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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Detalhes bibliográficos
Autores: Fraile, José M., Mayoral, José A., Muñoz, Ana, Santafé-Valero, Jorge
Tipo de documento: artigo
Estado:Versión aceptada para publicación
Data de publicação:2013
País:España
Recursos:Consejo Superior de Investigaciones Científicas (CSIC)
Repositório:DIGITAL.CSIC. Repositorio Institucional del CSIC
OAI Identifier:oai:digital.csic.es:10261/111134
Acesso em linha:http://hdl.handle.net/10261/111134
Access Level:Acceso aberto
Palavra-chave:Carbene insertion
Heterogeneous catalysis
Copper catalysts
Benzylic insertion
Descrição
Resumo: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.