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Theses

Méthodes de modélisation en synthèse asymétrique : étude de la réduction d'a-cétoesters glycosylés

Abstract : The objective of this work is to interpret experimental results of the stereo-controlled reduction of glycosyl a- ketoesters through quantum mechanical computational. Indeed, experimental data for the diastereoselectivity seem to be in contradiction with the predictions made by Corey's model. DFT calculations for a series of model systems show that the low flexibility of the ketoester group may explain such differences in selectivity. Moreover, the catalyst-reagent-borane complexes are not stable. In order to study systems of experimental interest, the semiempirical approach PM3 has been used. The standard approach predicts an erroneous selectivity due to a bad parameterization of the core-core repulsion functions. In this work, we have proposed a new parametrization of the method that largely improve the description of reaction mechanism in asymmetric synthesis.
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Submitted on : Thursday, March 29, 2018 - 10:46:04 AM
Last modification on : Thursday, September 24, 2020 - 2:06:14 PM

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Walid Harb. Méthodes de modélisation en synthèse asymétrique : étude de la réduction d'a-cétoesters glycosylés. Autre. Université Henri Poincaré - Nancy 1, 2003. Français. ⟨NNT : 2003NAN10168⟩. ⟨tel-01746848⟩

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