Sels d'aziridinium stables c-fonctionnalisés II: Stéréochimie de la quaternisation,synthèses stérèodirigées de composés n-trideutériométhylés et attribution de leurs configurations relatives par el'fet overhauser nucléaire

Aziridines bearing a functionality on a ring carbon and an alkyl or deuteriomethyal group on nitrogen have been quaternized at different temperatures. The configurations of the resulting, stable, diastereomeric aziridinium ions have been assigned by Nuclear Overhauser effect. The stereoselectivity in quaternization is discussed.     

Maxisets for Model Selection

We address the statistical issue of determining the maximal spaces (maxisets) where model selection procedures attain a given rate of convergence. By considering first general dictionaries, then orthonormal bases, we characterize these maxisets in terms of approximation spaces. These results are illustrated by classical choices of wavelet model collections. For each of them, the maxisets are described in terms of functional spaces. We give special attention to the issue of calculability and measure the induced loss of performance in terms of maxisets.     

Demogenetic study of three populations within a region with strong founder effects

OBJECTIVES: The population of the Saguenay-Lac-St-Jean (SLSJ) region (Quebec, Canada) is known to have a relatively high prevalence of certain hereditary disorders, which can be explained by the consequences of founder effects. This study aims at providing new insights on the origins and subregional stratification of these founder effects. METHODS: The genealogies of 300 individuals were reconstructed and analyzed using the BALSAC population register. RESULTS: Inbreeding and kinship levels are higher in Lower Saguenay than in Upper Saguenay and Lac-St-Jean. The population of Lower Saguenay also distinguishes itself because of a fewer number of distinct ancestors. CONCLUSION: Beyond the genetic features that characterize the whole region, SLSJ also displays intraregional variability. Thus it is important to take into account the settlement patterns and the demographic history of this population for a better appraisal of its contemporary genetic structure.     

Sels d'aziridinium stables,C-fonctionnalisés

Aziridines bearing a functionnality on a ring carbon have been treated with methyl fluorosulfonate to afford the corresponding aziridinium salts in high yields. These compounds were unambiguously characterised by the ring opening reactions using lithium chloride. Two quantitative methods for effecting counter-ion exchange are described.     

Sels d'aziridinium stables C-fonctionnalisés III: Synthèse et caractérisation d'aziridines protonées épimères à l'azote

Aziridinium ions were prepared from aziridines bearing a functionality on a ring carbon and as isolated crystalline fluorosulfate salts either by protonation in fluorosulfuric acid solution or by alkylation with methyl fluorosulfate. The structural assignement of these ions is based on nmr spectra and on quenching experiments with sodium carbonate. The configurations of the epimeric ions have been assigned by the nuclear Qverhauser effect and the stereoselectivity in protonation is disucussed.