Abstract The development, scope, and application of the highly enantioselective organocatalytic aziridination of α, β-unsaturated aldehydes is presented. The aminocatalytic azirdination of α, β-unsaturated aldehydes enables the asymmetric formation of β-formyl aziridines with up to> 19: 1 dr and 99% ee. The aminocatalytic aziridination of α- monosubstituted enals gives access to terminal α-substituted-α-formyl aziridines in high ...