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Theses

Structure d'agrégats mixtes impliquant des amidures chiraux : Etude par RMN multinoyaux 1H / 6Li / 13C / 15N et calculs DFT

Abstract : Chiral 3-aminopyrrolidine lithium amides (3APLi) form mixed aggregates with
alkyllithium compounds (3APLi : AlkLi) that have been fully characterized in solution. A
multinuclear (1H/6Li/13C/15N) low-temperature NMR study and a set of Density
Functional Theory calculations were performed during this thesis showing that:
- lithium chelation forces the 3APLi to adopt a norbornyle-like conformation, a
point fully confirmed by a double labeling experiment (15N intracyclic
nitrogen and 6Li amide and methyllithium);
- lithium halides LiX (X = Cl, Br) tend to form very robust 3APLi : LiX mixed
complexes. It has been found that methyllithium is rapidly, totally and
irreversibly chased out of the 3APLi : AlkLi mixed aggregate when a lithium
halide is added to the medium;
- 3APLi aggregate indifferently with two different alkyllithiums as
demonstrated with a MeLi and nBuLi mixture.
Those analysis and observations are in good overall agreement with most chemical
observations and e.e. variations observed at the bench level.
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Franck Pate. Structure d'agrégats mixtes impliquant des amidures chiraux : Etude par RMN multinoyaux 1H / 6Li / 13C / 15N et calculs DFT. Autre. Université de Rouen, 2006. Français. ⟨tel-00158084⟩

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