Photocatalyst‐Free Chiral Phosphoric Acid‐Catalyzed Enantioselective Minisci‐Type Alkylation of <i>N</i>‐Heteroarenes

Abstract In this study, we present an efficient radical approach for the enantioselective Minisci‐type alkylation of N ‐heteroarenes, using chiral phosphoric acid (CPA) as a catalyst under mild conditions, without the need for metals, photocatalysts, and other additives. Prochiral α‐aminoalkyl radicals generated from RAEs were successfully introduced to N ‐heteroarene derivatives, including pyridine, quinoline, and isoquinoline, resulting in a range of valuable chiral alkylated N ‐heteroarenes with secondary amines in high yields and good to excellent enantioselectivities (up to 98 % ee ). The chiral phosphoric acid catalyst not only activates the substrate and induces asymmetry but also facilitates essential electron transfer processes.