Zeitschriftenartikel:
D. Svatunek, T. Hansen, K. Houk, T. Hamlin:
"How the Lewis Base F- Catalyzes the 1,3-Dipolar Cycloaddition between Carbon Dioxide and Nitrilimines";
Journal of Organic Chemistry,
86
(2021),
5;
6 S.
Kurzfassung englisch:
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.
Schlagworte:
Computational organic chemistry; Cycloadditions
"Offizielle" elektronische Version der Publikation (entsprechend ihrem Digital Object Identifier - DOI)
http://dx.doi.org/10.1021/acs.joc.0c02963
Elektronische Version der Publikation:
https://publik.tuwien.ac.at/files/publik_303205.pdf
Erstellt aus der Publikationsdatenbank der Technischen Universität Wien.