Synthesis of Amides and Esters by Palladium(0)-Catalyzed Carbonylative C(sp3)−H Activation

The 1,4-palladium shift strategy allows the functionalization of remote C−H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp³)−H activation, 1,4-palladium shift, and amino- or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β-carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ-alkylpalladium intermediate arising from the palladium shift is fast using PPh₃ as the ligand, and leads to the amide rather than the previously reported indanone product.     

Detailed experimental and kinetic modeling study of 3-carene pyrolysis

3-Carene is an important potential biofuel with properties similar to the jet-propellant JP-10. Its thermal decomposition and combustion behavior is to date unknown, which is essential to assess its quality as a fuel. A combined experimental and kinetic modeling study has been conducted to understand the initial decomposition of 3-carene. The pyrolysis of 3-carene was investigated in a jet-stirred quartz reactor at atmospheric pressure, at temperatures varying from 650 to 1050 K, covering the complete conversion range. The decomposition of 3-carene was observed to start around 800 K, and it is almost complete at 970 K. Online gas chromatography shows that primarily aromatics are generated which suggests that 3-carene is not a good fuel candidate. The potential energy surface for the initial decomposition pathways determined by KinBot shows that a hydrogen elimination reaction dominates, giving primarily cara-2,4-diene. Next to this molecular pathway, radical pathways lead to aromatics via ring opening. The kinetic model was automatically generated with Genesys and consists of 2565 species and 9331 reactions. New quantum chemical calculations at the CBS-QB3 level of theory were needed to calculate rate coefficients and thermodynamic properties relevant for the primary decomposition of 3-carene. Both the conversion of 3-carene and the yields of the primary products (ie, benzene and hydrogen gas) are well predicted with this kinetic model. Rate of production analyses shows that the dominant pathways to convert 3-carene are hydrogen elimination reaction and radical chemistry.     

Highlights on the Binding of Cobalta-Bis-(Dicarbollide) with Glucose Units

Metalla-bis-dicarbollides, such as the cobalta-bis-dicarbollide (COSAN) anion [Co(C₂B₉H₁₁)₂]⁻, have attracted much attention in biology but a deep understanding of their interactions with cell components is still missing. For this purpose, we studied the interactions of COSAN with the glucose moiety, which is ubiquitous at biological interfaces. Octyl-glucopyranoside surfactant (C8G1) was chosen as a model as it self-assembles in water and creates a hydrated glucose-covered interface. At low COSAN content and below the critical micellar concentration (CMC) of C8G1, COSAN binds to C8G1 monomers through the hydrophobic effect. Above the CMC of C8G1, COSAN adsorbs onto C8G1 micelles through the superchaotropic effect. At high COSAN concentrations, COSAN disrupts C8G1 micelles and the assemblies become similar to COSAN micelles but with a small amount of solubilized C8G1. Therefore, COSAN binds in a versatile way to C8G1 through either the hydrophobic or superchaotropic effect depending on their relative concentrations.     

An experimental and modeling study of the oxidation of n-heptane,ethylbenzene, and n-butylbenzene in a jet-stirred reactor at pressures up to 10 bar

In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C₇ diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C₈ fuels and of 19 products for the C₁₀ one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities.     

Application of Tsunoda reagent to the convenient synthesis of drug-like pyrazoles

The versatility of the under-utilised (cyanomethylene)tributylphosphorane (CMBP, Tsunoda reagent) was demonstrated on two occasions in a drug discovery context. Firstly, the high reactivity of the phosphorane allowed the alkylation of a weakly acidic pyrazole when standard Mitsunobu conditions were unsuccessful. Secondly, the clean reaction profile generally obtained using CMBP allowed the direct use of the crude mixture in a subsequent Suzuki cross coupling. This reagent has utility when isolation of the Mitsunobu reaction product (e.g. containing a boronate) is not desirable.     

Optimal asset allocation for pension funds under mortality risk during the accumulation and decumulation phases

In a financial market with one riskless asset and n risky assets whose prices are lognormal, we solve in a closed form the problem of a pension fund maximizing the expected CRRA utility of its surplus till the (stochastic) death time of a representative agent. We consider a unique asset allocation problem for both accumulation and decumulation phases. The optimal investment in the risky assets must decrease during the first phase and increase during the second one. We accordingly suggest it is not optimal to manage the two phases separately, and outsourcing of allocation decisions should be avoided in both phases. JEL: G23, G11 MSC 2000: 62P05, 91B28, 91B30, 91B70, 93E20     

A counter-example to the characterization of the discontinuous value function of control problems with reflectionUn contre-exemple à la caractérisation de la fonction-valeur discontinue d'un problème de contrôle réfléchi

We consider a finite horizon deterministic optimal control problem with reflection. The final cost is assumed to be merely a locally bounded function which leads to a discontinuous value function. We address the question of the characterization of the value function as the unique solution of an Hamilton–Jacobi equation with Neumann boundary conditions. We follow the discontinuous approach developed by Barles and Perthame for problems set in the whole space. We prove that the minimal and maximal discontinuous viscosity solutions of the associated Hamilton–Jacobi can be written in terms of value functions of control problems with reflection. Nethertheless, we construct a counter-example showing that the value function is not the unique solution of the equation. To cite this article: O. Ley, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 469–473.     

Observations of cavitation erosion pit formation

Previous investigations showed that a single cavitation bubble collapse can cause more than one erosion pit (Philipp & Lauterborn [1]). But our preliminary study showed just the opposite – that in some cases a single cavitation pit can result from more than one cavitation event. The present study shows deeper investigation of this phenomenon. An investigation of the erosion effects of ultrasonic cavitation on a thin aluminum foil was made. In the study we observed the formation of individual pits by means of high speed cameras (>1000 fps) and quantitatively evaluated the series of images by stereoscopy and the shape from shading method. This enabled the reconstruction of the time evolution of the pit shape. Results show how the foil is deformed several times before a hole is finally punctured. It was determined that larger single pits result from several impacts of shock waves on the same area, which means that they are merely special cases of pit clusters (pit clusters where pits overlap perfectly). Finally it was shown that a thin foil, which is subjected to cavitation, behaves as a membrane. It was concluded that the physics behind erosion depends significantly on the means of generating cavitation (acoustic, hydrodynamic, laser light) and the specimen characteristics (thin foil, massive specimen), which makes comparison of results of materials resistance to cavitation from different experimental set-ups questionable.Further development of the shape from shading method in the scope of cavitation erosion testing will enable better evaluation of cavitation erosion models.     

Use of a microelectromechanical mirror for adaptive optics in the human eye

Ophthalmic instrumentation equipped with adaptive optics offers the possibility of rapid and automated correction of the eye's optics for improving vision and for improving images of the retina. One factor that limits the widespread implementation of adaptive optics is the cost of the wave-front corrector, such as a deformable mirror. In addition, the large apertures of these elements require high pupil magnification, and hence the systems tend to be physically large. We present what are believed to be the first closed-loop results when a compact, low-cost, surface micromachined, microelectromechanical mirror is used in a vision adaptive-optics system. The correction performance of the mirror is shown to be comparable to that of a Xinetics mirror for a 4.6-mm pupil size. Furthermore, for a pupil diameter of 6.0-mm, the residual rms error is reduced from 0.36 to 0.12 microm and individual photoreceptors are resolved at a pupil eccentricity of 1 degrees from the fovea.