A density functional theory study of copper-catalyzed aziridination of olefins

Density functional theory calculations are reported for the reaction mechanism of selected XCuNHX(X = Cl, Br, I) with olefins to form three-membered ring products. The copper reagents react with olefins via an asynchronous attack on one CH₂ group of ethylene with a relatively low barrier (<78 kJ/mol). These computational results are in good agreement with experimental results, and this suggests that the nitrene transfer process is favored. The BrCuNHBr is found to be the most reactive reagent in the XCuNHX (X = Cl, Br, I) series of reagents. These results are qualitatively consistent with the agreement between copper-catalyzed species character and experimental conditions needed for efficient reaction.