Photocatalyst‐Free Chiral Phosphoric Acid‐Catalyzed Enantioselective Minisci‐Type Alkylation of N‐Heteroarenes

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.