Mechanistic Study of the Titanocene(III)-Catalyzed Radical Arylation of Epoxides

An atom‐economical and catalytic arylation of epoxide‐derived radicals is described. The key step of the catalytic system is a sequential electron and proton transfer for the rearomatization of the radical σ‐complex and catalyst regeneration. Kinetic, computational, spectroscopic, and cyclovoltammetric investigations highlight the key issues of the reaction mechanism and catalyst stabilization by collidine hydrochloride. Studies employing radicophiles rule out the participation of cations as reactive intermediates. Catalytic arylations the radical way: The mechanistic intricacies of an atom‐economical and catalytic method for radical arylation have been unraveled. The key step of the catalytic cycle is an electron transfer from a radical to the titanocene catalyst.