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.     

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.     

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.     

A new flavanone glucoside from <Emphasis Type="Italic">Abrus precatorius</Emphasis>

A new flavanone glycoside, (2S)5,7,4′-trihydroxyflavanone-8-C-β-D-(6″-O-acetyl)glucopyranoside (1), together with six known flavonoids, isohemiphloin (2), vitexin (3), cirsimaritin (4), hispidulin (5), apigenin (6), and eupatorin (7), was isolated from the leaves and stems of Abrus precatorius. Their structures were elucidated on the basis of physical and spectral analysis. Rotamers exist for compounds 1, 2, and 3. Compounds 1–3, 6, and 7 were isolated from this plant for the first time.     

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.     

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.     

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.     

A new triterpene glycoside from <Emphasis Type="Italic">Premna microphylla</Emphasis>

A new triterpene glycoside, namely 28-O-α-L-rhamnopyranosyl (1→2)-β-D-glucopyranoside tormentic acid ester, was isolated from the leaves of Premna microphylla, together with two known triterpenes, i.e., arjunolic acid (2) and hyptatic acid A (3). Its structure was established by mass-spectrometric and spectroscopic methods, especially 2D NMR techniques. This is the first report of the isolation of triterpenes from this plant. Published in Khimiya Prirodnykh Soedinenii, No. 2, pp. 173–174, March–April, 2009.     

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.     

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.     

Ellagic acid glycosides from the stem bark of <Emphasis Type="Italic">Aphananthe aspera</Emphasis>

Five ellagic acid glycosides were isolated from Aphananthe aspera and their structures were identified as 3-O-methylellagic acid-4′-O-α-L-rhamnopyranoside (1), 3-O-methylellagic acid-4′-O-β-D-xylopyranoside (2), 3,3′-di-O-methylellagic acid-4′-O-β-D-xylopyranoside (3), 3,3′, 4-tri-O-methylellagic acid-4′-O-β-D-glucopyranoside (4), and 3,3′-di-O-methylellagic acid-4′-O-α-L-rhamnopyranoside (5) on the basis of spectroscopic analysis. Compound 1 is new, and all the compounds were isolated for the first time from the title plant. Published in Khimiya Prirodnykh Soedinenii, No. 5, pp. 458–459, September–October, 2007.     

A furostanol saponin and phytoecdysteroid from roots of <Emphasis Type="Italic">Helleborus orientalis</Emphasis>

A furostanol saponin mixture and a known phytoecdysteroid were isolated from the roots of Helleborus orientalis Lam. Their structures were established as 26-[(β-D-glucopyranosyl)oxy]-22α-hidroxyfurosta-5,25(27)-dien-1β,3β,11α-triol (1a), 26-[(β-D-glucopyranosyl)oxy]-22α-methoxyfurosta-5,25(27)-dien-1β,3β,11α-triol (1b), and 20-hydroxy-β-ecdyson-3-O-β-D-glycoside (2). Acid hydrolysis of 1a,b gave (1β,3β,11α,22α)-22,26-dimethoxyfurosta-5,25(27)-dien-1,3,11-triol (aglycone 1) and of 2 gave 20-hydroxy-β-ecdyson (aglycone 2). Their structures were elucidated by spectral analysis. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 75–77, January–February, 2007.     

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.     

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.     

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.     

Synthesis of diblock copolymers with cellulose derivatives. 3. Cellulose derivatives carrying a single pyrene group at the reducing-end and fluorescent studies of their self-assembly systems in aqueous NaOH solutions

