Mechanistic study of enantioselective - alpha-arylation of ketone with diaryliodonium salt catalyzed with Cu and chiral bis-phosphinoxide

This thesis work is focused on the mechanistic study of a Cu-based catalytic system for a stereoselective α-arylation of carbonyl compounds previously developed in our group. This system presents several interesting features as it exploits chiral phosphine oxides as ligands for transition metal catalysis. In this thesis work we seek to answer two main questions: 1) What is the catalytically active species? A kinetic analysis will be performed with the purpose of confirming the reaction kinetic orders previously observed for the reagents and to define the kinetic order of the catalyst. 2) Are radical species actually involved in the reaction mechanism? In order to answer this question, we will employ two tools that are often used in mechanistic analyses of this kind: radical traps, and radical clock experiments. Overall, this work will lead to the identification of a clearer reaction mechanism for our α-arylation reaction, and to the discovery of a new Cu-catalyzed ring-closing Heck reaction that will provide new insights into the general reactivity of elusive Cu(III)-Ar species