A Bimolecular Diels–Alder Reaction Mediated by Inclusion in a Polar Bis-calix[4]pyrrole Octa-Imine Cage
We describe using a dynamically self-assembled octa-imine cage as a molecular flask to accelerate a bimolecular Diels–Alder reaction. We investigate the cage’s binding properties using 1H NMR spectroscopic titrations, ITC experiments, and X-ray crystallography. We detect and characterize the formati...
| Autores: | , |
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| Formato: | artículo |
| Fecha de publicación: | 2025 |
| País: | España |
| Recursos: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2072/483460 |
| Acesso em linha: | https://hdl.handle.net/2072/483460 https://doi.org/10.1021/jacs.5c03361 |
| Access Level: | acceso abierto |
| Palavra-chave: | Química 54 |
| Resumo: | We describe using a dynamically self-assembled octa-imine cage as a molecular flask to accelerate a bimolecular Diels–Alder reaction. We investigate the cage’s binding properties using 1H NMR spectroscopic titrations, ITC experiments, and X-ray crystallography. We detect and characterize the formation of the ternary complex (Michaelis) in solution. A detailed kinetic analysis of the reaction data supports that the cage’s acceleration is provided by including the two reactants, resulting in an effective molarity (EM) of ∼40 M. Exo-selectivity and shift of the reaction’s chemical equilibrium are also encountered in the cage’s confined space. Our results mimic enzymes’ ability to bind two substrates in a polar cavity, using directional interactions, and accelerate their stereoselective reaction, with the potential for cavity engineering to enable other reactions. |
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