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

Dennis Svatunek; Thomas Hansen; Kendall N. Houk; Trevor A. Hamlin

doi:10.1021/acs.joc.0c02963

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

Dennis Svatunek
, Thomas Hansen
, Kendall N. Houk
, Trevor A. Hamlin^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

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.

Original language	English
Pages (from-to)	4320-4325
Number of pages	6
Journal	The Journal of organic chemistry
Volume	86
Issue number	5
Early online date	12 Feb 2021
DOIs	https://doi.org/10.1021/acs.joc.0c02963
Publication status	Published - 5 Mar 2021

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Copyright 2021 Elsevier B.V., All rights reserved.

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Cite this

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

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. ",

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AU - Hamlin, Trevor A.

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AB - 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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