Glycosides of marine invertebrates. VIII. Steroid glycosides of the holothurianIsostichopus badionotus

The steroid glycoside fraction ofIsostichopus badionotus, consisting of a mixture of D-xylosides of steroid alcohols, has been isolated by column chromatography on silica gel. The mixture of aglycones obtained after acid hydrolysis was separated with the aid of argentation chromatography into several fractions. GLC-MS analysis, and also the use of IR and¹³C NMR spectroscopy has shown that the steroid glycosides ofI. badionotus are xylosides of Δ⁰-, Δ⁷-, Δ²²-, and Δ^7.22-, C₂₇-, C₂₈-, and C₂₉-steroids of the cholestane series.     

Glycosides of marine invertebrates. VIII. Steroid glycosides of the holothurianIsostichopus badionotus

The steroid glycoside fraction ofIsostichopus badionotus, consisting of a mixture of D-xylosides of steroid alcohols, has been isolated by column chromatography on silica gel. The mixture of aglycones obtained after acid hydrolysis was separated with the aid of argentation chromatography into several fractions. GLC-MS analysis, and also the use of IR and¹³C NMR spectroscopy has shown that the steroid glycosides ofI. badionotus are xylosides of ⁰-, ⁷-, ²²-, and ^7.22-, C₂₇-, C₂₈-, and C₂₉-steroids of the cholestane series.Pacific Ocean Institute of Bioorganic Chemistry of the Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. National Institute of Oncology and Radiobiology of the Ministry of Public Health of the Republic of Cuba, Havana. Translated from Khimiya Prirodnykh Soedinenii, No. 6, pp. 799–802, November–December, 1979.     

Trisulfated glycosides from the holothurianCucumaria japonica

Three new triterpene glycosides have been isolated from an alcoholic extract of the Pacific Ocean commercial holothurian Cucumaria japonica: cucumariosides A _T 1 (I), A _T 2 (II), and A _T 3 (III). The structures of these glycosides have been established by chemical and physical methods.     

Sterol glycosides from the Far Eastern holothurianCucumaria japonica

Sterol -D-xylopyranosides and arabinopyranosides in a ratio of 9:1 have been isolated from a lipid extract of the musculocutaneous sac of the Far Eastern holothurianC. japonica. The main components of both glycosidic fractions were identified as derivatives of cholesta-7,22-diene-3-ol, cholest-22-en-3-ol, 5-cholestan-3-ol, 24-ethylcholesta-7,22-dien-3-ol, and 24-methylene-, 24-methyl-, and 24-ethyl-cholest-22-en-3-ols.Institute of Immunology, Ministry of Health of the USSR, Moscow. M. M. Shemyakin Institute of Biorganic Chemistry, Academy of Sciences of the USSR, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 54, pp. 615–620, September–October, 1984.     

Glycosides of marine invertebrates. Structure of holothurin A2 from the holothurianHolothuria edulis

The structure of a new glycoside fromHolothuria edulis, holothurin A₂, has been established with the aid of periodate oxidation, methylation, Smith degradation, and¹³C NMR spectroscopy. The structure of the glycoside has been determined as holost-9(11)-ene-3β,12α,17α-triol 3-0-{2-0-[3-0-methyl-β-D-glucopyranosyl-(1→3)-0-β-D-glucopyranosyl-(1→4)-0-β-D-quinovopyranosyl]-4-0-sulfate-β-D-xylopyranoside}.     

Structure of cucumarioside G1 — A new triterpene glycoside from the holothurianCucumaria fraudatrix

A new triterpene glycoside — cucamarioside G₁ — has been isolated from the Pacific Ocean holothurianCucumaria fraudatrix. On the basis of physicochemical characteristics and the results of chemical transformations, its structure has been established as 16-acetoxy-3-[O-(3-O-methyl--D-xylopyranosyl)-(1 3)-O--D-glucopyranosyl-(1 4)--D-quinovopyranosyl-(1 2)-(4-O-sulfato--D-xylopyranosyloxy)]-holosta-7,24-diene.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 244–248, March–April, 1985.     

Glycosides of marine invertebrates. XIV. Structure of holothurin B1 from the holothurianHolothuria floridana

The complete structure of a triterpene oligoside — olothurin B₁ — from the holothurianH. floridana of the sublittoral of the island of Cuba has been established.     

