Minor and trace sterols in marine invertebrates 65. 23-Epidihydrocalysterol: a new cyclopropane-containing sponge sterol.

A new cyclopropane-containing sterol was isolated from the marine sponge Cribrochalina vasculum. The new sterol was characterized by nuclear magnetic resonance and mass spectrometry and the structure was shown to be (23R,24S,28R)-dihydrocalysterol. Implications concerning the biosynthesis of cyclopropane and cyclopropene sterols in sponges are discussed.     

Minor and trace sterols from marine invertebrates 56. Novel coprostanols from the marine sponge Petrosia ficiformis

Twelve stanols possessing the rare 5 beta-dihydro nucleus have been isolated from the marine sponge Petrosia ficiformis. These stanols have not previously been encountered in any samples of P. ficiformis which we have examined and appear to be the result of bacterial metabolism of the endogenous sponge sterols.     

Minor and trace sterols from marine invertebrates 28. A novel polyhydroxylated sterol from the soft coral Anthelia glauca

A novel sterol containing four hydroxy groups has been isolated from the soft coral $\text{Anthelia glauca.}$ Its structure, 5α-ergostane-3β, 5,6β,7β-tetrol ($\text{1}$), has been deduced by spectroscopic methods and confirmed by comparison with a synthetic analog.     

Minor and trace sterols in marine invertebrates. 61. Isolation and structure elucidation of new A-nor sterols from the marine sponge Phakellia aruensis

An examination of the Australian sponge Phakellia aruensis led to the isolation and identification of sterols with six different nuclei. Eight new sterols were isolated which included three delta 15-A-nor sterols, three delta 7-A-nor sterols, and two saturated A-nor sterols. Their structures were established through mass spectrometry and 1H-NMR spectral studies.     

Minor and trace sterols in marine invertebrates 39.1 24ξ,25ξ-24,26-cyclocholest-5-en-3β-ol,a novel cyclopropyl sterol.

The novel cyclopropyl sterol, 24ξ, 25ξ-24, 26-cyclocholest-5-en-3β-ol (24, 26-cyclocholesterol), has been isolated from the sponge $\text{Spheciospongia sp}$. ($\text{Spirastrella vagabunda}$ Ridley) and its structure established by spectral analysis and by correlation with papakusterol.     

Minor and trace sterols in marine invertebrates. 62. Novel coprostanols with unusual side chains from the marine sponge Calyx nicaeensis

Seventeen stanols with a variety of unusual side chains and possessing the rare 5 beta-dihydro nucleus have been isolated from the sponge Calyx nicaeensis. These stanols probably result from bacterial metabolism of the endogenous sponge sterols.     

Minor and trace sterols in marine invertebrates. 1. General methods of analysis.

3beta-Hydroxy sterols occurring at a concentration of at least 0.001% of the sterol mixtures of Pseudoplexaura porosa and Plexaura homomalla have been fractionated using a series of refined techniques and subsequently analyzed using combined gas chromatography-mass spectrometry (GC-MS) in the development of a procedure for examining the minor and trace components of marine sterol mixtures. A total of 49 sterols were found which spanned a molecular weight range of 274 to 440. In addition delta4-3-keto analogs of cholesterol, 24-methylcholesterol and gorgosterol were found in the extracts of P. homomalla. Initial separation of various natural sterol-containing conjugates and free sterols was found to have a number of advantages. Fractional digitonin precipitation and alumina column chromatography were found to possess greater sterol separation abilities than previously recognized. Many of the minor sterols were found to possess novel structures including a series of short side chain sterols, 19-nor sterols, 5beta-stanols and 4-monomethyl sterols for which structure elucidation work is continuing.     

