Native Amides as Enabling Vehicles for Forging sp 3 - sp 3 Architectures via Interrupted Deaminative Ni-Catalyzed Chain-Walking.

Herein, we disclose an interrupted deaminative Ni-catalyzed chain-walking strategy that forges sp 3 - sp 3 architectures at remote, yet previously unfunctionalized, methylene sp 3 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 sp 3 - sp 3 bond formations that are otherwise inaccessible in conventional chain-walking events.