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.     

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.     

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.     

Triterpene glycosides from <Emphasis Type="Italic">Astragalus</Emphasis> and their genins. LXXVII. Cyclomacrogenin B,a new cycloartane triterpenoid

Ten pure compounds, three of which were identified as β-sitosterol, β-sitosterol β-D-glucopyranoside, and D-3-O-methyl-chiro-inositol, were isolated from roots of Astragalus macropus Bunge (Leguminosae). The structure of the new cycloartane triterpenoid cyclomacrogenin B was established as 24R-cycloartan-1α,3β,7β,24,25-pentaol. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 502–504, September-October, 2008. Original article submitted May 26, 2008.     

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.     

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.     

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.     

New triterpenoid glycosides fromThalictrum minus L.

From the terrestrial part ofThalictrum minus L. (Ranunculaceae) a novel triterpenoid diglycoside was isolated. The genin of this glycoside is a new cycloartane triterpenoid. The structure of the glycoside was established on the basis of 1D and 2D NMR spectroscopy and FAB mass spectrometry as 22S,25-epoxy-3-O-β-d-galactopyranosyl-29-O-β-d-glucopyranosyl-9β, 19-cyclo-20S-lanostane-3β,16β,24S,29-tetrol. For Part 10 see Ref. 1. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 602–605, March, 1999.     

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.     

Cyclochivinoside B from the aerial part of <Emphasis Type="Italic">Astragalus chivensis</Emphasis>

The known glycoside aleksandroside I and the new cycloartane glycoside cyclochivinoside B, 24S-cycloartan-3β,6α,16β,24,25-pentaol 3,25-di-O-β-D-glucopyranoside, were isolated from the aerial part of Astragalus chivensis. Their structures were established using chemical transformations and two-dimensional spectra (TOCSY, ROESY, HMBC, HSQC, COSY). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 138–140, March–April, 2007.     

New oligomeric proanthocyanidin glycosides platanoside-A and platanoside-B from <Emphasis Type="Italic">Platanus orientalis</Emphasis> trunk bark

Two new oligomeric proanthocyanidin glycosides were isolated from trunk bark of Platanus orientalis. Their structures and relative configurations were found to be 7-O-β-D-Glcp-(–)-epicatechin-(4β-8)-(–)-epicatechin(4β-8)-(–)-epicatechin-3-O-gallate (platanoside-A) and 7-O-β-D-Glc \textp\xrightarrow6 {\text{p}}\xrightarrow{6} galloyl-(+)-catechin-3-O-gallate(4α-8)-(–)-epicatechin-3-O-gallate-(4β-8)-(–)-epicatechin-3-O-gallate-(4β-8)-5-O-β-D-Glcp-(–)epicatechin-3-O-gallate (platanoside-B).     

Triterpene glycosides from <Emphasis Type="Italic">Astragalus</Emphasis> and their genins. LXXXI. Chemical transformation of cycloartanes. VII. Synthesis of cyclosiversigenin lactone

The lactone 20R-25-norcycloartan-3β,6α,16β-triol-20,24-olide was synthesized from cyclosiversigenin. Presented at the 1st International Symposium on Edible Plant Resources and the Bioactive Ingredients, Xinjiang, China, July 25–27, 2008. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 324–327, May–June, 2009.     

Mechanistic studies on cationic ring-opening polymerisation of cyclodextrin derivatives using various Lewis acids

