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Activation d'électrophiles peu communs pour des couplages catalysés au cobalt : réactions et mécanisme

Abstract : This research project led to the development of new coupling reactions catalysed by relatively abundant metal, cobalt, and involving coupling partners more available or easily synthesised from biomass sources. The first chapter is dedicated to the implementation of Negishi-type couplings through the activation of amide derivatives in order to form diverse asymmetrical ketones with simple and robust setups. The second chapter reveals the first examples of catalytic coupling reactions involving C–CN activation from benzonitrile derivatives with cobalt and includes the setting-up of (i) a cross-electrophile coupling between benzonitriles and aryl halides in order to synthesize various biaryl compounds and (ii) a cyanation method of halogenated arenes thanks to a simple carbonated non-toxic cyanatingagent. Besides, the understanding of the processes involved in metal-catalysed coupling reactions is crucial for both the improvement of known methodologies and the design of new ones. Therefore, the third chapter details the mechanistic study carried outto better understand the aforementioned cross-electrophile coupling. Mechanistic insights obtained includingcharacterisation of active species as well as cyclic voltammetry, and supported by DFT calculations, suggest a mechanism involving a ligand exchange step from two different low-valent cobalt species of different oxidation states. Finally, the desire determine more precisely an active cobalt species towards benzonitrile derivatives led to the discovery of two new low-valent cobalt complexes, which reactivity towards various electrophiles, including benzonitriles, has been evaluated.
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Céline Dorval. Activation d'électrophiles peu communs pour des couplages catalysés au cobalt : réactions et mécanisme. Catalyse. Institut Polytechnique de Paris, 2020. Français. ⟨NNT : 2020IPPAX089⟩. ⟨tel-03160955⟩

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