Minor polyhydroxysteroids from the starfish Crossaster papposus

Minor polyhydroxysteroids from the starfishCrossaster papposus have been isolated and characterized: 5-cholestane-3,6,8,15,16,26-hexanol and 24-methyl-5-cholesta-14,22E-diene-3,6,8,26-tetraol 26-O-(3-O-methyl--D-glucopyranoside) (crossasteroside P₃). The structures of the compounds were established on the basis of spectral methods.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, p. 218–221, March–April, 1990.     

Steroids of the furostan and spirostan series from Nolina microcarpa II. structures of nolinospiroside D and nolinofurosides D, E, and F

Proofs are given of the structures of two new glycosides of the furostan series isolated from the leaves of the plantNolina microscarpa S. Wats. (family Dracaenaceae). Nolinofuroside D is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-galactopyranoside 26-O--D-glucopyranoside (I), and nolinofuroside F is (25S)-furost-5-ene-1,3,22,26-tetraol 1-O--D-fucopyranoside 26-O--D-glucopyranoside 3-O--L-rhamnopyranoside (VII). The latter was characterized as its 22-O-methyl ether (VIII). Nolinofuroside E (IV) has the structure of (25S)-furost-5-ene-1,3,22,26-tetraol 26-O--glucopyranoside 1-O-[O--L-rhamnopyranosyl-(12)--D-fucopyranoside], which followed from the structure of the fermentation product (VI). The products of the fermentation of the above-named compounds were present in the plant in only trace amounts. Only one of them — nolinospiroside D (III) — has not been described previously. This monoside of the spirostan series is (25S)-spirost-5-ene-1,3-diol 1-O--D-galactopyranoside.M. V. Frunze Simferopol' State University. Institute of Chemistry of Plant Substances, Uzbek Academy of Sciences, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 678–686, September–October, 1991.     

Triterpene glycosides of Pulsatilla dahurica structures of glycosides A,B, C,and D

The isolation of four triterpene glycosides from the roots of the dahurian anemonePulsatilla dahurica (Fisch. ex DC) Spreng, is described together with their identification, on the basis of chemical transformations, spectral characteristics, and literature analogies, as hederagenin 3-O--L-arabinoside, hederagenin 3-O-[O--D-glucopyranosyl-(12)--L-arabinopyranoside], hederagenin 3-O--L-arabinopyranoside 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside], and hederagenin 3-O-[O--D-glucopyranosyl-(14)--L-arabinopyranoside] 28-O-[O--L-rhamnopyranosyl-(14)--D-glucopyranosyl-(16)--D-glucopyranoside].Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, Nos. 3,4, pp. 349–356, May–August, 1992.     

New polyhydroxysteroids from the far-eastern starfish Henricia sp.

From the far-eastern starfishHenricia sp. we have isolated and characterized the new polyhydroxysteroid (24S)-5-cholestane-3,4,6,8,15,24-hexaol and three new glycosides: (24S)-5-cholestane-3,4,6,8,15,24-hexaol 3-O-(2,4-di-O-methyl--D-xylopyranoside) (henricioside H₁), 24-methyl-5-cholesta-4,22E-diene-3,6,8,15,16,26-hexaol 3-O-(2,3-di-O-methyl--D-xylopyranoside) (henricioside H₂), and the 22,23-dihydro derivative of henricioside H₂ (henricioside H₃).Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Scientific Center, Russian Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 249–253, March–April, 1993.     

Steroid compounds from ophiuroids II. Sulfated steroids from Ophiura sarsi and Ophiura leptoctenia

The previously described cholest-5-ene-3,4,21-triol 3-(sodium sulfate) has been obtained from extracts of the Far Eastern ophiuroidOphiura leptoctenia. Two new sulfated steroid polyols have been isolated from the ophiuroidO.sarsi; cholest-5-ene-3,4,21-triol 3,21-di(sodium sulfate) and cholest-5-ene-2,3,21-triol tri(sodium sulfate). The new polyol 4-acetoxycholest-5-ene-3,21-diol has been identified among the products of the desulfation of this ophiuroid.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 483–487, July–August, 1990.     

