Copper–carbene intermediates in the copper-catalyzed functionalization of O–H bonds

Ana Pereira (1) , Yohan Champouret (2) , Carmen Martin (1) , Eleuterio Alvarez (3) , Michel Etienne (2) , Tomas R. Belderrain (1) , Pedro J. Pérez (1)

1 Universidad de Huelva
2 LCC - Laboratoire de chimie de coordination
3 Universidad de Sevilla

Copper–carbene [TpxCu=C(Ph)(CO2Et)] and copper–diazo adducts [TpxCuη1-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.

Domaines: Chimie de coordination

Ana Pereira, Yohan Champouret, Carmen Martin, Eleuterio Alvarez, Michel Etienne, et al.. Copper–carbene intermediates in the copper-catalyzed functionalization of O–H bonds. Chemistry - A European Journal, 2015, 21 (27), pp.9769-9775. ⟨10.1002/chem.201500776⟩. ⟨hal-01916804⟩