On the Origin of the Promoting Effect Exerted by Magnesium in the ZnCl(2)-Catalyzed Synthesis of N,N-Diisopropylethylamine

[Image: see text] The reaction of magnesium or zinc amides with alkyl or benzyl halides is an attractive approach to make C–N bonds, especially for electron-poor organic halides. The magnesium-promoted preparation of hindered non-nucleophilic amine (N,N-diisopropylethylamine) from ethyl chloride and zinc diisopropylamide has been studied. In this paper, instead of the application scope of this method, we focused on the mechanisms of the catalytic processes and the associated electronic origins. According to the calculations, the C–N coupling process in all selected systems proceed preferably in an ethylium-transfer mode. Further, rather than undergoing the Grignard reaction route, the more pronounced electronic interactions within the transition structure as induced by the “innocent” magnesium atom should be responsible for the observed high catalytic activity of the Mg/ZnCl(2) combination.