Catalytic Nitrene Transfer by an FeIV-Imido Complex Generated by a Comproportionation Process

Nitrene transfer reactions have emerged as one of the most powerful and versatile ways to insert an amine function to various kinds of hydrocarbon substrates. However, the mechanisms of nitrene generation have not been studied in depth albeit their formation is taken for granted in most cases without definitive evidence of their occurrence. In the present work, we compare the generation of tosylimido iron species and NTs transfer from Fe^II and Fe^III precursors where the metal is embedded in a tetracarbene macrocycle. Catalytic nitrene transfer to reference substrates (thioanisole, styrene, ethylbenzene and cyclohexane) revealed that the same active species was at play, irrespective of the ferrous versus ferric nature of the precursor. Through combination of spectroscopic (UV-visible, Mössbauer), ESI-MS and DFT studies, an Fe^IV tosylimido species was identified as the catalytically active species and was characterized spectroscopically and computationally. Whereas its formation from the Fe^II precursor was expected by a two-electron oxidative addition, its formation from an Fe^III precursor was unprecedented. Thanks to a combination of spectroscopic (UV-visible, EPR, Hyscore and Mössbauer), ESI-MS and DFT studies, we found that, when starting from the Fe^III precursor, an Fe^III tosyliodinane adduct was formed and decomposed into an Fe^V tosylimido species which generated the catalytically active Fe^IV tosylimide through a comproportionation process with the Fe^III precursor.     

A hyperbolic three-phase flow model

We introduce a hyperbolic entropy-consistent model to describe three-phase flows, which ensures that void fractions, mass fractions and pressures remain positive through single waves occurring in the one dimensional solution of the Riemann problem. To cite this article: J.-M. Hérard, C. R. Acad. Sci. Paris, Ser. I 342 (2006).     

Kinetics of polarization reversal in irradiated thin PZT films

The effect of irradiation with electrons and neutrons and of exposure to synchrotron radiation on cyclic switching of polarization in thin films of lead zirconate titanate Pb(Zr,Ti)O₃ (PZT) was studied. It is shown that variations in the shape of switching currents are due to the generation of a spatially nonuniform bound internal field with account for an increase in the rate of bulk screening caused by irradiation. A correlation between structural variations and the evolution of the switching current measured during and after irradiation is established.     

Stereoselective synthesis of trifluoromethyl-substituted 1,2-diamines by aza-Michael reaction with trans-3,3,3-trifluoro-1-nitropropene

Aza-Michael addition of optically pure 4-phenyl-2-oxazolidinone to 3,3,3-trifluoro-1-nitropropene proceeds smoothly at low temperature with a high yield. Diastereoselectivity of the addition depends on the base used and lithiated species proved to be highly efficient affording 92% de. Optically pure 1,2-diamino-3,3,3-trifluoropropane is prepared in 58% yield from the aza-Michael addition product through a three-step procedure.     

Improved synthesis of tocopherol fatty alcohols and analogs: microglial activation modulators

The synthesis of tocopherol fatty alcohols (TFAs), potent microglial activation modulators, was achieved via C-alkylation of trimethylhydroquinone. Several analogs, in particular water-soluble prodrugs, have been synthesized using a Wittig reaction and their antioxidant activities have been evaluated.     

Closure laws for a two-fluid two-pressure modelLois de fermeture pour un modèle à deux pressions d'écoulement diphasique

Closure laws for interfacial pressure and interfacial velocity are proposed within the frame work of two-pressure two-phase flow models. These enable us to ensure positivity of void fractions, mass fractions and internal energies when investigating field by field waves in the Riemann problem. To cite this article: F. Coquel et al., C. R. Acad. Sci. Paris, Ser. I 334 (2002) 927–932.     

Intravascular and Intracellular Hepatic Relaxivities of Superparamagnetic Particles: An Isolated and Perfused Organ Pharmacokinetics Study

The relative contributions of intravascular and intracellular compartments to the proton transverse relaxation of the isolated and excised rat liver were determined during the phagocytosis of superparamagnetic particles. The evolution of the proton transverse magnetization of the organ perfused with increasing doses of starch-coated magnetic microspheres was followed up using a Carr–Purcell–Meiboom–Gill sequence with various echo times. From the multiexponential fit of the echo train, the amplitudes and the relaxation ratesR₂of the liver tissue were obtained. The results clearly indicate that shortly after contrast medium administration, an internalization takes place which can be followed by the rapid and biphasic evolution of the transverse relaxation rate of the water protons. A very fast decaying component looking like an initial loss of the magnetization is observed together with an increase of the relaxation rate of the remaining water tissue. This regime is strongly dependent on both the echo time and the iron concentration, a behavior characteristic of the agglomeration of magnetic particles. The examination of the liver tissues by electron microscopy shows that this clustering arises in cytoplasmic vacuoles.     

Ethyl-4,4,4-trifluoroacetoacetate (ETFAA), a powerful building block for enantiopure chirons in trifluoromethyl-β-amino acid series

Herein are studied new transformations of ethyl-4,4,4-trifluoroacetoacetate (ETFAA), giving access to a series of enantiopure chirons bearing both a trifluoromethyl group and an amino moiety. The key intermediate is obtained optically pure by a resolution procedure.