Gold‐Catalyzed Oxidative [2+2+1] Annulations of Aryldiazo Nitriles with Imines To Yield Polyarylated Imidazolium Salts

Gold‐catalyzed oxidative 2+2+1] annulations between two imines and one α‐cyano arylgold carbene afforded polyarylated imidazolium salts and molecular hydrogen efficiently. Control experiments suggest that the gold catalyst alone facilitates the main annulation, whereas Ag⁺ avoids the formation of inactive LAuCN. DFT calculations suggest that the success of this annulation relies on a 6 π‐electrocyclization of cyano‐free intermediates with cis ‐configured imines as initial reagents.