gem‐Difluoroolefination of Amides

A metal‐free one‐pot process for the gem‐difluoroolefination of amides is described. The reaction is based on interaction of generated in situ α‐chloroiminium salts with difluorinated phosphorus ylide formed from difluorocarbene and triphenylphosphine. The olefination involves nucleophile‐assisted dephosphorylation and proceeds within one hour at low temperature. The gem‐difluoroenamines were used in further transformations leading to a variety of fluoroalkylated amines. Amides can be converted into gem‐difluoroalkenes. The reaction involves interaction of α‐chloroiminium salts with difluorinated phosphorus ylide formed from difluorocarbene and triphenylphosphine.