Abstract3‐Dimethylamino‐2,2‐dimethyl‐2H‐azirine (1) reacts with a number of NH–acidic compounds to give adducts of interesting structural variety. In analogy to the reaction of OH‐acidic substrates, the reaction mechanism can be understood to proceed via initial protonation of the aminoazirine, subsequent attack of the nitrogen nucleophile on the iminiumaziridine and ring expansion of the three‐membered ring to form a zwitterionic intermediate. Depending very much on the charge‐distribution delivered by the variety of substituents, this zwitterionic intermediate is going to be stabilised by different routes, e.g. water elimination, ring enlargement or rearrangement, to yield new N‐het