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

[Image: see text] The mechanism of the Lewis base F(–) catalyzed 1,3-dipolar cycloaddition between CO(2) and nitrilimines is interrogated using DFT calculations. F(–) activates the nitrilimine, not CO(2) as proposed in the literature, and imparts a significant rate enhancement for the cycloaddition....

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Detalles Bibliográficos
Autores principales: Svatunek, Dennis, Hansen, Thomas, Houk, Kendall N., Hamlin, Trevor A.
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2021
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8023701/
https://www.ncbi.nlm.nih.gov/pubmed/33577314
http://dx.doi.org/10.1021/acs.joc.0c02963
Descripción
Sumario:[Image: see text] The mechanism of the Lewis base F(–) catalyzed 1,3-dipolar cycloaddition between CO(2) and nitrilimines is interrogated using DFT calculations. F(–) activates the nitrilimine, not CO(2) 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 CO(2).

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