Selective Functionalization of Arene C(sp<sup>2</sup>)–H Bonds by Gold Catalysis: The Role of Carbene Substituents
Juan Diego Pizarro, Inga L. Schmidtke, Ainara Nova, Manuel R. Fructos, Pedro J. Pérez
Abstract
The complete regioselective incorporation of carbene units to nonactivated arene rings has been achieved employing gold(I) catalysts bearing alkoxydiaminophosphine ligands, with readily available, nonelaborated ethyl 2-phenyldiazoacetate as the carbene source. These results are in contrast with the scarce precedents which required highly elaborated diazo substrates. Density functional theory (DFT) calculations have revealed the important role of the R group in the C(R)CO2Et fragment, which dramatically affects the energy profile of this transformation.
Topics & Concepts
CarbeneDiazoCatalysisChemistryRegioselectivityDensity functional theorySurface modificationMedicinal chemistryStereochemistryPhotochemistryCombinatorial chemistryOrganic chemistryComputational chemistryPhysical chemistryCyclopropane Reaction MechanismsCatalytic Alkyne ReactionsCatalytic C–H Functionalization Methods