Nickel‐Catalyzed Chemo‐ and Diastereoselective Dearomative Dialkylation of Indoles with Two Different Alkyl Halides

Abstract The catalytic dearomative dicarbofunctionalization of indoles constitutes one of the most efficient ways to access poly‐substituted indolines that are prevalent in many natural products and drugs. However, despite significant advances, three component dearomative dicarbofunctionalization of indoles has remained elusive. Herein, we report an unprecedented nickel‐catalyzed dearomative dialkylation of indoles with two different alkyl halides via three component cross‐electrophile coupling under mild conditions with the construction of two vicinal C(sp 3 )─C(sp 3 ) bonds at C2 and C3 sites. The catalytic protocol offers an efficient and straightforward route for the modular assembly of diverse carbon quaternary center‐containing dialkylated indoline derivatives with a broad substrate scope (75 examples), excellent functional group tolerance and high chemo‐ and diastereoselectivities. Mechanistic studies, combining a series of experiments and DFT calculations, reveal that the catalytic reaction proceeds via a radical pathway.