Disclosing the Intra-Catalyst Non-Covalent Interactions in Tetrahydropyran-Based Dipeptidic Catalysts
Herein, we describe how minor structural modifications to our bifunctional organocatalysts based on sugar amino acids (SAAs) can alter the network of non-covalent interactions (NCIs) within the catalyst, leading to significant changes in their catalytic activity. This is attributed to the intra-cata...
| Autores: | , , , , |
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| Tipo de recurso: | artículo |
| Estado: | Versión publicada |
| Fecha de publicación: | 2025 |
| País: | España |
| Institución: | Consejo Superior de Investigaciones Científicas (CSIC) |
| Repositorio: | DIGITAL.CSIC. Repositorio Institucional del CSIC |
| OAI Identifier: | oai:digital.csic.es:10261/386616 |
| Acceso en línea: | http://hdl.handle.net/10261/386616 |
| Access Level: | acceso abierto |
| Palabra clave: | Non-covalent interactions organocatalysis Michael addition kinetics density functional calculations chemistry Organic chemistry |
| Sumario: | Herein, we describe how minor structural modifications to our bifunctional organocatalysts based on sugar amino acids (SAAs) can alter the network of non-covalent interactions (NCIs) within the catalyst, leading to significant changes in their catalytic activity. This is attributed to the intra-catalyst NCIs, which induce conformational changes that are reflected in the transition state of the rate-determining step of the Michael addition of aldehydes to trans-β-nitrostyrenes. Through kinetic experiments, conformational analysis, and DFT calculations, we found that the presence of a methoxy group at the C4 position of the tetrahydropyran ring reduces the catalytic activity by a factor of five compared to the catalyst without the methoxy group. Additionally, we have identified the different intra-catalyst NCIs, both attractive and repulsive, that drive the conformational changes, ultimately modifying the energy levels of the transition states of the rate- and enantioselectivity-determining step of the reaction. |
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