Theoretical investigations of Co-catalyzed allylic aminations

Abstract

Cobalt-bisoxazolinephosphine-catalyzed regio- and enantioselective allylic amination of racemic n-propyl allylic carbonate and aniline was investigated by DFT calculations at the ωB97XD/6–31G(d,p) level (SDD for Co). The computational results revealed that cobalt-catalyzed allylic amination underwent mainly through oxidative addition of n-propyl allylic carbonate, coordination of aniline to cobalt, hydrogen migration, isomerization of allyl group, and reductive elimination. The oxidative addition of n-propyl allylic carbonate was the rate-determining step, the reductive elimination was the regioselectivity-limited and enantioselectivity-controlling step, and the most favorable product was of (R)-chirality, which was compatible with the experimental results. The oxidative addition, hydrogen migration, reductive elimination, and the reactivity of racemic n-propyl allylic carbonates were discussed at full length in this text.