Glycosides of marine invertegrates. XI. Two new triterpene glycosides from holothurians of the familyStichopadidae

By repeated column chromatography on silica gel new glycosides have been isolated from the holothuriansAstichopus multifidus andStichopus chloronotus — astichoposide C and stichoposide C (I and II, respectively). Their structures have been studied with the aid of chemical and physicochemical methods. The complete structures of the glycosides have been established as 23(S)-acetoxy-3β-{4′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-β-D-glucopyranosyl]-2′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-O-β-D-xylopyranosyl-(1→4)-β-D-quinovopyranosyl]-β-D-xylopyranosyloxy}holosta-7,25-diene and -holost-7-ene.     

Glycosides of marine invertebrates. VII. Structure of holothurin B fromHolothuria atra

Holothurin B, which contains a sulfate group in a carbohydrate chain, has been isolated from the holothurianHolothuria atra. Its complete structure has been established by chemical and physicochemical methods.     

Glycosides of marine invertebrates. X. The structure of stichoposides A and B from the holothurianStichopus cloronotus

The structures of two triterpene oligosides from the holothurianStichopus cloronotus (Brandt) have been established; they are: 23-acetoxy-3-[O--D-quinovopyranosyl-(12)--D-xylopyranosyloxy]holost-7(8)-ene and 23-acetoxy-3-[O--D-glucopyranosyl-(12)--D-xylopyranosyloxy]holost-7(8)-ene.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 2, pp. 181–184, March–April, 1981.     

Glycosides of marine invertebrates. XII. Structure of a new triterpene oligoglycoside from holothurians of familyStichopodidae

From an ethanolic extract of the holothuriansStichopus chloronotus by column chromatography on silica gel a new triterpene oligoside has been isolated the structure of which has been established as 23(S)-acetoxy-3β-{4′-O-[O-(3-O-methyl-β-D-glucopyranosyl)-(1→3)-β-D-glucopyranosyl]-2′-O-[O-(3-O-methyl-β-D-glucopyranosyl(-(1→3)-O-β-D-xylopyranosyl-(1→4)-β-D-glucopyranosyl]-β-D-xylopyranosyloxy}holost-7-ene. A hypothesis has been put forward concerning the biosynthesis of the carbohydrate chains in the glycosides of holothurians of the orderAspidochirota from bioside blocks.     

Glycosides of marine invertebrates. XXVI. Holothurin A from the Pacific Ocean holothurianHolothvria squamifera. Isolation of the native aglycone

The known triterpene tetraoside holothurin A has been isolated from the Pacific Ocean holothurianHolothuria squamifera. By using two independent methods — enzymatic cleavage and two-stage Smith degradation — 22,25-epoxyholost-9(11)-ene-3β,12α,17α-triol, C₃₀H₄₆O₆, which is the native aglycone of holothurin A, was obtained. The structure of the native aglycone has been established on the basis of the results of IR, mass, and PMR spectroscopy.     

Glycosides of marine invertebrates. XIII. New holothurinogenins of holothurin B1 fromHolothuria floridana

We have isolated for the first time the native aglycone of a triterpene glycoside of the holoturin series — holothurin B₁ — and have established its structure as holost-9-ene-3β,12α,17α-triol. The structures of two new holostane derivatives have been established — holosta-8,11-diene-3β,17α-diol and 3β,17α-dihydroxyholost-9-en-12-one. A scheme of transformation of the native genin of holothurin B₁ under the conditions of the acid splitting of the glycoside has been put forward.     

Isolation of native aglycones from triterpene glycosides of the Pacific Ocean holothurianCucumaria japonica

New native aglycones — 3-hydroxyholosta-7,25-dien-16-one and holosta-7,25-dien-3-ol — have been isolated from the glycosidic fraction of the holothurianCucumaria japonica. It has been shown that holostane derivatives with a 16-keto group can be transformed on reduction with sodium tetrahydroborate into previously unknown compounds with an 18 16-lactone fragment.Pacific Ocean Institute of Bioorganic Chemistry, Far-Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 55–59, January–February, 1985.     

Glycosides of marine invertebrates. VII. Structure of holothurin B fromHolothuria atra

Holothurin B, which contains a sulfate group in a carbohydrate chain, has been isolated from the holothurianHolothuria atra. Its complete structure has been established by chemical and physicochemical methods.Pacific Ocean Institute of Bioorganic Chemistry of the Far Eastern Scientific Center, Academy of Sciences of the USSR, Vladivostok. M. V. Frunze Simferopol State University. Translated from Khimiya Prirodnykh Soedinenii, No. 4, pp. 522–527, July–August, 1979.