Catalyst‐Controlled Chemodivergent Annulation to Indolo/Pyrrolo‐Fused Diazepine and Quinoxaline

Catalyst‐controlled chemodivergent annulation between o ‐indolo anilines and diazo compounds has explored for the synthesis of indolo‐fused diazepine and quinoxaline. Under the Rh(III) catalyst, reaction proceeded through the free amine assisted C2−H activation followed by amidation leading to the diazepino[1,7‐ a ]indole in a highly selective manner. While with Ru(II) catalyst, reaction involves formation Ru−carbene complex followed by −NH 2 group insertion and cascade cyclization via metallo‐ene type reaction, β‐hydride elimination to furnish the indolo[1,2‐ a ]quinoxaline as the predominating product. This strategy directs modular approach towards the construction of unique indolo‐fused diazepine/quinoxaline as well as pyrrolo‐fused diazepine/quinoxaline scaffolds in excellent yields.