Theoretical study of rhodium(I) carbene complexes: the structural versatility of phosphino- compared with aminocarbenes

Density functional calculations are reported for complexes of general formula [(carbene)RhClL(2)] featuring model phosphino- and aminocarbenes. Both the cis and trans isomers of the rhodium(I) eta(1)-complexes (1-9) were investigated, and the influence of the rhodium co-ligands (L=ethylene, phosphine, or carbon monoxide) was evaluated. In the case of phosphinocarbenes and carbon monoxide as a ligand, a somewhat unusual coordination mode was observed, in which a significant intramolecular Cl-->C(carbene) interaction is present. The propensity of phosphino- and aminocarbenes to behave as four electron donors was also investigated both structurally and energetically on the related eta(2)-complexes 10-18. These results as a whole emphasize the structural versatility of phosphino- compared with aminocarbene complexes.     

Tetrahydroxydiboron (Bis-boric Acid): a Versatile Reagent for Borylation,Hydrogenation, Catalysis,Radical Reactions and H2 Generation

Diboron compounds with a B−B bond, discovered with B₂Cl₄ a century ago, have been developed only since the turn of this century for catalyzed borylation reactions, mostly with the well-know reagent bis(binacolato)diboron, (B₂pin₂). On the other hand, chemistry of tetrahydroxydiboron (THDB), also named bis-boric acid, is relatively underdeveloped. In this review, the properties of THDB as a borylation, reductant (including transfer hydrogenation), catalyst, source of radicals and generator of H₂ from water upon hydrolysis are summarized.     

U and Pu separation with U/TEVA resin: Influence of some parameters on chromatographic cycle performances

Journal of Radioanalytical and Nuclear Chemistry - Due to unexpected Pu behavior using the U/TEVA resin and the most-recognized reagents, some key separation stages need to be studied for the...     

Two new tetrahydrofuran derivatives from the fungus Mucor spp. SNB-VECD11D isolated from the Chrysomelidae Acalymma bivittula

Two new tetrahydrofuran derivatives, mucorinic acids A (1) and B (2) as well as the three known secondary metabolites dehydroabietic acid (3), Δ8-dihydroabietic acid (4) and 8-pimarenic acid (5) were isolated from a solid culture of the fungus Mucor spp. isolated on insect Acalymma bivittula. The structure of these compounds was elucidated by analysis of NMR and MS spectroscopic data. Compounds were tested in antimicrobial and insecticidal assays. Dehydroabietic acid exhibited moderate larvicidal activity on Aedes aegypti larvae with 65% mortality at 10 ppm. Both new compounds 1 and 2 showed interesting antibacterial activity on Staphylococcus aureus and methicillin resistant S. aureus with MIC values in the 8–16 μg/ml.     

Stereochemical Aspects in the Asymmetric Michael Addition of Chiral Imines to Substituted Electrophilic Alkenes

The Michael-type addition of chiral imines, derived from racemic alpha-substituted cyclanones and optically active 1-phenylethylamine, to electrophilic alkenes, in neutral conditions, constitutes one of the most efficient methods for the stereocontrolled construction of quaternary carbon centers. In order to create an additional stereogenic center at the alpha- or beta-position to the quaternary one, the behavior of a variety of alpha- and beta-substituted alkenyl acceptors was examined. In general, these additions are highly regioselective, the alkylation taking place predominantly, if not exclusively, at the more substituted alpha-side of the imine function; however, in some cases (electrophilic alkenes 28 and 49), significant amounts (10-15%) of regioisomeric adducts were obtained. With the exception of methyl propiolate 52, a remarkable control of the absolute configuration of the adducts were always observed with these Michael acceptors. According to the general rule we have previously proposed, the alkylation process takes place preferentially on the less hindered pi-face of the more substituted secondary enamine, in tautomeric equilibrium with the starting imine. An excellent diastereocontrol was always obtained by using the present alpha- and beta-substituted alkenes. These stereochemical outcomes can be interpreted by invoking that the reaction proceeds through a compact approach of the reactants, the hydrogen atom at the nitrogen center of the enamine being transferred to the alpha-vinylic carbon atom of the acceptor, concertedly with the creation of the C-C bond. In this respect the "endo-approach" 58, in which the electron-withdrawing group of the acceptor faced to the nitrogen atom of the enamine (case of acceptors 10, methyl methacrylate, 24, 28, 43, 47, and 49) largely prevails over the "exo-approach" 59 (case of acceptor 38). This predominant "endo-preference" can be reasonably interpreted in terms of a cooperative effect between steric and stereoelectronic factors.     

Synthesis of Renewable meta‐Xylylenediamine from Biomass‐Derived Furfural

We report the synthesis of biomass‐derived functionalized aromatic chemicals from furfural, a building block nowadays available in large scale from low‐cost biomass. The scientific strategy relies on a Diels–Alder/aromatization sequence. By controlling the rate of each step, it was possible to produce exclusively the meta aromatic isomer. In particular, through this route, we describe the synthesis of renewably sourced meta‐xylylenediamine (MXD). Transposition of this work to other furfural‐derived chemicals is also discussed and reveals that functionalized biomass‐derived aromatics (benzaldehyde, benzylamine, etc.) can be potentially produced, according to this route.     

Homoclinic Solutions for Swift-Hohenberg and Suspension Bridge Type Equations

We establish the existence of homoclinic solutions for a class of fourth-order equations which includes the Swift-Hohenberg model and the suspension bridge equation. In the first case, the nonlinearity has three zeros, corresponding to a double-well potential, while in the second case the nonlinearity is asymptotically constant on one side. The Swift-Hohenberg model is a higher-order extension of the classical Fisher-Kolmogorov model. Its more complicated dynamics give rise to further possibilities of pattern formation. The suspension bridge equation was studied by Chen and McKenna (J. Differential Equations136 (1997), 325-355); we give a positive answer to an open question raised by the authors.     

Dynamics of multiple degree Ginzburg–Landau vortices

For the two-dimensional complex parabolic Ginzburg–Landau equation we prove that, asymptotically, vortices evolve according to a simple ordinary differential equation, which is a gradient flow of the Kirchhoff–Onsager functional. This convergence holds except for a finite number of times, corresponding to vortex collisions and splittings, which we describe carefully. The only assumption is a natural energy bound on the initial data. To cite this article: F. Bethuel et al., C. R. Acad. Sci. Paris, Ser. I 342 (2006).