Density Functional Theory Calculations for Multiple Conformers Explaining the Regio- and Stereoselectivity of Ti-Catalyzed Hydroaminoalkylation Reactions.

Hybrid Density Functional Theory (DFT) calculations for multiple conformers of the insertion reactions of a methylenecyclopropane into the Ti-C bond of two differently α-substituted titanaaziridines explain the experimentally observed differences in regioselectivity between catalytic hydroaminoalkylation reactions of methylenecyclopropanes with α-phenyl-substituted secondary amines and corresponding stoichiometric reactions of a methylenecyclopropane with titanaaziridines, which can only be achieved with α-unsubstituted titanaaziridines. In addition, the lack of reactivity of α-phenyl-substituted titanaaziridines as well as the diastereoselectivity of the catalytic and stoichiometric reactions can be understood.