Synthesis and reactivity of non-activated 2-(chloromethyl)aziridines

An efficient synthesis of non-activated 2-(chloromethyl)aziridines and 2-chloromethyl-2-methylaziridines as new representatives of the class of 2-(halomethyl)aziridines was developed. Furthermore, the reactivity of these azaheterocycles was assessed and compared to that of their brominated counterparts, pointing to a similar profile for 2-(chloromethyl)aziridines and 2-(bromomethyl)aziridines on the one hand, and a different behaviour of 2-chloromethyl-2-methylaziridines versus 2-bromomethyl-2-methylaziridines concerning their aptitude towards ring expansion to azetidines on the other hand.