-acetoxy-9β-angeloyloxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (1), 3β-senecioyloxy -1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (2), 6α-hydroxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (3) and 3β-acetoxy- 6β-angeloyloxy-1β,10β-epoxy-8α-hydroxyeremophil-7(11)-en-8β (12)-olide (4) in the Chinese herbal extract from Ligulariopsis shichuana. The optimum buffer system was 20 mM borate buffer (pH 10.00). Voltage was 25 kV and detection at 214 nm. Regression equations revealed linear relationships (correlation coefficients 0.9986, 0.9990, 0.9992 and 0.9995) between the peak area of each compound and its concentration. The relative standard deviations of migration times and peak areas were <1.35 and 3.94% within 1 day, respectively. The effects of several CE parameters on the resolution were studied systematically. The contents of four eremophilenolides in Ligulariopsis shichuana were successfully determined with satisfactory repeatability and recovery.     

Synthesis of 20S-protopanaxadiol 20-O-β-D-glucopyranoside, a metabolite of Panax ginseng glycosides, and compounds related to it

A preparative semi-synthetic method was developed to prepare 20S-protopanaxadiol 20-O-β-Dglucopyranoside (1), a metabolite of Panax ginseng glycosides. The 20-O-•-D-glucopyranosides of 20S-hydroxydammar-24-en-3,12-dione, 3β,20S-dihydroxydammar-24-en-12-one, and 3β,12α, 20S-trihydroxydammar-24-ene were synthesized for the first time. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 364–369, July–August, 2006.     

Effective synthesis of methyl 3β-amino-3-deoxybetulinate

A practical method for preparing methyl 3β-amino-3-dexoybetulinate that is based on column chromatographic separation of 3α- and 3β-t-butoxycarbonates and subsequent removal of the protecting group using formic acid is proposed. The structure of methyl 3β-N-(t-butoxycarbonyl)-3-deoxybetulinate was established by an x-ray structure analysis. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 488–490, September-October, 2008.     

Synthesis of α-amino-β-keto-esters (β-oxodipeptides)

The synthesis of α-amino-β-keto-esters (β-oxo dipeptides) was studied. Corresponding α-amino-β-ketoesters were prepared from BOC-(L)-Valine and BOC-(L)-isoleucine by coupling with (D,L)-threonine hydrochloride and oxidation with Dess-Martin periodinane (DMP) with a total yield of 48% and 38%, respectively. __________ Translated from Chemistry Online, 2007, 70(10): 793–796 [译自: 化学通报]     

The reaction of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with dihalomethanes

Methylene-bis[N′-oxydiazene-N-(β-hydroxyalkyl)N-oxides] were synthesized by the reaction of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with diahalomethanes. The effect of the nature of the starting reagents and the reaction condtions on the yields of the target compounds was studied. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2266–2269, November, 1998.