Bilosespens A and B: two novel cytotoxic sesterpenes from the marine sponge Dysidea cinerea

[formula: see text] Two novel sesterpenes, bilosespens A and B (1 and 2) were isolated from the Red Sea sponge Dysidea cinerea collected in the Dahlak archipelago, Eritrea. The structure of the mixture of the two inseparable compounds was established by spectroscopic analysis, mainly by 1D and 2D NMR measurements. The mixture of bilosespens A and B is cytotoxic to a few human cancer cells.     

Quantitative NMR spectrometry of phase-transfer catalysts: Part 1. Determination of Extraction Constants and Water of Hydration

Proton magneticf resonance spectrometry was applied for evaluation of the distribution ratios and apparent extraction constants of tetraalkylammonium and tetraalkylphosphonium salts in two liquid-phase systems. Triethylbenzyl- and tetrabutylammonium chloride in dichloromethane and chlorobenzene, respectively, were shown to be salted out in the presence of aqueous sodium hydroxide solutions. ¹H-n.m.r. spectrometry was also used to determine the degree of hydration of quaternary onium salts in two-phase systems. The results were compatible with those obtained by the Karl Fischer method.     

New alkylated scalarins from the sponge dysidea herbacea

Six new biogenetically interesting alkylated scalarins, scalardysin-A and B, scalar-herbacin-A and B and the latter's acetates were isolated from $\text{Dysidea-herbacea}$. Structures are suggested for the various compounds based on their spectral data.     

New prostaglandin (PGF) derivatives from the soft coral Lobophyton depressum

Four PGF derivatives (15S)-PGF_2α-11-acetate methyl ester ($\text{1}$a), the 18-acetoxy derivative of compound $\text{1}$a ($\text{2}$a) as well as their two corresponding free carboxylic acids ($\text{1}$b) & $\text{2}$b) were isolated from a soft-coral and their structure elucidated, mainly on basis of their spectral data.     

Latrunculins: NMR study,two new toxins and a synthetic approach

A complete ¹H and ¹³C NMR assignment of one of the latrunculins (B) was accomplished with the aid of 2D NMR COSY and CH shift-correlation experiments. The various H-H Coupling constants have been datermined and a conformation of the macrolide and the tetrahydropyran (THP) ring suggested on basis of the J-values and measured NOE's. The absolute configuration of latrunculin-A($\text{1}$) was determined on the grounds of its earlier X-Ray analysis, and a chemical degradation to a known compound. Two novel latrunculins, -C($\text{3}$) and -D($\text{4}$), were isolated from the Red Sea sponge $\text{L. magnifica}$ and their structures elucidated. Starting with L-cysteine a synthon for the latrunculins has been synthesized.     

Cycloadditions of 3,4-dimethyl-1-thio-1-phenyl phosphole

Phosphole sulfide 1 undergoes cycloaddition to give a new 15-phosphasteroid. The ¹³C-NMR and ²J_PC-coupling constants of several compounds prepared similarly are discussed, permitting structure assignment to one of the 7-phosphabicyclo[2.2.1]heptane adduct 5. Thiophosgene reacts with the PS moiety of 1, giving 12 after hydrolysis, through a PS to PO transformation coupled in case of 1 with a proton migration.     

8-Phosphabicyclo[3.2.1]octanes—III4: The reaction between oxyallyl cations and phosphole derivatives

The reaction of oxyallyl cations with phosphole sulfide as well as phosphole oxides was investigated and was found to give the expected 8-phosphabicyclo[3.2.1]octanic system (2, 4 and 7) apart from other unexpected products (3 and 5). In the case of the phosphole sulfide (1), the oxyallyl cation is believed to react preferentially with the P=S group, rather than the dienic moiety, leading to a P=S to P=O transformation or to a very particular reaction resulting in 5. This occurs through an intermediate (j) in which a C=S group reacts in a [2 + 4] cycloaddition with the phosphole as a diene. The structure and stereochemistry of the various products were established by the aid of their spectral data in conjunction with spectral data of some related compounds. A formal PhPO elimination is believed to occur through an intermediate phosphinate resulting from Bayer-Villiger like oxidation, which then loses the [PhPO₂] group.Phosphole sulfide (1), previously found to react as a dienophile, was shown to enter a [2 + 4] cycloaddition as a diene with powerful dienophiles like 4-methyl-1,2,4-triazoline-3,5-dione (10).     

Three-dimensional relativistic-covariant poisson brackets

Using the algebraic properties of Poisson brackets, we extend the three-dimensional brackets (for a single free particle) to conform to the demands of special relativity. This yields, in an essentially unique way, the manifestly covariant extension [x ,p _v]=+p p _v/m ² c ². Position and time then become fully dynamical variables expressible in terms of the canonical conjugateq _i andp _i and the time parameter asx _i =q _i +p _i(q ·p)/m ²c² andt = +E(q ·p)/m ²c⁴. In the quantized version, the length associated with a particle of massm is shown to be an integral multiple of the Compton wavelength _C =/mc.     

Salarins a and B and tulearin a: new cytotoxic sponge-derived macrolides

Three novel nitrogenous macrolides designated salarin A and B (1 and 2) and tulearin A (3) were isolated from the Madagascar Fascaplysinopsis sp. sponge. The structures of the compounds were elucidated by interpretation of MS and 1D and 2D NMR spectra. Both salarins carry an acetylcarbamate moiety, and in addition, 1 contains a triacylamine group and 2 a methoxymethylketone lactam. Tulearin A carries the naturally rare carbamate ester. The compounds were found to be toxic to brine shrimp larvae, and salarin A and tulearin A were also cytotoxic to leukemia cells.     

Taumycins A and B, two bioactive lipodepsipeptides from the Madagascar sponge Fascaplysinopsis sp

Two closely related lipodepsipeptides, taumycins A and B (1 and 2) have been isolated from the Madagascar sponge Fascaplysinopsis sp. The two compounds have the same 12-membered oxodepsipeptide ring system in common. Both were toxic to brine shrimp larvae, and taumycin A (1 microM), but not taumycin B, inhibited growth of the human UT-7 leukemic cell line. The structure of the two compounds, likely to be derived from microorganisms, was established by MS and 1D and 2D NMR data.