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. 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.     

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.     

Triterpene glucosides of <Emphasis Type="Italic">Astragalus</Emphasis> and their genins. LXXIV. Cyclotrisectoside,the first trisdesmoside of cyclocephalogenin

The two trisdesmoside cycloartane glycosides astragaloside VII and cyclotrisectoside were isolated from Astragalus dissectus (Leguminosae) and identified. The latter was 20R,25-epoxy-24S-cycloartan-3β,6α,16β,24-tetraol 3-O-β-D-xylopyranoside-6,24-di-O-β-D-glucopyranoside and was a new natural compound. Presented at the Sixth International Symposium on the Chemistry of Natural Compounds (SCNC, Turkey, Ankara, 28–29 June 2005). __________ Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 132–134, March–April, 2007.     

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.     

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     

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.     

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.     

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.     

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.     

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.     

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 <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.     

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.     

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.     

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.     

Triterpene glycosides from <Emphasis Type="Italic">Astragalus</Emphasis> and their genins. LXXXII. Cyclomacroside B,a new glycoside

The structure of the new cycloartane glycoside cyclomacroside B that was isolated from Astragalus macropus Bunge (Leguminosae) was shown to be 1,7-di-O-acetyl-24R-cycloartan-1α,3β,7β,24,25-pentaol 3-O-α-Lrhamnopyranoside-24-O-β-D-xylopyranoside.     

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.     

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.     

Triterpene glycosides from <Emphasis Type="Italic">Astragalus</Emphasis> and their genins. LXXXV. Structure of cyclomacroside E

The structure of a new cycloartane-type triterpene glycoside, cyclomacroside E, which was isolated from roots of Astragalus macropus Bunge (Leguminosae), was established as 3-O-α-L-rhamnopyranoside,24-O[(β-D-xylopyranosyl)(1→2)-β-D-xylopyranoside]-24R-cycloartan-1α,3β,7β,24,25-pentaol.