Ring-opening carbonyl–olefin metathesis of norbornenes

A computational and experimental study of the hydrazine-catalyzed ring-opening carbonyl–olefin metathesis of norbornenes is described. Detailed theoretical investigation of the energetic landscape for the full reaction pathway with six different hydrazines revealed several crucial aspects for the design of next-generation hydrazine catalysts. This study indicated that a [2.2.2]-bicyclic hydrazine should offer substantially increased reactivity versus the previously reported [2.2.1]-hydrazine due to a lowered activation barrier for the rate-determining cycloreversion step, a prediction which was verified experimentally. Optimized conditions for both cycloaddition and cycloreversion steps were identified, and a brief substrate scope study for each was conducted. A complication for catalysis was found to be the slow hydrolysis of the ring-opened hydrazonium intermediates, which were shown to suffer from a competitive and irreversible cycloaddition with a second equivalent of norbornene. This problem was overcome by the strategic incorporation of a bridgehead methyl group on the norbornene ring, leading to the first demonstrated catalytic carbonyl–olefin metathesis of norbornene rings.

A computational and experimental study has uncovered a second generation hydrazine that enables the catalytic ring-opening carbonyl–olefin metathesis of norbornenes.     

Controllable growth of chains and grids from polyoxomolybdate building blocks linked by silver(I) dimers

Molecular growth processes utilizing a beta-octamolybdate synthon and {Ag2} dimers are described and the directing influence of "encapsulating" cations and coordinating solvent is also demonstrated. The growth of two 1D chains, (nBu4N)2n[Ag2Mo8O26]n (1) and (nBu4N)2n[Ag2Mo8O26(CH3CN)2]n (2), is achieved when nBu4N+ ions are used, and the diameter of the chains can be expanded by the coordination of CH3CN solvent (2). The formation of a type of gridlike structure in which 1D chains are crossed-over each other in alternatively packed layers is achieved in DMSO as the solvent; DMSO acts as a linking group to give (nBu4N)2n[Ag2Mo8O26(dmso)2]n (3), which, similar to 1 and 2, still incorporates the Bu4N+ ions that exert an "encapsulating" influence. However, in (HDMF)n[Ag3(Mo8O26)(dmf)4]n (4) the relatively bulky Bu4N+ ions are exchanged for protonated DMF cations, thereby allowing the chains to condense to a 2D array. The building block concept is further enforced by the isolation of a "monomeric" unit (Ph4P)2[Ag2Mo8O26(dmso)4] (5), which is isolated when the Ph4P+ ions are so "encapsulating" as to prevent aggregation of the {Ag-Mo8-Ag} building blocks. The nature of the AgAg dimers in each of the compounds 1-4 is examined by DFT calculations and the interplay between these Ag-Ag interactions and the structure types is described.     

Photoinduced morphism of gemini surfactant aggregates

The photochemical behaviour of an azobenzene chromophore inserted in a gemini surfactant imparts photocontrol to the resulting amphiphile assemblies, including the collapse, upon irradiation, of the multi lamellar vesicles formed in aqueous solution.     

Efficient synthesis of [3H]-sanglifehrin A via selective oxidation/reduction of alcohols at C31 and C35

[Reaction: see text]. Sanglifehrin A is a novel complex natural product showing strong immunosuppressive activity and remarkably high affinity for cyclophilin A. To assess its pharmacokinetic properties in vivo, an efficient synthetic route was developed to introduce a tritium label in position C35 of sangliferin A via an oxidation/reduction strategy. The synthetic approach is particularly attractive, because the C35-oxo intermediate 7 is available in good yield on large scale and the reducing agent, lithium tri-sec-butylborotritide, is readily available. An attempt to apply a similar strategy to the alcohol in position C31 led primarily to C31-epi-hydroxy sanglifehrin A under a variety of conditions.     

Determination of 2-mercaptopropionylglycine and its metabolite, 2-mercaptopropionic acid, in plasma by ion-pair reversed-phase high-performance liquid chromatography with post-column derivatization.

