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.     

Flavonoid glycosides fromThalictrum squarrosum St. ex Willd. andThalictrum minus L.

Two flavonoid allose diglycosides were found in the terrestrial part ofThalictrum squarrosum St. ex Willd. andT. minus L. (Ranunculaceae). 7,4′-Di-O-β-allopyranosylapigenin was isolated fromT. minus. InT. squarrosum, its monoacetate was also found and characterized as 7-O-(6-O-acetyl-β-allopyranosyl)-4′-O-(β-allopyranosyl)apigenin. The sites of attachment of the carbohydrate residues were determined by HMBC; the location of the acetate group was identified by ROESY. Both substances were isolated from these plants for the first time. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 392–394, February, 1999.     

Polysaccharides of Fabaceae. I. Galactomannan of Astragalus sericeocanus seeds

Galactomannan (yield 3.58% of seed mass) of molecular weight 876 kDa was isolated from seeds of Astragalus sericeocanus Gontsch. (Fabaceae). Its solutions had high viscosity [η], 764.6 mL/g, and optical density [α]_D +65.3°. The polysaccharide consisted of galactose and mannose in molar ratio 1:1.58. The main chain of the galactomannan macromolecule was constructed of 1,4-β-D-mannopyranose units, 63% of which were substituted at C-6 by single α-D-galactopyranose units. ¹³C NMR spectroscopy established that the galactomannan contained units of differently substituted galactose mannobiose units: Man-Man, (Gal)Man-Man, and/or Man-Man(Gal) in addition to (Gal)Man-Man(Gal), the ratio of which was 0.15:0.51:0.34. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 555–557, November–December, 2008.     

New flavonoid oligoside fromAconitum barbatum Pers.

A new flavonoid oligoside,viz. 3-O-[3,4-)di-O-acetyl-β-xylopyranosyl)-α-rhamnopyranosyl]-7-o-(α-rhamnopyranosyl)kaempferol, was isolated from the above-ground part of the plantAconitum barbatum Pers. The product was identified by spectral methods. Published inIzvestiyu Akademii Nauk. Seriya Khimicheskaya. No. 11, pp. 1935–1937, November, 2000.     

Triterpene glycosides from <Emphasis Type="Italic">Astragalus</Emphasis> and their genins. LXXX. Cyclomacroside D,a new bisdesmoside

The structure of the new cycloartane glycoside cyclomacroside D, which was isolated from Astragalus macropus Bunge (Leguminosae) and is 24R-cycloartan-1α,3β,7β,24,25-pentaol 3-O-α-L-rhamnopyranoside–24-O-β-D-xylopyranoside, was proved. Presented at the 7th International Symposium on the Chemistry of Natural Compounds (SCNC, Tashkent, Uzbekistan, October 16–18, 2007). Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 48–50, January–February, 2009.     

A new phytoecdysteroid

A new phytoecdysteroid,viz, 2-deoxy-3-epi-4β, 20-dihydroxycedysone ((20R,22R)-3α,4β 14α,20,22,25-hexahydroxy-5β-cholest-7-en-6-one), named coronatasteronc, was isolated fromSerratula coronata and identified by NMR spectroscopy. Published inIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1954–1955, November, 2000.     

New triterpenoid glycosides fromThalictrum minus L.

Two triterpenoid diglycosides of the cycloartane series were isolated from the terrestrial part ofThalictrum minus L. (Ranunculaceae). Genins of these glycosides are side-chain structural isomers—3-O-β-d-galactopyranosyl-29-O-β-d-glucopyranosyl-9β, 19-cyclo-20(S)-lanost-24(Z)-ene-3β, 16β, 22(S), 26, 29-pentaol and 3-O-β-d-galactopyranosyl-29-O-β-d-glucopyranosyl-9β, 19-cyclo-20(S)-lanost-25-ene-3β, 16β,22(S), 24ζ, 29-pentaol. The structures of these glycosides were established using 1D and 2D NMR spectroscopy and FAB mass spectrometry. For Part 9, see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1434–1437, July, 1998.     

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.     

Triterpene glycosides from <Emphasis Type="Italic">Astragalus</Emphasis> and their genins. LXXVI. Glycosides from <Emphasis Type="Italic">A. sieversianus</Emphasis>

Nine compounds including six cycloartane glycosides cyclosieversiosides A, B, F, G, and H and astrasieversianin IX; β-sitosterol, β-sitosterol β-D-glucopyranoside, and D-3-O-methyl-chiro-inositol were isolated and identified from roots of Astragalus sieversianus Pall. (Leguminosae) growing in the Republic of Kyrgyzstan. Presented at the 6th International Symposium on the Chemistry of Natural Compounds (SCNC, Ankara, Turkey, June 28–29, 2005. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 253–256, May–June, 2008.     

Triterpene Glycosides from <Emphasis Type="Italic">Astragalus</Emphasis> and Their Genins. LXXI. Cycloorbicoside D,a New Glycoside from <Emphasis Type="Italic">Astragalus orbiculatus</Emphasis>

The new cycloartane glycoside cycloorbicoside D, which has the structure 23ξ,24ξ-cycloartan-3β6α,16β,23,24,25-hexaol 3-O-β-D-xylopyranoside, was isolated from the aerial part of Astragalus orbiculatus Ledeb. (Leguminosae). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 345–346, July–August, 2005.     

