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 −NH2 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.