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 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.     

Structures de Hodge mixtes et faisceaux réflexifs semistablesMixed Hodge structures and semistable reflexive sheaves

Let X be a smooth projective variety over an algebraically closed field of characteristic 0. We prove that the category of μ-semistable reflexive sheaves of slope μ equivariant for the action of some group on X is Abelian. The same claim for $\text{X=}\text{P}{}^2{}_{\mathrm{<mtext>C</mtext>}}$ and a stronger semistability condition gives us a geometric proof of the fact that the category of mixed Hodge structures is Abelian. To cite this article: O. Penacchio, C. R. Acad. Sci. Paris, Ser. I 335 (2002) 475–480.     

Expedient synthesis of villosin and its isomer (E)-labda-8(17),12,14-trien-15(16)-olide

The synthesis of the title compounds has been achieved in concise, highly regiocontrolled fashion from commercially available (+)-sclareolide. In addition, we offer evidence that the structure of a newly reported natural product from Zingiber ottensii is incorrect.     

Total synthesis of malayamycin A and analogues

The total synthesis of the bicyclic C-nucleoside malayamycin A is described starting with d-ribonolactone. A new method was developed to obtain preparatively important quantities of β-pseudouridine, which was used as an intermediate. The synthesis of a carba N-nucleoside analogue of malayamycin A is also described.     

Well-posed absorbing layer for hyperbolic problems

Summary. The perfectly matched layer (PML) is an efficient tool to simulate propagation phenomena in free space on unbounded domain. In this paper we consider a new type of absorbing layer for Maxwell's equations and the linearized Euler equations which is also valid for several classes of first order hyperbolic systems. The definition of this layer appears as a slight modification of the PML technique. We show that the associated Cauchy problem is well-posed in suitable spaces. This theory is finally illustrated by some numerical results. It must be underlined that the discretization of this layer leads to a new discretization of the classical PML formulation. Received May 5, 2000 / Published online November 15, 2001