Novel cellobiose and cellulose (DP _n =ca. 30) derivatives, N-(1-pyrenebutyloyl)-4-O-(β-d-glucopyranosyl)-β-d-glucopyranosylamine (6), N-(15-(1-pyrenebutyloylamino)-pentadecanoyl)-4-O-(β-d-glucopyranosyl)-β-d-glucopyranosylamine (7), N-(1-pyrenebutyloyl)-β-cellulosylamine (13), N-(15-(1-pyrenebutyloylamino)-pentadecanoyl)-β-cellulosylamine (14) carrying a pyrene group as a single fluorescent probe at the reducing end, were prepared in order to investigate their self-assembly systems in solutions. The relative intensity of the excimer emission at ca. 480 nm due to dimerized pyrenes (intensity I _E) to the monomer emission at ca. 380 nm due to isolated pyrene (intensity I _M), i.e., I _E/I _M, was monitored in various solutions. In water/dimethyl sulfoxide (DMSO) mixed solvent (0–98%, v/v), the ratio I _E/I _M remained low (0.04) for compound 6 over the range of water concentrations, indicating that pyrenes at C-1 position of compound 6 were diffused. On the other hand, the ratio I _E/I _M increased (0.04–4.96) for compound 7 with the increase in water concentration, indicating that pyrenes at C-1 position were associated. In aqueous NaOH solutions (4.4–17.5%, w/w), compound 14 showed a large increase in the ratio I _E/I _M (0.84–8.14) with the increase in NaOH concentration, compared to compound 13 (0.06–0.41). It was found that the association of hydrophobic groups at the reducing-end of cellulose could be controlled by the hydrophilic–hydrophobic balance of compounds and the solvent polarity.     

Cycloascauloside a from Astragalus caucasicus leaves

The new cycloartane glycoside cycloascauloside A with the structure 20S,24R-epoxycycloartan-3β, 6α,16β,25-tetraol 3-O-[α-L-rhamnopyranosyl(1→6)]-β-D-(2′-O-acetyl)-glucopyranoside was isolated from leaves of Astragalus caucasicus Pall. The structure was established based on IR, PMR, and ¹³C NMR spectra and physicochemical properties of the compound itself and the products of its chemical transformations. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 359–361, July–August, 2006.     

Two new benzoyl esters of glucose from Lagotis yunnanensis

Two new benzoyl esters of glucose 1-O-(E)-4′-methoxybenzoyl-β-D-glucopyranose (1) and 1-O-(E)-4′-methoxybenzoyl-β-D-gluconic acid (2) were isolated from Lagotis yunnanensis, together with six previously known iridoid glucosides. The structures of these compounds were elucidated on the basis of spectral analysis, including 2D NMR spectroscopy. Published in Khimiya Prirodnykh Soedinenii, No. 6, pp. 529–530, November–December, 2006.     

A new alloside from <Emphasis Type="Italic">Neocheiropteris palmatopedata</Emphasis>

A new compound, 2,4,6-trihydroxybenzoic acid 4-O-β-D-allopyranoside (1), together with four known compounds, sucrose (2), fructose (3), ecdysterone (4), and β-sitosterol (5) was isolated from the roots of Neocheiropteris palmatopedata (Baker) Christ. The new compound was identified based on extensive spectroscopic studies including HR-ESI-MS, FAB-MS, ¹H NMR, ¹³C NMR, DEPT, ¹H–¹H COSY, HSQC, HMBC, and NOESY spectra, and the known compounds were identified by their spectroscopic data analysis, comparison with reports in the literature, and co-chromatography with authentic standards. Compounds 2, 3, and 5 were obtained from the Neocheiropteris genus for the first time, and 4 was originally isolated from the plant.     

Triterpene glycosides from <Emphasis Type="Italic">Lonicera</Emphasis>. Isolation and structural determination of seven glycosides from flower buds of <Emphasis Type="Italic">Lonicera macranthoides</Emphasis>

The structures of seven triterpene glycosides (1–7), of which the 23-O-acetyl, 28-O-β-D-glucopyranosyl-(1→6)-O-β-D-glucopyranosyl ester of hederagenin 3-O-β-D-glucopyranosyl-(1→3)-O-α-L-rhamnopyranosyl-(1→2)-O-α-L-arabinopyranoside (2) was new, from the flower buds of Lonicera macranthoides were established using chemical and NMR spectroscopic methods. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 32–34, January–February, 2008.