Ligand Design Enables Introduction of Nonaromatic Arylating Agents in Palladium-Catalyzed C–H Arylation of Arenes

Conventional palladium-catalyzed methods for constructing biaryls and terphenyls often rely on costly arylating agents, which also face challenges including instability and the need for prefunctionalizations of arenes. Herein, we report an alternative strategy by harnessing the cyclic allyl alcohol and 1,4-epoxy naphthalene as arylating agents for the C-H arylation of arenes. This approach employs ligand design to enhance both the catalytic efficiency and regioselectivity in the C-H activation of arenes, thereby providing a sustainable, atom-economical pathway for late-stage C-H arylation. One of the key design aspects includes the strategic incorporation of steric encumbrance within a monodentate ligand framework, which accelerates reductive elimination without diminishing the efficiency of other catalytic steps. Furthermore, the density functional theory (DFT) study suggests that the extended π-electron cloud of the adjacent aryl ring of the ligand may engage in noncovalent interactions with incoming substrates to induce specific selectivity in the products. Experimental studies, along with DFT calculations, established the reaction mechanism, determined the origin of selectivity, identified the nature of the rate-determining step, and highlighted the role of dual ligands in the regioselectivity.