Copper‐Catalyzed Highly Enantioselective Addition of a Silicon Nucleophile to 3‐Substituted 2H‐Azirines Using an Si−B Reagent

3‐Substituted 2H‐azirines can be considered strained cyclic ketimines, and highly enantioselective addition reactions of silicon nucleophiles to either acyclic or cyclic ketimines have been elusive so far. The present work closes this gap for those azirines by means of a copper‐catalyzed silylation using a silyl boronic ester as a latent silicon nucleophile. The resulting C‐silylated, unprotected (N−H) aziridines are obtained in high yields and with excellent enantioselectivities and can be further converted into valuable compounds with hardly any erosion of the enantiomeric excess.