A simple and fast high-performance liquid chromatographic method was developed for the simultaneous measurement of 2-mercaptopropionylglycine (Tiopronine) and its metabolite (2-mercaptopropionic acid) in human plasma after the administration of a pharmaceutical dosage form (Acadione). The sample treatment before high-performance liquid chromatographic analysis consisted of the reduction of the corresponding disulphides by tri-n-butylphosphine and protein precipitation with ethanol. Separation was achieved by ion-pair high-performance liquid chromatography on a reversed-phase column (LiChrospher RP 18e) with cetrimonium bromide as counter ion and detection by fluorimetry after post-column derivatization with a selective thiol reagent, i.e. pyrenemaleimide. The high frequency of the analyzed samples and validation results make the method suitable for pharmacokinetic studies, and this was demonstrated by the first results obtained after the administration of an oral dose of 500 mg of Tiopronine to two healthy subjects.     

Arsenic speciation in marine organisms: from the analytical methodology to the constitution of reference materials

An analytical procedure for total arsenic and arsenic species quantification in marine organisms has been developed. Fresh materials are freeze-dried and reduced to powders before analysis. Arsenic is determined either by energy dispersive X-ray fluorescence (EDXRF) directly or by inductively coupled plasma optical emission spectrometry (ICP/OES) after microwave digestion. Arsenic speciation is performed on the extracted sample using liquid chromatography coupled to ICP/OES for arsenobetaine and arsenocholine determination and to the hydride generation-quartz furnace atomic absorption spectrometric technique for arsenite, arsenate, monomethylarsonic and dimethylarsinic acids quantification. Special precautions are taken to avoid losses or contaminations as well as to prevent analytical errors during the quantification stage. Other methods are applied and the corresponding results compared for each step of the procedure. The method is finally validated by means of intercomparison studies within the Measurements and Testing Programme of the European Community (formely BCR).     

Asymmetric [2,3]-rearrangement of glycine-derived allyl ammonium ylids

The first examples of highly enantioselective [2,3]-sigmatropic rearrangements of acyclic allylic ammonium ylids are reported. Thus, a range of N-{2'-[(N'-allyl-N',N'-dialkyl)ammonium]}acetyl camphor sultams undergo rearrangement at 0 degrees C in DME solution with high diastereofacial control (up to 99:1 dr) to give allylglycines in generally high yield. The power of the method has been demonstrated in a rapid and efficient synthesis of (R)-allyl glycine.     

Electroactive ligands: the first metal complexes of tetrathiafulvenyl-acetylacetonate

The reaction of tris(alkylthio)tetrathiafulvalene thiolates with 3-chloro-2,4-pentanedione affords tetrathiafulvalene (TTF) moieties substituted by the acetylacetone function (TTFSacacH), precursors of novel redox-active ligands: the acetylacetonate ions (TTFSacac). These TTFSacacHs have been characterized by X-ray diffraction analyses, and similar trends have been observed, such as a TTF core almost planar and the acetylacetone substituent located in a plane almost perpendicular to the plane formed by the TTF core. Their chelating ability has been demonstrated by the formation of the corresponding M(TTFSacac)2(pyridine)2 complexes in the presence of M(II)(OAc)2.H2O (M = Ni2+, Zn2+). These complexes with TTFSacac moieties, Ni(TTFSacac)2(pyridine)2, 6b, and Zn(TTFSacac)2(pyridine)2, 7b, have been characterized by X-ray diffraction analyses, showing in all structures the metal(II) center chelated by two TTFacac units in the equatorial plane and the octahedral coordination geometry around the metal completed by two axial pyridine ligands. Cyclic voltammetry and UV-visible-near infrared spectroscopic measurements have evidenced a sizable interaction between the two electroactive ligands and the stabilization of a mixed-valence state in the one-electron oxidized complexes.     

Condensation du complexe hexafluoroacetone - fluorure de potassium sur les cetones alpha - halogenees

During its condensation with α-halo ketones, the hexafluoro- acetone-potassium fluoride complex behaves as a weak nucleophile and a strong base. Nucleophilic substitution produces α-perfluoroalkoxy ketones. Abstraction of a proton α to the carbonyl function leads to the formation of ether-ketones substituted by the group C(CF₃)₂. In some cases, hydrogen halide elimination can occur.