Tunable Preparation of α‐Aminoacyl Fluorides and α‐Fluoroamides via Base‐Induced Cascade Multiple‐Cleavage Processes from Bromodifluorohydrin Reagents and Amines

A concise strategy for the divergent synthesis of α-fluoroamides and α-aminoacyl fluorides is developed via multiple bond-cleavage processes of 2-bromo-2,2-difluoro alcohols in the presence of amines. The transformation proceeds under mild conditions, displays a broad substrate scope, and features operational simplicity. Mechanistic studies, supported by density functional theory calculations, suggest the involvement of a putative gem-difluoroepoxide intermediate that triggers a cascade of atom recombination events.