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.