DFT Study on Zr-Catalyzed Alkene Hydroaminoalkylation: Origin of Regioselectivity, Diastereoselectivity, and Influence of Substrate

A DFT study was carried out to investigate a zirconium-catalyzed hydroaminoalkylation of alkenes with N-silylated benzylamine. A global reactivity index (GRI) analysis showed that that substrates act as electrophiles while the active zirconaaziridine behaves as a nucleophile. Furthermore, the distortion/interaction analysis unveiled the role of the distortion and interaction energies in controlling the regioselectivity and diastereoselectivity when different alkene substrates are used. These results provide an in-depth analysis on how the substrate type influences the product selectivity. © 2020 American Chemical Society. All rights reserved.