Persistent Organonickel Complexes as General Platforms for Csp2-Csp3 Coupling Reactions

Coupling reactions between aryl electrophiles and alkyl/perfluoroalkyl precursors have inspired elegant methodologies that leverage electrochemical, photochemical, or thermal activation modalities. This work consolidates these myriad strategies to a single set of conditions and enables previously unknown alkyl-aryl couplings. These reactions rely on the discovery of unusually persistent organonickel complexes that serve as stoichiometric platforms for C(sp2)-C(sp3) coupling. Aryl, heteroaryl, or vinyl complexes of Ni can be inexpensively prepared on multigram scale by mild electroreduction from the corresponding C(sp2) electrophile. Organonickel complexes can be isolated and stored or telescoped directly to reliably diversify drug-like molecules. Finally, the procedure was miniaturized to µL scales by integrating soluble battery chemistries as redox initiators, which enabled a high-throughput exploration of substrate diversity.