Calix[6]arènes présentant une chiralité inhérente

Abstract : Inherent chiralty, which arises from a concave structure associated with asymetric substitution, is the most common form of chiralty and is fundamental in enzymatic recognition : although aminoacids have an asymetric center, the folding of proteins creates the inherently chiral active site of enzymes and is responsible for the extraordinary selectivity of enzymatic reactions. Calix[6]arenes have been used as a tool to study complex enzymatic processes. They have also been used to build artificial molecular receptors for cations, anions or neutral molecules through very specific interactions. The goal of this thesis is the synthesis of inherently chiral calix[6]arenes by introducing different functionalities devoid of asymetric centers, and the study of the recognition of chiral molecules. First, we developped a biomimetic and supramolecular strategy to monofunctionalize a zinc calix[6]arene complex bearin three imidazole arms or a tris(2-aminoethyl)amine cap, with high selectivity. By using the recognition abilities of theses substrates, several molecules were liked only one of the three equivalent sites of the big rim of the calixarene. The limits of the biomimetic « monoclick » reaction were also quantified. The monofunctionalized complexes are new objects whose abilities as molecular receptors greatly differ from the previous « funnel complexes » described by our team. The control of the access of the cavity of Zn(II), Cu(II) and Cu(I) complexes to exogenous ligands was thoroughly studied with different competitive ligands. Also, we proved that the access to the cavity could be controled with an electrochemical switch. We also developed strategies to synthesize inherently chiral calix[6]arenes from monofunctionalized complexes and we synthesized the first inherently chiral funnel complex. Its chirality was evidenced by the inclusion of chiral and achiral guests. We also provided the proof of concept that these particular phenomena could be simply studied with 19F NMR spectroscopy.
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Nicolas Menard. Calix[6]arènes présentant une chiralité inhérente. Chimie organique. Université René Descartes - Paris V, 2012. Français. ⟨NNT : 2012PA05P657⟩. ⟨tel-01154339⟩

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