Computational Research on Ag(I)-Catalyzed Cubane Rearrangement: Mechanism, Metal and Counteranion Effect, Ligand Engineering, and Post-Transition-State Desymmetrization

Ag(I) salts have demonstrated superior catalytic activity in the cubane-cuneane rearrangement. This research presents a comprehensive mechanistic investigation using high-level computations. The reaction proceeds via oxidative addition (OA) of Ag(I) to the C-C bond, followed by C-Ag bond cleavage and subsequent dynamically concerted carbocation rearrangement. The OA of Ag(I) exhibits significant more electrophilic nature than classical transition metal-induced OA, and the superior catalytic activity of Ag(I) is attributed to the accessibility of a highly electrophilic "bare" Ag