The imidate–amide rearrangement: an explanation for the ambident nucleophilic properties of neutral amides

Abstract

Rearrangement of N-methylbenzimidates to tertiary amides (in nitrobenzene at 138°) is readily catalysed by alkyl halides and other electrophilic species, suggesting that alkylation of neutral amides usually proceeds at the O-atom, with N-substitution arising from a subsequent rearrangement.