How the Lewis Base F<sup>–</sup>Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines
Dennis Svatunek, Thomas Hansen, K. N. Houk, Trevor A. Hamlin
Abstract
The mechanism of the Lewis base F– catalyzed 1,3-dipolar cycloaddition between CO2 and nitrilimines is interrogated using DFT calculations. F– activates the nitrilimine, not CO2 as proposed in the literature, and imparts a significant rate enhancement for the cycloaddition. The origin of this catalysis is in the strength of the primary orbital interactions between the reactants. The Lewis base activated nitrilimine–F– has high-lying filled FMOs. The smaller FMO-LUMO gap promotes a rapid nucleophilic attack and overall cycloaddition with CO2.
Topics & Concepts
CycloadditionChemistryLewis acids and bases1,3-Dipolar cycloadditionHOMO/LUMONucleophileCatalysisPhotochemistryBase (topology)Medicinal chemistryStereochemistryOrganic chemistryMoleculeMathematicsMathematical analysisCarbon dioxide utilization in catalysisCO2 Reduction Techniques and CatalystsCyclopropane Reaction Mechanisms