Affiliation:
1. Departamento de Química Orgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA) Facultad de Ciencias Químicas Universidad Complutense de Madrid 28040- Madrid Spain
Abstract
AbstractDetailed quantum‐chemical calculations have been carried out to understand both the origin of the catalysis in the urea‐catalyzed nucleophilic ring‐opening of nitrocyclopropanes and the acceleration induced by the presence of an internal Lewis acid in the catalyst. To this end, the mode of activation of these ureas is quantitatively analyzed in detail by means of the Activation Strain Model of reactivity in combination with the Energy Decomposition Analysis method. It is found that the presence of the Lewis acid in the urea further enhances the interaction between the reactants, by increasing both the electrostatic and orbital attractions, which translates into a reduced activation barrier. This insight is also used to assess the impact of the nature of the Lewis acid on the transformation, facilitating the rational design of more active catalysts.
Funder
Ministerio de Ciencia e Innovación
Reference81 articles.
1.
2. Hydrogen Bonding in Organic Synthesis ed. P. M. Pihko Wiley-VCH Weinheim 2009;
3. Chiral Brønsted Acids for Asymmetric Organocatalysis
4. For selected reviews see for instance: