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Copper–Carbene Intermediates in the Copper‐Catalyzed Functionalization of OH Bonds |
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| Authors: | Ana Pereira Dr Yohan Champouret Dr Carmen Martín Dr Eleuterio Álvarez Prof?Dr Michel Etienne Prof?Dr Tomás R Belderraín Prof?Dr Pedro J Pérez |
| Institution: | 1. Laboratorio de Catálisis Homogénea, Unidad Asociada al CSIC, CIQSO‐ Centro de Investigación en Química Sostenible and Departamento de Química y Ciencia de Materiales, Universidad de Huelva, 21007 Huelva (Spain), Fax: (+34)?959219942;2. CNRS;3. LCC (Laboratoire de Chimie de Coordination), 205, route de Narbonne, BP 44099, 31077 Toulouse Cedex 4 (France);4. Université de Toulouse;5. UPS, INPT, LCC, 31077 Toulouse Cedex 4 (France);6. Instituto de Investigaciones Químicas Isla de la Cartuja, CSIC‐Universidad de Sevilla, Avenida de Américo Vespucio 49, 41092‐Sevilla (Spain) |
| Abstract: | Copper–carbene TpxCu?C(Ph)(CO2Et)] and copper–diazo adducts TpxCu{η1‐N2C(Ph)(CO2Et)}] have been detected and characterized in the context of the catalytic functionalization of O?H bonds through carbene insertion by using N2?C(Ph)(CO2Et) as the carbene source. These are the first examples of these type of complexes in which the copper center bears a tridentate ligand and displays a tetrahedral geometry. The relevance of these complexes in the catalytic cycle has been assessed by NMR spectroscopy, and kinetic studies have demonstrated that the N‐bound diazo adduct is a dormant species and is not en route to the formation of the copper–carbene intermediate. |
| Keywords: | carbenes copper diazo compounds ligands NMR spectroscopy |