Transition-Metal-Catalyzed Ketone -Alkylation and Alkenylation with Simple Alkenes and Alkynes through a Dual Activation Strategy

In this personal account, we summarize our investigations on the -alkylation and -alkenylation reactions of ketones with nonactivated alkenes and alkynes, respectively. The serendipitous discovery of C-H alkylation/alkenylation of cyclic 1,2-diketones provided a proof of concept for a dual activation strategy. Extension to the -alkylation and -alkenylation of regular ketones was achieved by using 7-azaindoline as a bifunctional ligand. Subsequently, intramolecular coupling between ketones and olefins was achieved with Rh- and Ru-based systems, respectively. Finally, branched-selective -alkylation was achieved through an Ir-catalyzed enamide-mediated C-H alkylation. 1 Introduction 2 Serendipitous Discovery of -Alkylation and -Alkenylation of 1,2-Diketones through Enamine-Mediated C-H Activation 3 Intermolecular Ketone -Alkylation of Regular Ketones with Nonactivated Olefins 4 Intermolecular Ketone -Alkenylation of Regular Ketones with Nonactivated Alkynes 5 Intramolecular Ketone -Alkylation of Regular Ketones with Nonactivated Olefins 6 Branched-Selective -Alkylation of Regular Ketones with Nonactivated Olefins 7 Conclusions and Outlook