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Development of new copper-catalyzed cross-coupling reactions

par Grosso, Simone
Président du jury Delcorte, Arnaud
Promoteur Evano, Gwilherm ;Riant, Olivier
Publication Non publié, 2023-11-23

Thèse de doctorat

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Résumé :

Since everything we know and around us is made of atoms and molecules, organic chemistry is intimately part of our daily life. Among all the different areas of study of organic chemistry, catalysis is an extremely important area of chemistry for the development of new catalytic systems and new reactions. Utilizing transition metals as catalysts for novel reactions led to a fundamentally significant advancement in organic synthesis by enabling the discovery of previously unheard of reactions and, most importantly, new methods for forming chemical bonds between atoms. Because metal-catalyzed reactions have fundamentally changed the logic by which disconnections are made and organic molecules are synthesized, they are widely used in both industry and academia. Recently, copper-catalyzed cross-coupling reactions have been extended to carbonylative ones. In this context, the research work carried out during the course of this thesis is devoted to the development of new copper-catalyzed carbonylative cross-coupling reactions for the preparation of carbonyl derivatives. In addition, still remaining in the domain of copper catalysis, a second independent subject dedicated to the development of a new synthetic strategy for the preparation of trifluoromethylated alkenes based on a broadly applicable copper-catalyzed trifluoromethylation of vinylsiloxanes was studied in our laboratory. Therefore, this manuscript will be, quite naturally, divided into two distinct parts which will focus on the development of new copper-catalyzed carbonylative cross-coupling reactions (part 1) and the development of a new copper-catalyzed cross-coupling for the trifluoromethylation of vinylsiloxanes (part 2). These two subjects will be discussed in detail in the four chapters of this manuscript. The first chapter will consist of a bibliographical study which will aim to place the first part of this work in its context and which will be devoted to a literature overview of copper-catalyzed carbonylative cross-coupling reactions. A presentation of the most modern catalytic systems available for the formation of carbonyl derivatives will be presented with a detailed discussion of the selected articles. The second chapter will be devoted to the results obtained for the development of the first copper-catalyzed carbonylative cross-coupling reaction between aryl iodides and amines. Firstly, the optimization for the development of the copper-catalyzed carbonylative cross-coupling by a systematic variation of all crucial parameters will be presented. Then, with a methodical variation of the nature of both reaction partners the scope of this chemical transformation and its limitations will be described. The third chapter will first provide a brief introduction on the formation and reactivity of acylzirconocene complexes. Then, the results obtained for the development of a novel approach for the synthesis of aryl-alkyl ketones via a copper-catalyzed carbonylative arylation using alkyl acylzirconocene chlorides, readily prepared from alkenes and carbon monoxide, will be discussed in detail. The fourth chapter will start with a brief bibliographic introduction for the synthesis of trifluoromethylated alkenes, which will be followed by a discussion of the results obtained for the development of a new method for the preparation of trifluoromethylated olefins based on a broadly applicable copper-catalyzed trifluoromethylation of vinylsiloxanes, starting materials that are readily prepared, in a divergent manner, from alkynes. Finally, a general conclusion and an experimental part will close this manuscript.