Svatunek, D., Hansen, T., Houk, K. N., & Hamlin, T. A. (2021). How the Lewis Base F− Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines. Journal of Organic Chemistry, 86(5), 4320–4325. https://doi.org/10.1021/acs.joc.0c02963
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.
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