The one-pot preparation of allyl, epoxy and glycosyl perfluoroimidates and their reaction are described. Volatile perfluoronitriles were generated from perfluoroamides with an 'activated'dimethyl sulfoxide (DMSO) species at− 78° C. Allyl, epoxy and glycosyl perfluoroimidates were prepared in 44–92% yield following in situ nucleophilic addition of alcohol and sugar derivatives to nitriles. The obtained trifluoroacetimidates were more ...