How the Lewis Base F– Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines

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 cataly...

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Veröffentlicht in:Journal of organic chemistry 2021-03, Vol.86 (5), p.4320-4325
Hauptverfasser: Svatunek, Dennis, Hansen, Thomas, Houk, Kendall N, Hamlin, Trevor A
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creator Svatunek, Dennis
Hansen, Thomas
Houk, Kendall N
Hamlin, Trevor A
description 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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title How the Lewis Base F– Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines
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