Regioselective 1,n-Difunctionalization of Alkenes via Chain-Walking-Induced Activation of Remote Leaving Groups

The regioselective 1,n-difunctionalization of unactivated alkenes at remote positions is challenging due to the lack of a driving force to arrest chain walking at specific positions. Herein, we describe an alternative mechanistic approach that harnesses irreversible termination of chain walking to control regioselectivity. Mechanistic studies provide insight into key chain walking and deamination steps. The transformation broadly tolerates nitrogenous leaving groups, aryl coupling partners, and linear and cyclic alkenes to generate 1,n-difunctionalized products.