A 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 to answer the following questions: (1) What is the specific mechanism involved? (2) How does Ag differ from other metals in this context? (3) What is the nature of the oxidative addition by Ag(I) salts? (4) How does the choice of ligand or counteranion influence the reaction? Based on the mechanistic findings, a catalytic system based on a chiral ether ligand is predicted to exhibit milder Lewis acidity, lower reaction barriers, higher chemoselectivity, and the potential for achieving enantioselective synthesis through post-transition state desymmetrization.