Reducing rotatable bonds in one substrate accelerates a bimolecular Diels–Alder reaction in a bis-calix[4]pyrrole cage

We report the quantitative self-assembly of an endohedrally functionalized octa-imine cage from two calix[4]pyrrole scaffolds via dynamic covalent chemistry. The cavity combines size and shape complementarity with enzyme-like directional guest binding. Acting as a molecular flask, the cage stereosel...

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Detalhes bibliográficos
Autores: Huang, Jiaming, Martínez-Belmonte, Marta, Ballester, Pablo
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:2072/488969
Acesso em linha:http://hdl.handle.net/2072/488969
https://doi.org/10.1039/D5CC05981J
Access Level:acceso embargado
Palavra-chave:Química
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Descrição
Resumo:We report the quantitative self-assembly of an endohedrally functionalized octa-imine cage from two calix[4]pyrrole scaffolds via dynamic covalent chemistry. The cavity combines size and shape complementarity with enzyme-like directional guest binding. Acting as a molecular flask, the cage stereoselectively promotes a bimolecular Diels–Alder reaction, shifting the equilibrium toward the product. Restricting substrate rotation enhanced the reaction rate dramatically (kincluded/kbulk ≈ 600 M).