Copper-catalyzed trifluoromethylation of vinylsilanes

Details

Supervisors

Riant, Olivier

Faculty

Faculté des sciences

Degree label

Master [120] en sciences chimiques, à finalité spécialisée: chimie de l'industrie

Abstract

Vinylsilane chemistry is a powerful synthetic tool for introducing new C-C bonds into organic molecules. These compounds can be prepared in a stereocontrolled way and have a high chemical stability which led quickly to the development of several reactions. Among these, the most well-known is the palladium-catalyzed cross-coupling of Hiyama. Over the past few years, the copper-catalyzed equivalent has been developed and three major classes of electrophiles (benzyl bromides, allylic bromides and bromoalkynes) could be fixed using vinylsilanes as synthetic linchpin. The aim of this thesis was to extend the electrophiles to reach the (E)- and (Z)-trifluoromethylated alkenes in a stereocontrolled way. The development of this new methodology was carried out in three parts. (1) Selection and synthesis of hydrosilylation catalysts in order to prepare the synthetic linchpins: β-(E)- and β-(Z)-vinylsilanes. (2) Optimisation of a model trifluoromethylation reaction starting from a vinylsilane. (3) Synthesis of libraries of (E)- and (Z)-trifluoromethylated alkenes with the optimised conditions.