O-Cyclopropyl hydroxylamines, now accessible via a novel and scalable synthetic route, have been demonstrated to be bench-stable and practicalprecursors for the synthesis of N-heterocycles via a di-heteroatom [3,3]-sigmatropic rearrangement. In order to study the reactivity of these compounds in depth, a robust synthesis of both ring-substituted and ring-unsubstituted O-cyclopropyl hydroxylamines has