Intramolecular hydrogen bond activation for kinetic resolution of furanone derivatives by an organocatalyzed [3+2] asymmetric cycloaddition

Herein, a formal highly enantioselective organocatalyzed [3+2] cycloaddition of furanone derivatives and azomethine ylides is presented. The success of this reaction resides in an intramolecular hydrogen bond activation through an o-hydroxy group at aromatic ring of the imine, allowing the formation...

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Detalles Bibliográficos
Autores: Valle-Amores, Miguel A., Feberero, Claudia, Martín Somer, Ana, Díaz-Tendero Victoria, Sergio, Smith, Andrew D., Fraile Carrasco, Alberto, Alemán Lara, José Julián
Tipo de recurso: artículo
Fecha de publicación:2023
País:España
Institución:Universidad Autónoma de Madrid
Repositorio:Biblos-e Archivo. Repositorio Institucional de la UAM
Idioma:inglés
OAI Identifier:oai:repositorio.uam.es:10486/708736
Acceso en línea:http://hdl.handle.net/10486/708736
https://dx.doi.org/10.1039/D3QO01471A
Access Level:acceso abierto
Palabra clave:Intramolecular Hydrogen
Furanone
Cycloaddition
Física
Química
Descripción
Sumario:Herein, a formal highly enantioselective organocatalyzed [3+2] cycloaddition of furanone derivatives and azomethine ylides is presented. The success of this reaction resides in an intramolecular hydrogen bond activation through an o-hydroxy group at aromatic ring of the imine, allowing the formation of highly multifunctional bicyclic adducts with five stereogenic centers in a stereocontrolled manner. Furthermore, the reaction is paired to a highly efficient kinetic resolution of butenolides, achieving selectivity factors above 200. Using this methodology, furan-2(5H)-ones as well as furo[3,4-c]pyrrolidinones were obtained with high enantioselectivities. Quantum chemistry calculations reveal the crucial role of hydrogen bond formed between the catalyst donor-units and the two reagents, which modify their arrangement and promote effective facial discrimination resulting in a highly selective kinetic resolution. In addition, further applicability of the kinetic resolution process is shown