Enantioselective Access to <i>N</i> -Alkylindoles via NHC–Nickel-Mediated 1,2-Difunctionalization of 1-Vinylindoles

The indole scaffold is a ubiquitous pharmacophore in natural products and pharmaceuticals, yet the enantioselective construction of enantioenriched <i>N</i>-alkylindoles remains underdeveloped. We report a Ni-NHC-catalyzed enantioselective 1,2-dicarbofunctionalization of readily available 1-vinylindoles, providing a direct route to enantioenriched <i>N</i>-alkylindoles. This protocol accommodates a wide range of aryl triflates, indoles, and arylmagnesium bromides, delivering products in up to 99% ee. A complementary 1,2-hydrocarbofunctionalization was also realized, affording structurally diverse <i>N</i>-alkylindoles with high enantioselectivity. Together, these results establish a general strategy for divergent and efficient access to enantioenriched <i>N</i>-alkylindoles from simple vinylindole precursors.