Abstract N-Phosphonate terminal aziridines undergo lithium 2, 2, 6, 6-tetramethylpiperidide- induced N-to C-[1, 2]-anionic phosphonyl group migration under experimentally straightforward conditions, to provide a stereocontrolled access to synthetically valuable trans-α, β-aziridinylphosphonates. The utility of this chemistry has been demonstrated in the asymmetric synthesis of a β-aminophosphonate.