Carbenoid insertions into benzylic C-H bonds with heterogeneous copper catalysts

The copper complexes with bis(oxazoline) or azabis(oxazoline) ligands, once supported on laponite clay by electrostatic interactions, are able to catalyze the insertion of carbenoids in benzylic C-H bonds. In contrast with rhodium catalysts, they are more active with tertiary than with secondary bon...

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Detalles Bibliográficos
Autores: Fraile, José M., Mayoral, José A., Muñoz, Ana, Santafé-Valero, Jorge
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2013
País:España
Institución:Consejo Superior de Investigaciones Científicas (CSIC)
Repositorio:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/111134
Acceso en línea:http://hdl.handle.net/10261/111134
Access Level:acceso abierto
Palabra clave:Carbene insertion
Heterogeneous catalysis
Copper catalysts
Benzylic insertion
Descripción
Sumario:The copper complexes with bis(oxazoline) or azabis(oxazoline) ligands, once supported on laponite clay by electrostatic interactions, are able to catalyze the insertion of carbenoids in benzylic C-H bonds. In contrast with rhodium catalysts, they are more active with tertiary than with secondary bonds, through a similar mechanism as shown by Hammet correlation. Enantioselectivities are only moderate, with values up to 50% ee. The immobilized catalysts are partially recoverable and the best results are obtained in the case of reactions with high chemoselectivity. © 2013 Elsevier Ltd. All rights reserved.