Overcoming limitations in Chan-Lam amination with alkylboronic esters via aminyl radical substitution

)-N bonds. Here, we report an N-alkylation protocol that overcomes the limitations of Chan-Lam coupling by using versatile alkylboronic pinacol esters (APEs) as radical precursors via aminyl radical-mediated boron abstraction. This distinct approach enables a versatile N-alkylation applicable to a wide range of APEs and N-nucleophiles with diverse functional groups. Synthetic utility of this protocol is further demonstrated by its ease of scalability, sequential N-alkylation of substrate with multiple reactive sites, and the late-stage modification of several complex bioactive materials.