Synthesis of Indole-Fused Polycyclics via Rhodium-Catalyzed Undirected C–H Activation/Alkene Insertion

A Rh(III)-catalyzed undirected C–H activation/alkene insertion to synthesize diversified indole-fused polycyclics has been developed. Intramolecular electrophilic cyclization generated a 3-indolyl rhodium species that went through an aryl-to-aryl 1,4-rhodium migration to realize the C–H activation. The subsequent [4 + 2] carboannulation or hydroarylation of alkenes could be achieved, respectively, by simply adjusting the additives of the reaction.