Abstract
<jats:p>We investigated the reaction mechanism and stereo-control for asymmetric sulfamate tethered aza-Michael cyclization via a DFT-based computational study. Four distinct transition states (TS) were identified for the model reaction, two for Re-face and two for Si-face. Potential energy surface described for the model indicated two feasible pathways each on Re-face and Si-face, upon which the most feasible path that resulted in the major enantiomer was identified. Non-covalent interactions were studied to elucidate the intra- and intermolecular interactions present in substrate catalyst complex and investigate its role that affects the overall stability of the stationary points. Activation strain model was applied across all the path to quantify the distortion, and interaction energies present in the reaction profile. Additionally, the most feasible pathway identified was used to explain the kinetic resolution observed in the experimental study. These results refine the originally proposed mechanistic model and provide insights to guide the rational design of improved chiral catalysts for asymmetric aza-Michael reactions.</jats:p>