Pulchellin C and inuchinenolide C from Inula caspica

The pseudoguaianolide inuchinenolide C and the eudesmanolide pulchellin C have been isolated for the first time from the flower heads and leaves ofInula caspica Blume, and their spatial structures have been established by an x-ray structural experiment as 2,6-diacetoxy-6-hydroxy-1,7(H),8,10(H)-pseudoguai-11(13)-en-8,12-olide and 2,3-dihydroxy-5,7,8(H)-eudesma-4(15),11(13)-dien-8,12-olide, respectively.Institute of Organic Synthesis and Coal Chemistry, Academy of Sciences of the Kazakh SSR, Karaganda. A. N. Nesmeyanov Institute of Organometallic Compounds, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 748–757, November–December, 1990.     

Culcitoside C1 from the starfishCulcita novaeguineae andLinckia guildingi

By repeated chromatography on Polikhrom-1, silica gel, and Florisil, ethanolic extracts of two species of starfish,Culcita novaeguineae andLinckia guildingi, have yielded the new steroid glycoside culcitoside C₁ (I): 5-cholestan-3,4,6,8,15,24-hexaol 24-O-[2,4-di-O-methyl--D-xylopyranosyl-(12)--L-arabinofuranoside], C₃₉H₆₈O₁₄, mp 245–248°C, []_D -35.8°, c 0.6; methanol). Its structure was shown by the results of acid hydrolysis, acetylation and methylation, and¹H and¹³C NMR spectroscopy.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 801–804, November–December, 1985.     

Synthesis and1H NMR and13C spectroscopy of L-arabinopyranosyl biosides

Conclusions The 3-0- and 4-0-trityl ethers of the acetates of methyl -L- arid methyl -L-arabinopyranosides were synthesized. The glycosylation of the ethers with the aid of 3,4-di-0-acetyl-1,2-0-(1-exo-cyano)ethylidene--L-arabinopyranose and the subsequent deacetylation of the synthesized products yielded the disaccharides: methyl 4-0-(-L-arabinopyranosyl)-,methyl 4-0-(-L-arabinopyranosyl)-, and methyl 3-0-(-L-arabinopyranosyl)--L-arabinopyranoside; and methyl 4-0-(-L-arabinopyranosyl)-, methyl 4-0-(-L-arabinopyranosyl)-, methyl 3-0-(-L-arabinopyranosyl)-, and methyl 3-0-(-L-arabinopyranosyl)--L-arabinopyranoside.The assignment of the signals in the PMR and¹³C NMR spectra of the synthesized arabinopyranosyl biosides was carried out, allowing the determination of the type and configuration of the glycosidic bond by means of which the arabinopyranose residues are linked in the oligo- and polysaccharide chains.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 200–209, January, 1986.     

Steroids of the spirostan and furostan series from plants of the genus Allium. XXI. Structure of alliospiroside a and alliofuroside a from Allium cepa

Two new steroid glycosides have been isolated from the generative organs (pericarps and peduncles) ofAllium cepa L.: alliospiroside A and alliofuroside A. According to chemical transformations and spectral characteristics, alliospiroside A has the structure of (25S)-spirost-5-ene-1,3-diol 1-O-[O--L-rhamnopyranosyl-(1 2)--L-arabinopyranoside]. The structure of (25S)-furost-5-ene-1,3,22,26-tetraol 20-O--D-glucopyranoside 1-O-[O--L-rhamnopyranosyl-(1 2)--L-arabinopyranoside] has been established for alliofuroside A.Institute of the Chemistry of Plant Substances of the Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 188–196, March–April, 1986.     

Mass spectrometric study of monoalkyl-substituted thiacyclanes

Monosubstituted - and -alkylthiophans and -, -, and -alkylthiacyclohexanes were subjected to a comparative mass spectrometric study. The stability of the M⁺ ion increases on passing from - to -alkylthiophans and from - to - and -alkylthiacyclohexanes. In the case of -alkylthiophans and - and -alkylthia-cyclohexanes the principal process is associated with ejection of the substituent as a whole, whereas a portion of the alkyl substituent, with retention of one CH₂ group in the composition of the charged fragment, is eliminated from the molecular ions of -alkylthiophans and -alkylthiacyclohexanes.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 176–181, February, 1978.