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     

Recurrence and genericity

We prove a C¹-connecting lemma for pseudo-orbits of diffeomorphisms on compact manifolds. We explore some consequences for C¹-generic diffeomorphisms. For instance, C¹-generic conservative diffeomorphisms are transitive. To cite this article: C. Bonatti, S. Crovisier, C. R. Acad. Sci. Paris, Ser. I 336 (2003).     

Triangulations in CGAL

This paper presents the main algorithmic and design choices that have been made to implement triangulations in the computational geometry algorithms library .     

Sur les immeubles triangulaires et leurs automorphismes

Résumé  Les travaux de J. Tits ont conduit à la classification complète des immeubles euclidiens de dimension supérieure ou égale à 3. L’ensemble de ces immeubles à isomorphisme près est dénombrable et paramétré par les corps locaux qui leur correspondent. Dans cet article nous nous intéressons aux immeubles triangulaires, qui sont euclidiens de dimension 2 et pour lesquelles une paramétrisation analogue est impossible. Nous construisons une lamination Λ sur un espace topologique localement compact séparé, dont l’espace des feuilles est l’ensemble des immeubles triangulaires à isomorphisme près. On considère ainsi les immeubles triangulaires comme points d’un espace dont Λ est une désingularisation naturelle. Nous établissons des résultats de chirurgie sur les immeubles triangulaires à données locales fixées. Ils entra?nent par exemple que Λ est topologiquement transitive. Nous montrons qu’un immeuble triangulaire générique au sens de Baire a un groupe d’automorphismes trivial et qu’il contient toutes les géométries locales possibles. L’espace des immeubles triangulaires à isomorphisme près est un nouvel exemple d’espace non commutatif. Le second auteur a été en partie financé par JSPS.     

Simulation numérique directe de l'influence de la forme aval d'une plaque séparatrice sur une couche de mélangeDirect-numerical simulation of the splitting-plate downstream-shape influence upon a mixing layer

In this Note, we present direct numerical simulation results of a spatial mixing layer generated behind an upstream plate separating two boundary layers. The effect of the shape of the trailing edge of the plate is considered through comparisons between flows obtained from a bevelled or a blunt plate. In the former case, a spatial mixing layer consistent with previous experimental and numerical observations is obtained. In the latter case, the self-excited state that establishes in the near wake region dominates primary and secondary instability mechanisms while understating the importance of inflow perturbations. This behaviour is interpreted in terms of convective or absolute instability. The effects on turbulent statistics are also discussed. To cite this article: S. Laizet, E. Lamballais, C. R. Mecanique 334 (2006).     

On the maslov index

In this paper we give four definitions of Maslov index and show that they all satisfy the same system of axioms and hence are equivalent to each other. Moreover, relationships of several symplectic and differential geometric, analytic, and topological invariants (including triple Maslov indices, eta invariants, spectral flow and signatures of quadratic forms) to the Maslov index are developed and formulae relating them are given. The broad presentation is designed with a view to applications both in geometry and in analysis. © 1994 John Wiley & Sons, Inc.     

SG1 based alkoxyamines as radical initiators for the synthesis of lactones and lactames

Recently, it has been shown that alkoxyamines can be used as radical initiators in tin-free radical chemistry. Thus, it prompted us to develop the preparation of highly valuable alkoxyamines via ionic chemistry and the radical cyclization was triggered by thermal initiation. Following that procedure, bicyclic, spiro and eight-membered lactones were easily prepared in good yields with very high stereoselectivity.     

Méthode d'homogénéisation auto-cohérente en calcul à la ruptureSelf-consistent homogeneization method in yield design

This work is aimed towards determining the macroscopic strength criterion of a heterogeneous material with a random microstructure. We use the self-consistent concept by considering a reference material, which is of same nature as the constituents of the heterogeneous material. We deduce that the estimates of the macroscopic strength domain are the solutions to self-consistent equations and we give their derivation procedure. To cite this article: S. Turgeman, B. Guessab, C. R. Mecanique 330 (2002) 623–626.     

Computational Studies on Intramolecular Cycloadditions of Azidoenynes and Azidobutenenitriles to Give 6H‐Pyrrolo[1,2‐c][1,2,3]triazoles and 5H‐Pyrrolo[1,2‐d]tetrazoles

Energetics of intramolecular cycloadditions of azidoenynes and azidobutenenitriles to give 6H‐pyrrolo[1,2‐c][1,2,3]triazoles and 5H‐pyrrolo[1,2‐d]tetrazoles have been calculated at the B3LYP/6.311++G(3df,3pd) level of theory in ideal gas and in H₂O as solvent. Stabilities of the corresponding anions, tautomers, and isomers are discussed. Transition states of the cyclization of parent compounds are determined at the same level of theory.     

Competitive Gold‐Promoted Meyer–Schuster and oxy‐Cope Rearrangements of 3‐Acyloxy‐1,5‐enynes: Selective Catalysis for the Synthesis of (+)‐(S)‐γ‐Ionone and (−)‐(2S,6 R)‐cis‐γ‐Irone

We report a simple, highly stereoselective synthesis of (+)‐(S)‐γ‐ionone and (‐)‐(2S,6R)‐cis‐γ‐irone, two characteristic and precious odorants; the latter compound is a constituent of the essential oil obtained from iris rhizomes. Of general interest in this approach are the photoisomerization of an endo trisubstituted cyclohexene double bond to an exo vinyl group and the installation of the enone side chain through a [(NHC)Au^I]‐catalyzed Meyer–Schuster‐like rearrangement. This required a careful investigation of the mechanism of the gold‐catalyzed reaction and a judicious selection of reaction conditions. In fact, it was found that the Meyer–Schuster reaction may compete with the oxy‐Cope rearrangement. Gold‐based catalytic systems can promote either reaction selectively. In the present system, the mononuclear gold complex [Au(IPr)Cl], in combination with the silver salt AgSbF₆ in 100:1 butan‐2‐one/H₂O, proved to efficiently promote the Meyer–Schuster rearrangement of propargylic benzoates, whereas the digold catalyst [{Au(IPr)}₂(μ‐OH)][BF₄] in anhydrous dichloromethane selectively promoted the oxy‐Cope rearrangement of propargylic alcohols.