Palladium catalysis using dendrimers: molecular catalysts versus nanoparticles

Dendritic Pd catalysts, dendrimer-stabilized Pd nanoparticle (PdNP) catalysts, and their comparison and combined use for carbon–carbon coupling reactions are discussed with emphasis on the research carried out in the author’s laboratory during the last decade. Multinuclear star-shaped catalysts rather than dendritic catalysts can reach the efficiency of the best monometallic catalysts, whereas PdNPs stabilized by dendrimers can react with turnover numbers close to 10⁶ and bring useful mechanistic indications. In both areas, leaching issues are examined. Finally, results of the literature in asymmetric Pd catalysis by chiral dendrimers and Pd nanoparticles stabilized by chiral ligands are also reviewed, revealing the importance of the dendritic and molecular ligand design and the role of leaching Pd atoms.     

Green synthesis of para-Menthane-3,8-diol from Eucalyptus citriodora: Application for repellent products

A simple and efficient method was developed for the synthesis of para-Menthane-3,8-diol (PMD), a well-known repellent active against mosquitoes, from Eucalyptus citriodora essential oil by a treatment of citric acid in a biphasic medium (H₂O/essential oil). The E. citriodora contains as main component (+)-citronellal (74% in the present case), which cyclises (Prins reaction) to form cis/trans PMD isomers. As an example, an emulsion containing an aqueous solution of 7% citric acid and E. citriodora oil at 50°, conducted after 15 h stirring to 82% conversion of (+)-citronellal with a selectivity of 80% with the remaining presence of monoterpenes and sesquiterpenes in the medium. Investigations of lasting protection on human volunteers are carried out using a cage test bioassay protocol and Aedes aegypti mosquitoes. At 20% in ⁱPrOH, the new reaction mixture showed a complete protection of 303 min compared to 22 min with the pure essential oil. The modified oil was compared with N,N-diethyl-m-methylbenzamide (DEET), the most popular active used in repellent formulations. Thermogravimetric analyses (TGA) of E. citriodora, the modified oil, PMD, DEET, and (+)-citronellal were performed and showed a slow evaporation rate for PMD and DEET as well as for the modified oil, which may explain their long lasting protection action.     

Generalized Nash equilibrium problem, variational inequality and quasiconvexity

It is well known that the generalized Nash equilibrium problem, a model for multi-leader–follower games, can be reformulated as a quasivariational inequality. We show that, in fact, a reformulation in terms of a variational inequality can be obtained in the general setting of quasiconvex nondifferentiable decision functions. An existence result is deduced.     

Kinetic study of H‐atom transfer in imidazoline‐, imidazolidine‐, and pyrrolidine‐based alkoxyamines: Consequences for nitroxide‐mediated polymerization

The H‐atom transfer reaction was studied for a series of imidazoline, imidazolidine, and pyrrolidine‐based alkoxyamines containing either isobutyrate‐2‐yl or 1‐phenylethyl alkyl fragments. The C O bond homolysis rate constants and activation energies were determined by ¹H NMR product analysis as a function of temperature. Inter‐ and intramolecular H‐atom transfer reactions were distinguished by examination of alkoxyamine thermolysis products in the absence and in the presence of a radical scavenger (thiophenol or deuterated styrene). A correlation between the structure of the nitroxyl fragment of alkoxyamine and the H‐transfer reaction was found. The high steric demands of the substituents on the nitroxyl part of the isobutyrate‐2‐yl alkoxyamine decrease both types of reaction. For alkoxyamines containing the 1‐phenylethoxyamines, neither inter‐ nor intramolecular H‐atom transfer was observed. Controlled polymerization of methylmethacrylate initiated with imidazoline‐based alkoxyamine was observed, although the polymer obtained was not living. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6579–6595, 2009     

Response of periodic structures due to moving loadsRéponse de structures périodiques à des charges mobiles

A method is proposed to calculate the response of periodic structures subjected to moving loads. It is based on the Floquet decomposition which allows the restriction of the analysis for the overall system to a generic cell. The main contribution of the approach presented hereafter is that the response is directly deduced from transfer functions in the space-wavenumber domain calculated in an unbounded generic cell. Moreover, the equivalence of this new solution with the response of invariant structures obtained using Fourier transforms is established. To cite this article: H. Chebli et al., C. R. Mecanique 334 (2006).     

Diferrocenophosphaborin: A Planar‐Chiral,Redox‐Active and Anion‐Responsive Ambiphilic Ligand

A new class of Janus‐like ambiphilic ligands is introduced. The rigid diferrocene backbone in heterocycles 4‐SnP and 4‐BP creates an unprecedented chiral environment as demonstrated by multinuclear NMR and single‐crystal X‐ray studies. In addition, the ligands are redox‐responsive and the Lewis acidic borane moiety in 4‐BP can be exploited to further tune the properties: a clear decrease in the CO stretching frequency of a Vaska‐type Rh^I complex 5‐BP is observed upon addition of fluoride ions. Thus, the Lewis acid and Lewis base sites influence each other and their strength can be modulated by redox chemistry and anion binding.     

Highly Diastereoselective Synthesis of Methylenecyclobutanes by Merging Boron‐Homologation and Boron‐Allylation Strategies

A highly diastereoselective synthesis of methylenecyclobutanes possessing a quaternary stereocenter is reported, in which boron homologation of an easily‐generated cyclobutenylmetal species is performed, followed by an allylation reaction. Combining three steps in a one‐pot process further optimized the method, which afforded the expected adducts in excellent yields and stereoselectivity, starting from commercially available 4‐bromobutyne.