Enantioselective Oxidative (4+3) Cycloadditions between Allenamides and Furans through Bifunctional Hydrogen-Bonding/Ion-Pairing Interactions

BINOL-based N-trifluoromethanesulfonyl phosphoramides catalyze the enantioselective (4+3) cycloaddition between furans and oxyallyl cations, the latter being generated in situ by oxidation of allenamides. The chiral organic phosphoramide counteranion is proposed to engage in the activation of the ox...

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Detalles Bibliográficos
Autores: Villar Arango, Laura, Uria Pujana, Uxue, Martinez, Jose I., Prieto Aretxabaleta, Liher, Reyes Martín, Efraim, Carrillo Fernández, María Luisa, Vicario Hernando, José Luis
Tipo de recurso: artículo
Fecha de publicación:2017
País:España
Institución:Universidad del País Vasco
Repositorio:Addi. Archivo Digital para la Docencia y la Investigación
OAI Identifier:oai:addi.ehu.eus:10810/64346
Acceso en línea:http://hdl.handle.net/10810/64346
Access Level:acceso abierto
Palabra clave:asymmetric catalysis
cycloaddition
ion-pairing catalysis
organocatalysis
oxygen heterocycles
Descripción
Sumario:BINOL-based N-trifluoromethanesulfonyl phosphoramides catalyze the enantioselective (4+3) cycloaddition between furans and oxyallyl cations, the latter being generated in situ by oxidation of allenamides. The chiral organic phosphoramide counteranion is proposed to engage in the activation of the oxyallyl cation intermediate through cooperative hydrogen-bonding and ion-pairing interactions, enabling an efficient chirality transfer that provide the final adducts with high diastereo- and enantioselectivities. Remarkably, the reaction shows a wide substrate scope that includes a variety of substituted allenamides and furans