Minor and trace sterols in marine invertebrates 47. A re-investigation of the 19-nor stanols isolated from the sponge Axinella polypoides

The aim of this research was to establish the true composition of the 19-nor stanols isolated from the sponge Axinella polypoides and to determine accurate stereochemistry for each 19-nor stanol isolated. The following new 19-nor stanols were collected from this sponge: (i) (22E,24S)-24-methyl-19,27-bisnor-5 alpha-cholest-22-en-3 beta-ol, (ii) (22R,23R)-22,23-methylene-19-nor-5 alpha-cholestan-3 beta-ol, (iii) (24 xi)-24-propyl-19-nor-5 alpha-cholestan-3 beta-ol and (iv) (23R,24R)-23,24-dimethyl-19-nor-5 alpha-cholestan-3 beta-ol. The general structure and stereochemistry of all fifteen 19-nor stanols were established by analysis of the MS and H-NMR (300 MHz, CDCl3) data measured for each compound. The relative percentage of 19-nor stanols having delta 22 double bonds should be sufficient to suggest that this sponge could be a potential source of starting material for the partial synthesis of certain oral contraceptives, which also have a 19-nor steroid nucleus.     

Minor and trace sterols in marine invertebrates 53 (1): Further novel marine sterols resulting from triple and quadruple biomethylation of the cholesterol side-chain

The isolation and structure elucidation of nine new trace sterols with highly branched side chains from a Pseudaxinyssa species from the Australian Great Barrier Reef are described.     

Minor and trace sterols in marine invertebrates : VI. Occurrence and possible origins of sterols possessing unusually short hydrocarbon side chains

Sterols with biosynthetically unusually short side chains (fewer than eight carbon atoms expected for primary squalene cyclization products) have been identified in the extracts of numerous marine invertebrates. The structures of the short side chain and conventional side chain sterols have been determined for various species of Porifera and Coelenterata. Sterol structures were determined by comparison of their mass spectra and gas chromatographic retention times with those of authentic or synthetic samples. Evidence is presented supporting the natural occurrence of these compounds in the tissues of the marine invertebrates as opposed to formation by degradative processes during sample handling or laboratory work-up. The short side chain sterols were found to possess predominantly the androst-5-en-3β-ol nucleus with C-17 alkyl side chains ranging from zero to six carbon atoms. Concentrations of short side chain sterols range from trace levels to over 5% of the sterol mixture in various species. The possible origins of these short side chain sterols are evaluated in the light of current knowledge of sterol function, biosynthesis, dealkylation, microbial degradation, and autoxidation. Known sterol autoxidations are reviewed, and possible singlet oxygen and free radical mechanisms of sterol side chain autoxidation (at physiological temperatures) which may lead to sterols with shortened hydrocarbon side chain are suggested. The possible autoxidative generation of short side chain sterols from known marine sterols by the suggested mechanisms is evaluated through application of the REACT computer program. Predicted short side chains are tabulated for each parent marine sterol side chain and then compared with the compositions of the actual sterols found in the marine extracts examined. The possible natural environmental or in vivo autoxidative formation of the short side chain marine sterols is supported by these evaluations.     

Minor and trace sterols in marine invertebrates 55. The isolation, structure elucidation and synthesis of ergosta-5, 24(28), 25-trien-3 beta-ol

The isolation, structure determination and synthesis of ergosta-5, 24(28), 25-trien-3 beta-ol, as well as the synthesis of its 28-14C analog--a possible biosynthetic precursor of several marine sterols--is described.     

Minor and trace sterols in marine invertebrates XVII. 1 (24R)-24,26-dimethylcholesta-5,26-dien-3β-01, a new sterol from the sponge Petrosia ficiformis

More than thirty monohydroxy sterols were detected in the marine sponge $\text{Petrosia ficiformis}$, ranging from the ubiquitous 24-norcholesta-5, 22-dien-3β-o1 to the C³⁰ sterol, 24-propylidenecholesterol. A new minor sterol was isolated and shown by spectral analysis and comparison with a synthetic sample to be (24R)-24,26-dimethy1cho1esta-5,26-dien-3β-o1 [26(29)-dehydroap1ysterol] ($\text{12}$).     

Minor and trace sterols from marine invertebrates 29. (22E)-ergosta-5,22,25-trien-3β-ol and (22E,24R)-24,26-dimethylcholesta-5,22,25(27)-trien-3β-ol. Two new marine sterols from the sponge Pseudaxinella lunacharta

Two new marine sterols have been isolated from the sponge $\text{Pseudaxinella lunaecharta}$, and are shown to contain two double bonds in the side chains. The structures have been deduced by spectroscopic methods and confirmed by transformation of one of them to a known compound.     

