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).     

Quantum information processing in optical images

Optical images can be used to transport, store and process information in a parallel way. We discuss different results obtained in the domain of ‘quantum imaging’, aiming at exploiting at the same time the quantum properties of optical images and their intrinsic parallelism. We define the notion of standard quantum limit (SQL) in optical resolution, set by the quantum noise of usual coherent light, and show that it can be much lower than the diffraction limit. We also prove that this limit can be circumvented by especially designed nonclassical and multimode light. We present an experiment showing that OPOs oscillating inside an exactly confocal cavity actually produce such transverse multimode nonclassical light. We finally describe another experiment which has surpassed the SQL in the case of beam positioning, both in the 1D and 2D cases.     

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.     

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.     

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.     

Transition-metal-templated synthesis of rotaxanes and catenanes: From small molecules to polymers

This article provides an overview of the fundamental principles of the synthesis of metallocatenanes and metallorotaxanes. It also describes the synthesis and properties of electronic conducting polymers—polypyrrole and polythiophene—built around metallocatenanes and metallorotaxanes. The particular properties of this new class of polymers, including the possibility of transmetallation reactions being performed with them and the observation of electronic coupling between the metal centers and the conducting matrix, are discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3470–3477, 2003     

Infinitely renormalizable diffeomorphisms of the disk at the boundary of chaos

We show that, among area contracting embeddings of the 2-disk, infinitely renormalizable maps with a bounded geometry either have positive topological entropy or correspond to a cascade of period doubling.