Gold-Catalyzed Migratory Insertion of Alkynes

Migratory insertion is a key elementary step within organometallic chemistry, frequently encountered with most transition metals. However, in the realm of gold catalysis, the migratory insertion step has remained elusive for a long time. Herein, we disclose the migratory insertion of alkynes into Au­(III)–C bonds in a catalytic fashion. Experimental results suggest that the migratory insertion pathway predominates over the π-activation pathway, a finding further supported by the Density Functional Theory (DFT) calculations. The observed regioselectivity underscores the distinct advantages and complementarity of gold catalysis in comparison with palladium catalysis. Furthermore, the utility of the protocol has been demonstrated for the synthesis of various Polycyclic Aromatic Hydrocarbons (PAHs) via Scholl’s reaction.