Native Amides as Enabling Vehicles for Forging sp³–sp³ Architectures via Interrupted Deaminative Ni-Catalyzed Chain-Walking

Herein, we disclose an interrupted deaminative Ni-catalyzed chain-walking strategy that forges sp³–sp³ architectures at remote, yet previously unfunctionalized, methylene sp³ C–H sites enabled by the presence of native amides. This protocol is characterized by its mild conditions and wide scope, including challenging substrate combinations. Site-selectivity can be dictated by a judicious choice of the ligand, thus offering an opportunity to enable sp³–sp³ bond formations that are otherwise inaccessible in conventional chain-walking events.