Development of new copper-catalyzed cross-coupling reactions
(2023)
Files
PhDThesisSimoneGrosso-Developmentofnewcopper-catalyzedcross-couplingreactions.pdf
Open Access - Adobe PDF
- 19.34 MB
Details
- Authors
- Supervisors
- Abstract
- The research work carried out in 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.
- Affiliations
Citations
Grosso, S. (2023). Development of new copper-catalyzed cross-coupling reactions. https://hdl.handle.net/2078.5/29575