Carboxylate-Assisted Formation of Aryl-Co(III) Masked-Carbenes in Cobalt-Catalyzed C-H Functionalization with Diazo Esters

Herein we describe the synthesis of a family of aryl-Co(III)-carboxylate complexes and their reactivity with ethyl di-azoacetate (EDA). Crystallographic, full spectroscopic characterization and theoretical evidence of unique C-metalated aryl-Co(III) enolate intermediates is provided, unraveling a ca...

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Detalles Bibliográficos
Autores: Planas Fàbrega, Oriol, Roldán Gómez, Steven, Martin-Diaconescu, Vlad, Parella Coll, Teodor, Luis Luis, Josep Maria, Company Casadevall, Anna, Ribas Salamaña, Xavi
Tipo de recurso: artículo
Estado:Versión aceptada para publicación
Fecha de publicación:2017
País:España
Institución: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:10256/16598
Acceso en línea:http://hdl.handle.net/10256/16598
Access Level:acceso abierto
Palabra clave:Reaccions químiques regioselectives
Chemical reactions
Compostos orgànics -- Síntesi
Organic compounds -- Synthesis
Descripción
Sumario:Herein we describe the synthesis of a family of aryl-Co(III)-carboxylate complexes and their reactivity with ethyl di-azoacetate (EDA). Crystallographic, full spectroscopic characterization and theoretical evidence of unique C-metalated aryl-Co(III) enolate intermediates is provided, unraveling a carboxylate-assisted formation of aryl-Co(III) masked-carbenes. Moreover, additional evidence for an unprecedented Co(III)-mediated intramolecular SN2-type C-C bond formation in which the carboxylate moiety acts as a relay is disclosed. This novel strategy is key to tame the hot reactivity of a metastable Co(III)-carbene and elicit C-C coupling products in a productive manner