Synthesis and anti-tubulin evaluation of chromone-based analogues of combretastatins

Twenty new hybrid compounds with both combretastatin and flavone moieties were synthesized. These derivatives are classified according to the position of the trimethoxyphenyl ring at C-2 or C-3 of the chromone and presence or absence of a carbonyl as a linker between C-3 and the aryl ring. Most of these compounds were prepared from hesperidin or naringin, two natural and abundant Citrus flavonoids. Seven of these combretastatin analogues revealed anti-tubulin activity but in a medium range.     

Action of α-cyclodextrin on phospholipid assemblies

Interactions of α-cyclodextrin (α-CD) with dimyristoylphosphatidylcholine (DMPC) and Egg phosphatidylcholine (Egg-PC) were studied (i) by analyzing surface pressure-area isotherms and surface tension of phospholipid monolayers formed at the interface between air and α-CD aqueous solutions and (ii) by X-ray diffraction performed on fully hydrated α-CD/phospholipid binary mixtures. The cyclodextrin molecules strongly interact with the two-dimension phospholipid assembly. Their addition into the aqueous sub-phase leads to the removal of part of the phospholipids from the air-water interface: the higher the α-CD concentration, the higher the phospholipid depletion. This should preferentially involve interactions between cyclodextrin and the phosphatidylcholine head group as α-CD is water-soluble and not surface-active. At the three-dimension level, the bilayer packing of the phospholipid lamellar phase appears not affected by the presence of cyclodextrin as shown by X-ray scattering at small angles whereas wide-angle diffraction patterns reveal the formation of a crystalline phase organized in a pseudo-hexagonal lattice usually characteristic of α-CD dimers. These results point out that α-CD should interact with bilayer-forming phospholipid molecules but likely according to a process that would preserve intact at least a part of the multilamellar assembly.     

Metathetical reactions of carbonylate anions with dichlororuthenium complexes: Preparation and characterization of ruthenium—molybdenum and ruthenium—manganese complexes

The possibility of making metal—metal bonded heterobimetallic species by metathesis of ruthenium dichlorides with anionic carbonylates is demonstrated by the isolation of MoRu(μ-Cl)(μ-CO)(CO)₂(PPh₃)₂(η-C₅H₅) (1) and MnRuCl(μ-CO)₂(CO)₃(μ-dppm)₂ (2), obtained by action of [Mo(CO)₃(η-C₅H₅]^? on RuCl₂(PPh₃)₃ and of Mn(CO)₅^? on RuCl₂(dppm)₂, respectively. In contrast, reaction of Mn(CO)₅^? with RuCl₂(PMe₃)₄ yielded an ionic species 3 containing the diruthenium cation Ru₂Cl₃(PMe₃)₆⁺. More interestingly, the action of Mn(CO)₅^? on RuCl₂(PPh₃)₃ resulted in the formation of the unexpected complex MnRu(μ-PPh₂)(CO)₆(PPh₃)₂ (4) in which the phosphido group PPh₂ bridges the two metals; this process is shown to involve a hydride intermediate, and elimination of a molecule of benzene, both identified in the reaction mixture.     

Combined cation-exchange and extraction chromatography for the concomitant separation of Zr, Hf, Th, and the Lanthanides from geological materials

A new method was developed, aiming to overcome the iron and titanium interferences which severely limit the applications of a recently introduced extraction chromatography material, referred to as RE resin (formerly, RE Spec), to the analysis of geological samples. The separation scheme is based on the combined use, in tandem columns, of the conventional AG50WX4 cation-exchange resin and the RE extraction chromatography material, without any intervening evaporation step. The Lanthanides are recovered quantitatively, while recoveries for Zr, Hf and Th range from 94 to 98%. These three elements are determined using the isotope dilution method, thereby alleviating the need for a yield correction. Compared with conventional methods based on cation-exchange, this combined scheme offers a greater multi-element capability, significant miniaturisation, acid wastes reduction, and a higher degree of purity of the separated analytes with regard to unwanted elements such as Ba and residual Ca and Al. This concomitant isolation of 17 trace elements of great interest in the Earth and Environmental Sciences, achieved with excellent recoveries and satisfactory blank levels, can be used prior to high precision analysis of ultra-trace elements in geological samples by ICP-Mass Spectrometry.     

Bridging the gap between homogeneous and heterogeneous catalysis: ortho/para H(2) conversion, hydrogen isotope scrambling, and hydrogenation of olefins by Ir(CO)Cl(PPh(3))(2)

Some transition metal complexes are known to catalyze ortho/para hydrogen conversion, hydrogen isotope scrambling, and hydrogenation reactions in liquid solution. Using the example of Vaska's complex, we present here evidence by NMR that the solvent is not necessary for these reactions to occur. Thus, solid frozen solutions or polycrystalline powdered samples of homogeneous catalysts may become heterogeneous catalysts. Comparative liquid- and solid-state studies provide novel insight into the reaction mechanisms.     

Coordination and Dehydrogenation of Amine–Boranes at Metal Centers

There have been a number of approaches developed for the catalyzed dehydrogenation of amine–boranes as potential dihydrogen sources for hydrogen storage applications in recent years. Key advances in this area have been recently made thanks to catalytic and stoichiometric studies. In this Minireview, the fate of amine–boranes upon coordination to a metal center is discussed with a particular emphasis on B? H activation pathways. We focus on the few cases in which coordination of the resulting dehydrogenated product could be achieved, which includes the coordination of aminoborane, the simplest unit resulting from dihydrogen release of ammonia–borane.     

A Highly Effective Ruthenium System for the Catalyzed Dehydrogenative Cyclization of Amine–Boranes to Cyclic Boranes under Mild Conditions

We recently disclosed a new ruthenium‐catalyzed dehydrogenative cyclization process (CDC) of diamine–monoboranes leading to cyclic diaminoboranes. In the present study, the CDC reaction has been successfully extended to a larger number of diamine–monoboranes ( 4 – 7 ) and to one amine–borane alcohol precursor ( 8 ). The corresponding NB(H)N‐ and NB(H)O‐containing cyclic diaminoboranes ( 12 – 15 ) and oxazaborolidine ( 16 ) were obtained in good to high yields. Multiple substitution patterns on the starting amine–borane substrates were evaluated and the reaction was also performed with chiral substrates. Efforts have been spent to understand the mechanism of the ruthenium CDC process. In addition to a computational approach, a strategy enabling the kinetic discrimination on successive events of the catalytic process leading to the formation of the NB(H)N linkage was performed on the six‐carbon chain diamine–monoborane 21 and completed with a ¹⁵N NMR study. The long‐life bis‐σ‐borane ruthenium intermediate 23 possessing a reactive NHMe ending was characterized in situ and proved to catalyze the dehydrogenative cyclization of 1 , ascertaining that bis σ‐borane ruthenium complexes are key intermediates in the CDC process.     

Phosphinoborane and Sulfidoborohydride as Chelating Ligands in Polyhydride Ruthenium Complexes: Agostic σ‐Borane versus Dihydroborate Coordination

A question of coordination mode : Two new borane compounds are prepared. They act as bifunctional ligands as illustrated by their reaction with ruthenium polyhydrides which leads to the formation of two complexes (see scheme) displaying either a δ‐agostic interaction of a η²‐B? H bond involving a trivalent boron atom or a dihydroborate ligation.