Executive Summary : | This research aims to develop a combined electro- and metal dual catalysis concept for unexplored reductive and redox neutral cross-coupling reactions and investigate their detailed reaction mechanisms. The mechanistic understanding will help reveal the nature of electron transfer processes and facilitate the improvement of catalytic systems to achieve enhanced reaction selectivities and reactivities. Metal-catalyzed electrosynthesis can control redox states of the catalyst, preventing the use of highly air-sensitive M(0) catalysts, pyrophoric reagents, and phosphine ligands. The reactions can be performed at room temperature and in air. Despite extensive research on electrocatalyzed oxidative cross-coupling reactions, electrocatalyzed reductive cross-couplings and redox neutral transformations remain less developed. The project aims to explore metallaelectro-catalyzed cross-electrophile coupling reactions, avoiding large amounts of pyrophoric reducing agents and using electricity as a greener and cheaper "reagent." The key step in these reactions is the sequential reduction of metal complexes at the cathode surface to generate active metal species or intermediates. The proposal plans to investigate earth-abundant metal catalysts, such as nickel and cobalt complexes, in reductive, electrochemical coupling reactions to construct C(sp2)-C(sp3) and C(sp3)-C(sp3) bonds and extend the methodology to cascade reactions. Redox-neutral paired electrolysis is an attractive method, but the development of redox-neutral paired metallaelectro-catalyzed transformations has been less established. All compounds produced during the project will be subjected to bioassays and structure-based screening and archived for future use. |