Amino alcohol ligand-enabled Ni-catalyzed regio- and diastereoselective dearomative borylalkylation of indoles†

The transition-metal-catalyzed intermolecular three-component dearomative difunctionalization of indoles in a one-pot fashion remains largely unexplored. Herein, we present a novel Ni-catalyzed dearomative alkylborylation of indoles utilizing a ligand-enabled, directing group-assisted strategy. This regio- and diastereoselective reaction efficiently converts readily accessible indoles into valuable C3-borylated and C2-alkylated indolines. Additionally, we established a practical one-pot procedure for accessing valuable 2,3-disubstituted indoles with boron retained by combining this protocol with the subsequent oxidation of the resulting indolines. The robustness of this protocol is demonstrated through gram-scale reactions, facile late-stage decoration of complex drug-like molecules, and various downstream diversifications.