A general protocol for the enantioselective synthesis of 3‐heterosubstituted‐2‐amino‐1‐ols was developed based on metal‐ free intramolecular regio‐ and stereoselective diene aziridination and regioselective opening. Kinetic resolution of the resulting (1’‐NR and 1’‐SR)‐4‐oxazolidinones was performed using ABCs organocatalysts, expanding the application of this methodology.