Triterpene glycosides from Astragalus and their genins. LXXVIII. Chemical transformation of cycloartanes. VI. Partial synthesis of cycloadsurgenina

Cycloadsurgenin, 20R,24 S-epoxycycloartan-6α,25-diol-3,16-dione, was partially synthesized in four steps from cyclosieversigenin. Side products with the structures 17E,24S-cycloart-17-en-6α,24,25-triol-3,16-dione and 17Z,24 S-cycloart-17-en-6α,24,25-triol-3,16-dione were obtained in addition to the desired product. Presented at the 1st International Symposim on Edible Plant Resources and the Bioactive Ingredients, Xinjiang, China, July 25–27, 2008. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 591–595, 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.     

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.     

Structures of Rydberg transitions in the absorption spectra of methyl-substituted derivatives of bis(η6-benzene)chromium

The effect of methylation of ligands in bis(η⁶-benzene)chromium (1) on the structure of Rydberg transitions in absorption spectra has been studied. A detailed analysis and interpretation of all Rydberg elements of the vapor-phase spectra of bis(η⁶-benzene)chromium (2), bis(η⁶-o-xylene)chromium (3), bis(η⁶-m-xylene)chromium (4), and bis(η⁶-mesitylene)chromium (5) was carried out. The vapor-phase electronic absorption spectrum of bis(η⁶-p-xylene)chromium (6) was measured, and the assignment of the Rydberg bands was made for the first time. The first ionization potentials of complexes 2–5 were refined. The energy of detachment of the 3d_z ² electron and the parameters of the Rydberg excitations for molecule 6 were determined. The vibronic components of the 3d_z ²→R4p _x,y transition in the spectra of complexes 2 and 6 were assigned. The differences in the Rydberg structure of the spectra of compounds 2–6 were analyzed in terms of the selection rules for optical transitions in the corresponding symmetry groups. The vapor-phase spectra correspond to conformers with the symmetry groupsC _2v andC ₂ for complexes 2–4, with the symmetry groupsD _3h andD ₃ for compound 5, and with the symmetry groupD _2d for complex 6. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 897–903, May, 1998.     

Structure of the repeat unit of the Alteromonas addita type strain KMM 3600T O-specific polysaccharide

The O-specific polysaccharide of Alteromonas addita type strain KMM 3600T is constructed of trisaccharide repeat units containing L-rhamnose, D-glucose, and D-galactose. It was established that the O-specific polysaccharide consists of trisaccharide repeat units with the structure →3)-α-D-Galp-(1→3)-α-L-Rhap-(1→3)-α-D-Glcp-(1→ based on monosaccharide analysis, Smith degradation, PMR and ¹³C NMR spectroscopy, and two-dimensional COSY, HSQC, and HMBC. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 445–447, September-October, 2008.     

[3,4]-annulated pyrroles 1. Polynuclear heterocyclic systems based on pyrrolo[3,4-d]pyrimidine-2,4-dione

The intramolecular electrophilic substitution in 6-functionalized 1,3-dimethyl-1H-pyrrolo[3,4-d]pyrimidine-2,4(3H,6H)-diones was used for the synthesis of pyrimido[4′,5′:3,4]-pyrrolo[1,2-a]quinoxaline-8,10(7H,9H)-dione, pyrimido[4′,5′:3,4]pyrrolo[2,1-c][1,2,4]benzo-triazine-8,10(7H,9H)-dione, and 2H-pyrimido[4′,5′:3,4]pyrrolo[1,2-a]indole-2,4,11(1H, 3H)-trione derivatives. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2180–2185, December, 2006.     

PMR and <Superscript>13</Superscript>C NMR spectra of biologically active compounds. XIII.* Structure and stereochemistry of a new phenylpropanoid glycoside isolated from <Emphasis Type="Italic">Onopordum acanthium</Emphasis> seeds

The structure of a new compound was determined using PMR and ¹³C NMR spectroscopy (HHCOSY, HSBC, HMBC, ROESY) as 2-[3′-methoxy,4-O-β-D-galactopyranos-1-yl)benzyl]-3-(3″,4″-dimethoxybenzyl)-4hydroxybutyric acid, which was isolated for the first time from seeds of Scotch thistle Onopordum acanthium L. *For No. XII, see [1]. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 53–55, January–February, 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.     

1H NMR titration study of stimuli-responsive supramolecular assemblies: inclusion complexes between PEG–b-PEI copolymer-grafted dextran and naphthalene-appended γ-cyclodextrin via double-strand inclusion

We have previously prepared a stimuli-responsive inclusion complex between PEG–b-PEI–g-dextran graft copolymer (PEG–PEI–dex) and γ-cyclodextrin (γ-CD) in order to investigate unique inclusion phenomena, double-axle inclusion. For further study, a γ-CD derivative, mono-6-O-(2-sulfonato-6-naphthyl)-γ-CD (SN-γ-CD) was additionally synthesized for ¹H NMR titration study, which is expected to induce the competition of pendant naphthyl group with external polymer guests. Consequently, ¹H NMR titration results of the inclusion complex of PEG–PEI–dex with SN-γ-CD showed stoichiometric changes, temperature-dependence, and reversibly pH-responsive properties of the inclusion complexes in terms of chemical shift variation.     

Polysaccharides of Fabaceae. II. Galactomannan from <Emphasis Type="Italic">Astragalus danicus</Emphasis> seeds

Galactomannan of molecular weight 472 kDa was isolated from Astragalus danicus Retz. (Fabaceae) seeds and consisted of galactose and mannose units in a 1:1.40 molar ratio. The main chain of the macromolecule was constructed of 1,4-β-D-mannopyranose units, 71% of which were substituted at C-6 by single α-D-galactopyranose units. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 255257, May-June, 2009.