Deaminative 1,n-Difunctionalization of Alkenes Via Controlled Chain Walking

The regioselective 1,n-difunctionalization of unactivated alkenes at remote positions is highly challenging due to the lack of thermodynamic driving force to arrest chain walking at a specific nth site. Herein we describe a new modality for controlling such regioselectivity by harnessing chain walking to activate remote leaving groups. We report that alkenyl ammonium salts can undergo a Pd-catalyzed deaminative 1,n-dicarbofunctionalization reaction with aryl iodides in which the ammonium group controls the remote nth site of functionalization. This transformation features a broad tolerance for electron-poor, elec-tron-rich, and reactive aryl coupling partners as well as linear and cyclic alkenes to generate 1,n-difunctionalized products in modest to excellent yields. Mechanistic studies provide insight into key steps, including the role of the ammonium group in controlling chain walking.