The aza-Payne rearrangement may be effected in either the "forward" (epoxide to aziridine) or "reverse" (aziridine to epoxide) direction depending on the conditions employed. Electron-poor aziridines undergo the reverse rearrangement in the presence of hydride base, while the corresponding epoxy amines undergo the forward rearrangement in the presence of boron trifluoride etherate.
The thia-Payne rearrangement has only been observed in the forward direction (epoxide to thiiranium) with in situ opening of the thiiranium. Invertive nucleophilic opening at C-2 is possible through the use of trialkylaluminum reagents.