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Vers le contrôle de la chiralité axiale des (hétéro)biaryles en l’absence de métaux de transition via le couplage

Abstract : The aim of this thesis work was to provide novel access to axially chiral heterobiaryls following a transition metal free atropoenantioselective synthetic route. This project combines the Csp2-Csp2 Aryne coupling methodology, and an enantioselective approach, the ICE concept (ionic chiral environment). This concept relies on the implementation of chiral ligands as metal (Li) stabilizers with organolithium coupling partners. The chiral environment resulting from the chiral aggregates obtained must induce chirality during the coupling step. The first part of this work aimed to develop an heterocyclic version of the Aryne route in achiral conditions. The results of this study revealed a clear correlation between the electronic nature of the heterocyclic partner and its reactivity in the Aryne coupling. Thiophene, especially, proved to furnish promising results and allowed us to further develop the method. Second part of this work aimed to develop the reaction in the appropriate solvent conditions so that chiral mixed metal aggregates could be envisioned. This study outlined the remarkable effect of external chelating ligands (polyethers, polyamines, aminoalkoxides,…) and salt additives (Li, Zn, K,…) on the aryne coupling reaction in apolar media. The best reaction conditions emerging from this work were then successfully applied to others heterocyclic coupling partners. In parallel, theoretical calculations using density functional theory showed good agreement with experimental work and allowed us to propose mechanistic scheme for the reaction. Last part of this work focused on the reaction of hindered heterocyclic coupling partners with thiophene and benzothiophene derivatives
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Submitted on : Thursday, April 18, 2019 - 8:55:59 AM
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Catherine Demangeat. Vers le contrôle de la chiralité axiale des (hétéro)biaryles en l’absence de métaux de transition via le couplage. Chimie organique. Université de Lorraine, 2018. Français. ⟨NNT : 2018LORR0232⟩. ⟨tel-02103051⟩



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