Ketenimines as Intermediates To Access Difluoromethoxylated Scaffolds

We report herein the in situ generation of difluoromethoxylated ketenimines. This novel intermediate is readily obtained from the corresponding oxime through a Beckmann rearrangement. The reactivity potential of this species is demonstrated as it easily undergoes addition of various nucleophiles, with a great modularity of the starting oxime. The broad applicability of this transformation leads to a chemical library of original molecules bearing −OCHF2, an Emergent Fluorinated Group (EFG).