Chemical studies of marine invertebrates. XVI. Structure and absolute configuration of lobosterol, a novel polyoxygenated sterol from the alcyonacean Lobophytum pauciflorum (clelenterata, octocorallia).

Lobosterol [(24S)-24-methylcholestane-3beta,4beta,5beta,25-tetrol-6-one 25 monoacetate] has been isolated from the Alcyonacean Lobophytum pauciflorum. The structural elucidation of this novel polyoxygenated sterol was achieved by chemical and spectroscopic evidence, and by X-ray diffraction analysis.     

Minor and trace sterols of Dunaliella tertiolecta

The minor sterols have been isolated from the unicellular chlorophyte alga Dunaliella tertiolecta and identified by GC/MS and ¹³C NMR as a mixt     

Biophysical properties of unusual phospholipids and sterols from marine invertebrates

Liposomes composed of 1,2-di-(5Z,9Z)-5-9-hexacosadienoyl-sn-glycero-3-pho sph ocholine underwent an endothermic phase transition at 42 degrees C. Cholesterol or the marine sterols studied did not affect this transition to an appreciable extent, but rather were excluded from the phospholipid bilayers. Membranes composed of 1,2-di-(5Z,9Z)-5,9-hexacosadienoyl-sn-glycero-3-pho sph ocholine displayed very similar phase properties. Effects of the marine sterols on dipalmitoylphosphatidylcholine bilayers were also investigated.     

Ophirasterol, a new C31 sterol from the marine sponge Topsentia ophiraphidites

Analysis of the sterol fraction obtained from the Colombian Caribbean sponge Topsentia ophiraphidites revealed that this sponge is a rich source of C30 and C31 sterols. Among them, a new C31 sterol, named ophirasterol, was isolated, and its structure was established as (22E,24R)-24-(1-buten-2-yl)cholesta-5,22-dien-3beta-ol (1) by spectral means and comparison with synthetic C-24 epimers with known configuration. Other isolated C30 and C31 sterols were the known 24-ethyl-24-methyl-22-dehydrocholesterol (2), 24-isopropyl-22-dehydrocholesterol (3), 24-isopropylcholesterol (4), 24-ethyl-24-methylcholesterol (5), 24-isopropenyl-25-methyl-22-dehydrocholesterol (6) and 24-isopropenyl-25-methylcholesterol (7), and 24-isopropenyl-22-dehydrocholesterol (8).     

A new sterol sulfate,Sch 572423, from a marine sponge,Topsentia sp

Bioassay-guided fractionation of an active fraction from a marine sponge Topsentia sp. in our marine fraction library (MFL) led to the isolation and identification of halistanol sulfate (1) and a new sterol sulfate Sch 572423 (2). Compounds 1 and 2 were identified as P2Y(12) inhibitors with IC(50) of 0.48 and 2.2 microM, respectively. The general method of purification for the MFL library and the structure elucidation of compound 2 are described.     

New polyhydroxylated sterols stylisterols A-C and a novel 5,19-cyclosterol hatomasterol from the Okinawan marine sponge Stylissa sp

New polyhydroxylated sterols, stylisterol A-C (1-3), and a novel 5,19-cyclosterol, hatomasterol (4) were isolated from the Okinawan sponge Stylissa sp. Structural determinations of these compounds were made by spectroscopic analysis and chemical conversion. Assessment of cytotoxicity toward HeLa cells was also determined.     

24xi-Methylcholestane-3beta, 5alpha, 6beta, 12beta, 25-pentol 25-monoacetate, a novel polyoxygenated marine sterol.

24xi--Methylcholestane-3beta, 5alpha, 6beta, 12beta, 25-pentol 25-monoacetate has been isolated from an Alyconarian and its structure was established in part through extensive high resolution mass spectral and nmr studies and partly through the nonidentity of one of its degradation products with 24xi-methylcholestane-3beta, 5alpha, 6beta, 12alpha-tetrol synthesized from deoxycholic acid.