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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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
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author Svatunek, Dennis
Hansen, Thomas
Houk, Kendall N.
Hamlin, Trevor A.
author_facet Svatunek, Dennis
Hansen, Thomas
Houk, Kendall N.
Hamlin, Trevor A.
author_sort Svatunek, Dennis
collection PubMed
description [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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spelling pubmed-80237012021-04-07 How the Lewis Base F(–) Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines Svatunek, Dennis Hansen, Thomas Houk, Kendall N. Hamlin, Trevor A. J Org Chem [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). American Chemical Society 2021-02-12 2021-03-05 /pmc/articles/PMC8023701/ /pubmed/33577314 http://dx.doi.org/10.1021/acs.joc.0c02963 Text en © 2021 The Authors. Published by American Chemical Society Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Svatunek, Dennis
Hansen, Thomas
Houk, Kendall N.
Hamlin, Trevor A.
How the Lewis Base F(–) Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines
title How the Lewis Base F(–) Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines
title_full How the Lewis Base F(–) Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines
title_fullStr How the Lewis Base F(–) Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines
title_full_unstemmed How the Lewis Base F(–) Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines
title_short How the Lewis Base F(–) Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines
title_sort how the lewis base f(–) catalyzes the 1,3-dipolar cycloaddition between carbon dioxide and nitrilimines
url 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
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