Truce–Smiles Rearrangements by Strain Release: Harnessing Primary Alkyl Radicals for Metal‐Free Arylation

Abstract The ring‐opening of 3‐aminocyclobutanone oximes enables easy generation of primary alkyl radicals, capable of undergoing an unprecedented strain‐release, desulfonylative radical Truce–Smiles rearrangement, providing divergent access to valuable 1,3 diamines and unnatural β‐amino acids. Characterized by mild conditions and wide scope of migrating species, this protocol allows the modular assembly of sp 3 ‐aryls under transition metal‐free, room‐temperature conditions.