Prochiral 3-substituted azetidines bearing a chiral N-substituent may undergo ring-opening reactions with electrophiles, such as benzyl or propargyl bromide, to generate diastereomeric products with moderate selectivity. In the case of the resulting 3-bromo-N-propargylamines, reaction with sodium azide followed by intramolecular azide-alkyne cycloaddition led to substituted tetrahydro triazolodiazepine derivatives. These findings expand the utility of azetidine scaffolds for the construction of more complex nitrogen-containing heterocycles.