Complexes de zirconocènes comme intermédiaires pour la synthèse de pyrrolidines et l'allylation d'imines

Abstract : This memory deals with the use of zirconocenes for the asymmetric synthesis of pyrrolidines and the allylation of imines. In the first part of this work, the hydrozirconation/cyclization sequence has been applied to the preparation of pyrrolidine-based ligands for asymmetric catalysis. A range of ligands incorporating ferrocenyl moieties with controlled planar chirality has been preparated in this way, and tested in Tsuji-Trost reaction. In the second part, another application is presented: the synthesis of constrained amino-acids analogs. Thus, phenylalanine and tryptophane analogs were preparated in the optically pure form. The synthesis of the tryptophane derivative required the development of a new protocol for generating allylzirconocene bearing indole moieties. The last part concerns the generalization of this methodology using low valent zirconium chemistry (ZrII). A number of allylzirconocenes bearing heteroaromatic groups have been prepared and coupled with imines. An unprecedented control of α/γ regiochemistry was achieved, depending on the imine structure.
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Pierre-Olivier Delaye. Complexes de zirconocènes comme intermédiaires pour la synthèse de pyrrolidines et l'allylation d'imines. Chimie organique. Université de Reims Champagne-Ardenne, 2010. Français. ⟨tel-01824947⟩

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