Steroid compounds of marine sponges. VII. Preparation of derivatives of sokotrasterol and halistanol sulfates and structure-activity interrelationships among these compounds

Five new sulfated derivatives of sokotrasterol and halistanol have been obtained: 24-nor-5α-cholane-2β,3α,6α,23-tetraol 2β,3α,6α-tri(sodium sulfate); 24-nor-5α-cholane-2β,3α,6α,23-tetraol 2β,3α,6α-tri(sodium sulfate) 23-palmitate; 24ε,25-dimethyl-5α-cholestane-2β,3α,6α-triol 3α-(sodium sulfate); 24ε,25-dimethyl-5α-cholestane-2β,3α,6α-triol 6α-(sodium sulfate); and 24ε,25-dimethyl-5α-cholestane-2β,3α,6α-triol 2β,6α-di(sodium sulfate). The inhibiting and membranolytic properties of the polysulfated steroids from sponges and their derivatives have been studied. It has been shown that physiological activity in this series of compounds depends on biphilicity.     

Steroid compounds of marine sponges

A new sulfated steroid triol — 26-norsokotrasterol sulfate — has been identified in extracts of the sponge(Trachyopsis halichondroides). Its structure has been shown as 24,25,26-trimethyl-5-cholest-23-ene-2, 3, 6-triol trisulfate. No steroid substances with side chains having the structure of that in 26-norsokotrasterol sulfate have previously been found.Pacific Ocean Institute of Bioorganic Chemistry. Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedinenii. No. 3. pp. 371–375, May–June, 1988.     

Steroid compounds of marine sponges. IX. Sterol composition of three species of Far Eastern sponges

Pacific Ocean Institute of Bioorganic Chemistry Far Eastern Branch USSR Academy of Sciences, Vladivostol. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 461–463, May–June, 1988.     

Steroid compounds of marine sponges. I. Sterols ofEsperiopsis digitata

From extracts of the Far Eastern spongeEsperiopsis digitata, by column chromatography on silica gel we have isolated three fractions of steroid compounds. The fractions isolated have been analyzed with the aid of TLC, GLC-MS, PMR, and¹³C NMR. The least polar fraction (1) had a R_f value identical with that of cholesterol and represents the total free steroids. After argentation column chromatography, 13 components were identified in it, the main one being cholesterol. The more polar fraction (2) consisted of a combination of 3-hydroxychol-5-en-24-al and 3-hydroxy-24-norchol-5-en-23-al. The most polar of the fractions isolated — fraction (3) — consisted of a single component which was identified as cholesta-5,25-diene-3,24-diol.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. 740–746, November–December, 1983.     

Steroid compounds of marine sponges. XI. Steroids of the Australian spongeTrachyopsis sp.

The compositions of two steroid fractions from the Australian spongeTrachvopsis sp. have been investigated. The fractions of steroid sulfates consisted of the trisulfates of halistanol (76%) and of 24-isopropyl-5-cholest-22-ene-2,3,6-triol (20%). In the sterol fraction, axinyssasterol (64%) and 24-isopropyl-5-cholest-22Z-en-3-ol (30%) were identified.Pacific Ocean Institute of Bioorganic Chemistry, Far Eastern Branch, USSR Academy of Sciences, Vladivostok. Translated from Khimiya Prirodnykh Soedineni, No. 2, pp. 215–218, March–April, 1990.     

Steroid compounds of marine sponges. IV. New sterols with unusual side chains from the fungusHalichondria sp 1

Five new steroid alcohols have been isolated in the form of their acetates from extracts of the spongeHalichondria sp ₁ by column chromatography on silica gel and they have been identified as 24-isopropyl-5-cholest-22z-en-3-ol, 24-isopropylcholesta-5, 22Z-dien-3-ol, 24,24,26,26-tetramethylcholesta-5,25(27)-dien-3-ol, 24,24,26,26-tetramethylcholesta-5,22E,25(27)trien-3-ol, and 24-isopropenyl-25-methylcholesta-5,22E-dien-3-ol. The structures were established by an analysis of spectral characteristics.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. 232–239, March–April, 1985.     

Steroid compounds of marine sponges. III. 24-Ethyl-25-methylcholesta-5,22-dien-3β-OL — A new marine sterol from the spongeHalichondria sp.

A new sterol — 24 ethyl-25-methylcholesta-5,22-dien-3β-ol — has been isolated by column chromatography on silica gel from extracts of the spongeHalichondria sp. Its structure has been established on the basis of an analysis of GLC-MS results and of PMR and¹³C NMR spectroscopy and has been confirmed by ozonolysis.     

Chemistry of alkenyl azlactones. VII. Preparation and properties of multiazlactones derived from mercaptan-functional compounds and oligomers

The reaction of polymercaptans and 2-alkenyl azlactones has been further investigated, and several new multiazlactones which are liquids at room temperature have been prepared and characterized. Michael addition yielding the multiazlactones was found to take place slowly in the absence of and rapidly in the presence of acid catalysts. If basic impurities capable of forming mercaptide ion were present, however, the reaction underwent a substantially different course producing primarily ring-opened products. A source of these basic impurities was determined to be the method of preparation of the alkenyl azlactone itself. When the azlactone was prepared from its acyclic N-substituted aminoacid precursor by cyclodehydration by use of ethyl chloroformate and triethylamine, a small amount of triethylamine remained that dramatically altered the course of reaction. Nonbasic cyclodehydration agents such as dicyclohexylcarbodiimide were effective at eliminating this side reaction, as well as was the practice of adding excess acid to the reaction system to neutralize the basic impurities.     

Steroid compounds of marine sponges. VIII. 24-Isopropyl-5α-cholest-22-ene-2β,3α,6α-triol trisulfate — A new steroid identified in the spongeTrachyopsis halichondrioides

A new sulfated steroid triol has been identified in extracts of the spongeTrachyopsis halichondrioides and its structure has been established as 24-isopropyl-5-cholest-22-ene-2,3,6-triol trisulfate. The possibility has been shown for the first time of the existence of identical side chains for free sterols and trisulfated steroids.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. 111–115, January February, 1986.     

Benzomorphan related compounds. VII. Synthesis of benzothienomorphans

The synthesis of some benzo [b] thieno [2,3-f] - and [3,2-f] morphans by the Grewe method is described. Spectroscopic data of these compounds and of the intermediate isomeric tetrahydropyridines are included. A side-product isolated from the aluminum bromide cyclization of the 2-(2-benzothienylmethyl)tetrahydropyridine IVd is reported and a mechanism for its formation is proposed.     

Reactivity and biological activity of the marine sesquiterpene hydroquinone avarol and related compounds from sponges of the order Dictyoceratida

A review of results of bioactivity and reactivity examinations of marine sesquiterpene (hydro)quinones is presented. The article is focused mostly on friedo- rearranged drimane structural types, isolated from sponges of the order Dictyoceratida. Examples of structural correlations are outlined. Available results on the mechanism of redox processes and examinations of chemo- and regioselectivity in addition reactions are presented and, where possible, analyzed in relation to established bioactivities. Most of the bioactivity examinations are concerned with antitumor activities and the mechanism thereof, such as DNA damage, arylation of nucleophiles, tubulin assembly inhibition, protein kinase inhibition, inhibition of the arachidonic cascade, etc. Perspectives on marine drug development are discussed with respect to biotechnological methods and synthesis. Examples of the recognition of validated core structures and synthesis of structurally simplified compounds retaining modes of activity are analyzed.