Synthese de pyrrolo[1,2-a]quinoleines

A-Acetoxypyrrolo[1,2a]quinolines 26-30 were synthesized by cyclization of 2-(1-pyrroly)phenylacetic acids 21-25 with acetic anhydride. The structures of the new compounds were determined by ¹H-nmr spectroscopy.     

C-O and C-C bond formation in the cyclisation of gem-(dialkoxymethyl)-1,6-dienes catalysed by tin(IV) triflimidate at room temperature

We described herein a Sn(NTf₂)₄-catalysed cyclisation of gem-(dialkoxymethyl)-1,6-dienes and derivatives where cyclohexane or tetrahydrofuran rings are formed following either a 6-enexo-endo-trig process or a 5-exo-trig process, respectively, depending on substitution patterns. The latter process features an unusual dealkylative ether cyclisation, triggered by the strong Lewis acid character of the tin(IV) triflimidate catalyst.     

Hydrogen activation on Mo-based sulfide catalysts,a periodic DFT study

Hydrogen adsorption on Mo[bond]S, Co[bond]Mo[bond]S, and Ni[bond]Mo[bond]S (10 1 macro 0) surfaces has been modeled by means of periodic DFT calculations taking into account the gaseous surrounding of these catalysts in working conditions. On the stable Mo[bond]S surface, only six-fold coordinated Mo cations are present, whereas substitution by Co or Ni leads to the creation of stable coordinatively unsaturated sites. On the stable MoS(2) surface, hydrogen dissociation is always endothermic and presents a high activation barrier. On Co[bond]Mo[bond]S surfaces, the ability to dissociate H(2) depends on the nature of the metal atom and the sulfur coordination environment. As an adsorption center, Co strongly favors molecular hydrogen activation as compared to the Mo atoms. Co also increases the ability of its sulfur atom ligands to bind hydrogen. Investigation of surface acidity using ammonia as a probe molecule confirms the crucial role of sulfur basicity on hydrogen activation on these surfaces. As a result, Co[bond]Mo[bond]S surfaces present Co[bond]S sites for which the dissociation of hydrogen is exothermic and weakly activated. On Ni[bond]Mo[bond]S surfaces, Ni[bond]S pairs are not stable and do not provide for an efficient way for hydrogen activation. These theoretical results are in good agreement with recent experimental studies of H(2)[bond]D(2) exchange reactions.     

Total synthesis of amorfrutin A via a palladium-catalyzed migratory prenylation–aromatization sequence

The total synthesis of amorfrutin A, a prenyl bibenzyl natural product has been achieved in five steps from 2,2,6-trimethyl-4H-1,3-dioxin-4-one. The key step of the synthesis is an efficient palladium(0)-catalyzed decarboxylative prenylation migration and aromatization sequence.     

Molecular design based on 3D-pharmacophore. Application to 5-HT subtypes receptors

A first definition of a pharmacophore for the serotonin reuptake inhibitors was carried out by considering a three-dimensional model which correlates the chemical structures of series of reuptake inhibitors with their biological affinities. A molecular design was described by analyzing two different 3D serotonin pharmacophores. This successful approach enabled us to consider the design of new serotonin ligands by the same method.     

Liquid chromatographic/mass spectrometric detection of the 3-(3-hydroxyalkanoyloxy) alkanoic acid precursors of rhamnolipids in Pseudomonas aeruginosa cultures

A series of pseudomolecular and fragment ions attributed to 3-(3-hydroxyalkanoyloxy)alkanoic acids (HAAs) were detected by liquid chromatography/mass spectrometry among the rhamnolipids observed in a Pseudomonas aeruginosa strain 57RP supernatant. The fragmentation mechanism leading to the formation of the fragment ions was determined by a deuterium exchange experiment and by using a standard HAA mixture obtained from the mild acidic hydrolysis of rhamnolipids of known composition. The structure and the response factor of these free HAAs were determined. The HAAs relative composition differs between free HAAs and those present in rhamnolipids, the former being enriched in lower molecular mass congeners and depleted in the heavier ones. Within an isomeric pair, the isomer with the shortest 3-hydroxyalkaloyl residue at the hydroxyl end was more abundant than the one with the heavier 3-hydroxyalkaloyl acid at this position, and the ratios of their relative abundances were similar for free HAAs and those in rhamnolipids. Experiments with deuterium-labeled rhamnolipids demonstrated that free HAAs are part of a pool used for rhamnolipid biosynthesis and are not rhamnolipid degradation products.     

Quantum cloning with an optical fiber amplifier

It has been shown theoretically that a light amplifier working on the physical principle of stimulated emission should achieve optimal quantum cloning of the polarization state of light. We demonstrate close-to-optimal universal quantum cloning of polarization in a standard fiber amplifier for telecom wavelengths. For cloning 1-->2 we find a fidelity of 0.82, the optimal value being 5 / 6=0.83.