<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Treatment of amines (I) with aldehydes and diazoacetate in the presence of B(O‐Ph)<sub>3</sub> and diol (S)‐VPO allows a highly stereo‐ and chemoselective access to cis‐substituted aziridines.</p> </abstract>