Stéréosélectivité et régiosélectivité de la réduction des cyclopropènes-2,3 et méthylène-2 cyclopropanes fonctionalisés en position 1

Reduction of 2 cyclopropenyl esters and alcohols with lithium aluminium hydride is selective; at low temperatures (0°) the double bond is not reduced, but at higher temperatures (65°) the reduction is complete and only the cyclopropylmethanol is obtained. The reduction of the double bond is regioselective (the most stable carbanion is formed) and stereospecific (the hydride attack on the double bond occurs cis to the functional group). This stereospecificity can be explained through the initial formation of an alkoxylaluminium hydride followed by an intramolecular reduction of the double bond. Similar results have been obtained in the reduction of functionalised methylenecyclopropanes.     

Novel one step synthesis of epoxides from β-hydroxy-selenides and sulfides

Epoxides are stereoselectively prepared in one step from β-hydroxy selenides and β-hydroxy sulfides in a process which involves dichlorocarbene     

Molecular weight determination of vinylidene chloride copolymers by gel-permeation chromatography and viscometry

This is the first report on the characterization of several pairs of random copolymers of vinylidene chloride by gel-permeation chromatography in conjunction with viscometry. Such copolymers have not previously Received much attention, so we first determined the individual viscosity–molecular weight relationship. The K–a values were compared with known values for the parent homopolymers. We then derived calibration curves (different for each composition) and the calculation of the average molecular weight. These results are compared to those obtained by direct methods, without fractionation, and to kinetic observations. This method avoids misinterpretation of viscosity data and elution volume. Chromatograms may indicate heterogeneity of the compounds as related to polymerization conditions.     

Dynamic Molecular Metamorphism Involving Palladium-Assisted Dimerization of π-Cation Radicals

A dynamic supramolecular approach is developed to promote the π-dimerization of viologen radicals at room temperature and in standard concentration ranges. The approach involves cis- or trans-protected palladium centers serving as inorganic hinges linking two functionalized viologens endowed with metal-ion coordinating properties. Based on detailed spectroscopic, electrochemical and computational data, we show that the one-electron electrochemical reduction of the viologen units in different dynamic metal/ligand mixtures leads to the formation of the same intramolecular π-dimer, regardless of the initial environment around the metallic precursor and of the relative ratio between metal and ligand initially introduced in solution. The large-scale electron-triggered reorganization of the building blocks introduced in solution thus involves drastic changes in the stoichiometry and stereochemistry of the palladium/viologen complexes proceeding in some cases through a palladium centered trans→cis isomerization of the coordinated ligands.     

Regioselective 1–4 addition of acyl and equivalents to α-enones

2-lithio-1,3-dithianes, bis(phenylthio)alkyllithiums and bis(methylseleno)alkyllithiums add 1–4 to α-enones if HMPT is present in the medium prior to the addition of enones. Most of the reactions occur under kinetic control.     

Specific fibre composition and metabolism of the <Emphasis Type="Italic">rectus abdominis</Emphasis> muscle of bovine Charolais cattle

Background  

An important variability of contractile and metabolic properties between muscles has been highlighted. In the literature, the majority of studies on beef sensorial quality concerns M. longissimus thoracis. M. rectus abdominis (RA) is easy to sample without huge carcass depreciation and may appear as an alternative to M. longissimus thoracis for fast and routine physicochemical analysis. It was considered interesting to assess the muscle fibres of M. rectus abdominis in comparison with M. longissimus thoracis (LT) and M. triceps brachii (TB) on the basis of metabolic and contractile properties, area and myosin heavy chain isoforms (MyHC) proportions. Immuno-histochemical, histochemical, histological and enzymological techniques were used. This research concerned two populations of Charolais cattle: RA was compared to TB in a population of 19 steers while RA was compared to LT in a population of 153 heifers.