Intermolecular Gold‐Catalyzed Nitrene Transfer Employing Aryl Azides: An Access to 7‐Functionalized 2‑Aminoindoles

We report on intermolecular gold‐catalyzed nitrene transfer, utilizing o‐functionalized aryl azides as nitrene transfer reagents. This catalytic reaction provides a modular route to 7‐functionalized 2‐aminoindoles. Due to the optimized reaction conditions (toluene, 80–100 °С), a variety of functional substituents proved compatible (36 examples; yields up to 98%). The reaction can be performed using both homogeneous and heterogeneous catalytic variants with a low catalyst loading (1 mol %). The synthetic potential of the obtained products was illustrated by post‐modifications of the indole backbone and peripheral substituents. A plausible reaction mechanism includes the generation of intermediate α‐imino carbenes directly from the o‐functionalized aryl azides or other nitrene sources, such as anthranils or benzofuroxans, which form during the reaction in the cases of the specific aryls.