Selective Construction of All-Carbon Quaternary Centers via Relay Catalysis of Indole C-H Functionalization/Allylic Alkylation.

Herein, a novel [Rh] 2 -catalyzed three-component reaction of readily accessible indoles, diazo compounds, and allylic compounds is developed via a relay carbene-induced C-H functionalization and allylic alkylation process, affording diverse C3-substituted indoles bearing all-carbon quaternary centers in good yields with high atom and step economy. Moreover, good enantioselective control is achieved using a (-)-DIOP type ligand, thus providing an efficient method for constructing enantioenriched indole derivatives bearing an all-carbon quaternary stereocenter.