In order to investigate the potential of cyclodextrins for the preparation of block-like substituted polysaccharides, we submitted mixtures of heptakis[2,3,6-tri-O-methyl]-β-cyclodextrin (Me₂₁-β-CD, 1) and heptakis[2,3,6-tri-O-methyl-d ₃]-β-cyclodextrin ((Me-d ₃)₂₁-β-CD, 2) to cationic ring-opening polymerisation (CROP). Reactions were performed with BF₃·OEt₂, methyl triflate (MeOTf), and Et₃OSbCl₆. Products were compared with respect to their degree of polymerisation (DP) and the average block length (BL). Highest DP was observed with BF₃·OEt₂, while Et₃OSbCl₆ was the most active initiator. Average block length decreased from 14 in the early stage of product formation to about 2 due to competing chain transfer reaction. ¹H NMR spectroscopy, GLC, GLC–MS, ESI-MS and MALDI-TOF-MS were applied for detailed investigations of side reactions. During incubation with BF₃·OEt₂, a stereroisomeric β-CD with one β-glucosidic linkage (Me₂₁-β-CD_6α1β, 3a (Me-d ₃)₂₁-β-CD_{6α 1β}, 3b) is formed as an intermediate, while linear Me₂₁- and (Me-d ₃)₂₁-maltoheptaose (4a/b) was detected in the early stage of the reaction promoted by MeOTf. In the case of Et₃OSbCl₆, both intermediates (3a/b, 4a/b) can be observed during the lag phase of polymerisation, but to a very low degree. End group analysis by GLC reveals that some alkyl exchange occurs at position 3 and 6 in the presence of Et₃OSbCl₆, and that polymerisation is also initiated by protons. Copolymerisation of heptakis[2,3,6-tri-O-benzyl]-β-cyclodextrin (Bn₂₁-β-CD, 5) and Me₂₁-β-CD (1) and subsequent debenzylation yielded a polymer of only 1,4-glcp-Me₃- and 1,4-glcp-residues. Reactivity of Bn₂₁-β-CD was significantly lower than of Me₂₁-β-CD, resulting in higher average block length of 1,4-glcp-Me₃-units.     

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.     

The structure and13C NMR spectra of mannitol oligo-β-d-glucopyranosides isolated from the brown seaweedChorda filum (L.) Lam

1-O-β-d-Glucopyranosyl-d-mannitol, 1,6-di-O-glucopyranosyl-d-mannitol, 1-O-β-gentiobiosyl-d-mannitol, 1-O-β-gentiobiosyl-6-O-β-d-glucopyranosyl-d-mannitol, and 1-O-β-d-gentiotriosyl-d-mannitol were isolated from the brown seaweedChorda filum and the assignment of signals in their¹³C NMR spectra was performed. Comparative analysis of the oligosaccharide composition and the structure of laminarans from seven brown algae demonstrates that the oligosaccharides are not always fragments of the corresponding laminarans. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1817–1820, October, 1993.     

Sulfated steroid glycosides from the Viet Namese starfish <Emphasis Type="Italic">Linckia laevigata</Emphasis>

Five sulfated steriodal compounds including one new glycoside called linckoside L7 (1) and four previously known glycosides 2–5 were isolated from the starfish Linckia laevigata. The structure sodium (22E, 24R)-3-O-(2-O-methyl-β-D-xylopyranosyl)-29-O-(β-D-xylopyranosyl)-24-ethylcholest-4,22-dien-3β,6β,8,15α,16β,29-hexaol 15-O-sulfate was proposed for L7. Linckoside L7 inhibited fertilization and egg-cell development in the sea urchin Strongylocentrotus intermedius. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 64–67, January–February, 2007.     

Structure of a steroid saponin from <Emphasis Type="Italic">Digitalis ciliata</Emphasis>

A new steroid glycoside was isolated from leaves of Digitalis ciliata (Scrophulariaceae) by fractionation of the total extracted substances. Its structure was determined as (25R)-5α-spirostan-3β-ol 3-O-β-D-glucopyranosyl-(1→3)[β-D-fucopyranosyl-(1→2)]-β-D-glucopyranosyl-(1→4)-β-D-galactopyranoside based on chemical transformations, physical constants, and spectral data. __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 135–137, March–April, 2007.     

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.     

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.     

Structures of new polar steroids from the Far-Eastern starfish <Emphasis Type="Italic">Ctenodiscus crispatus</Emphasis>

A fraction of sulfated polyhydroxylated steroids from the Far-Eastern starfish Ctenodiscus crispatus was investigated. The main component of this fraction was identified as (22E,24R,25R)-24-methyl-5α -cholest-22-en-3β,5,6β,15α,25,26-hexol 26-O-sulfate. For the compound stereoisomeric with respect to the side chain, the (24R,25S) or (24S,25R) relative configurations were assigned to the C(24) and C(25) chiral centers. The structures of two other compounds isolated from the fraction were identified as (22E, 24ξ)-26,27-bisnor-24-methyl-5α-cholest-22-en-3β,5,6β,15α,25-pentol 25-O-sulfate and (22E, 24ξ,25ξ)-24-methyl-5α-cholest-22-en-3β,5,6β,8,15α,25,26-heptol 26-O-sulfate. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1229–1234, May, 2005.