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

Abstract

Density functional theory calculations are reported for the reaction mechanism of selected XCu NHX(X = Cl, Br, I) with olefins to form three-membered ring products. The copper reagents react with olefins via an asynchronous attack on one CH 2 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.

Synthetic methods : Part (ii) Oxidation and reduction methods

“…The decomposition of copper Schiff base complexes used for aziridination has also been studied 101 and DFT modelling of Cucatalysed aziridination undertaken. 102…”

“…The decomposition of copper Schiff base complexes used for aziridination has also been studied 101 and DFT modelling of Cu-catalysed aziridination undertaken. 102 Scheme 34 Scheme 35 Other metals have also been employed for alkene aziridination in 2009. Phillips, Halfen and co-workers have published a mechanistic study on Fe-catalysed aziridination.…”