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

Abstract

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.

Catalytic C–H Functionalization of Trimethylamine

“…10 The relative configuration of 29 was elucidated by single-crystal X-ray diffraction analysis of the corresponding hydrochloride 29·HCl (Figure 4 ), 11 and it was found that 29 has the expected cis -orientation of the dimethylaminomethyl substituent and the cyclopropane hydrogen atoms. This finding is in good agreement with closely related DFT-calculations, 16 which have already shown that hydroaminoalkylation of a corresponding methylenecyclopropane with secondary amines can only occur from its convex side.…”

Condensed Matter Systems Exposed to Radiation: Multiscale Theory, Simulations, and Experiment

“…Areas of Applications : DFT has found numerous applications in chemistry and materials science by calculating the electronic ground-state properties of various systems. ,− In solid-state calculations, the LDA is still commonly used along with plane-wave basis sets, as an electron-gas approach is more appropriate for electrons delocalized through an infinite solid. However, in calculations involving molecular systems, more accurate long-range corrected XC functionals ( e.g.…”