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

J Org Chem. 2021 Mar 5;86(5):4320-4325. doi: 10.1021/acs.joc.0c02963. Epub 2021 Feb 12.

Authors

Dennis Svatunek^{1

2

3}, Thomas Hansen^{1

4}, Kendall N Houk³, Trevor A Hamlin¹

Affiliations

¹ Department of Theoretical Chemistry, Amsterdam Institute of Molecular and Life Sciences (AIMSS), Amsterdam Center for Multiscale Modeling (ACMM), Vrije Universiteit Amsterdam, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands.
² Institute of Applied Synthetic Chemistry, TU Wien (Vienna University of Technology), A-1060, Vienna, Austria.
³ Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, Los Angeles, United States.
⁴ Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2333 CC Leiden, The Netherlands.

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.

Publication types

Research Support, Non-U.S. Gov't