Density Functional Theory Study of Gold-Catalyzed 1,2-Diarylation of Alkenes: π‑Activation versus Migratory Insertion Mechanisms

Density functional theory calculations are carried out to better understand the first gold-catalyzed 1,2-diarylation reactions of alkenes reported in the recent literature. The calculations on two representative reactions, aryl alkene/aryl iodide coupling pair (the aryl–I bond is located outside the aryl alkene) versus iodoaryl alkene/indole coupling pair (the aryl–I bond is located in the aryl alkene), confirm that the reaction involves a π-activation mechanism rather than the general migratory insertion mechanism in previously known metal catalysis by Pd, Ni, and Cu complexes. Theoretical results rationalize the regioselectivity of the reactions controlled by the aryl–I bond position (intermolecular or intramolecular) and also the ligand and substituent effects on the reactivity.