Theoretical Study on Copper-Catalyzed S-Arylation of Thiophenols with Aryl Halides: Evidence Supporting the LCu(I)-SPh Active Catalyst and Halogen Atom Transfer Mechanism

A systematic theoretical study on reaction mechanisms for copper-catalyzed Ullmann S-arylation reactions of thiophenols with aryl halides is reported herein. The equilibriums and consequent relative concentrations of possible copper species in the reaction solution were carefully evaluated to determine the most probable active catalytic forms. Subsequently, reactivity studies of these copper species with aryl halides were performed in the context of several commonly proposed mechanisms for copper(I)-catalyzed Ullmann reactions, such as oxidative addition/reductive elimination, σ-bond metathesis, single electron transfer (SET), and halogen atom transfer (HAT) mechanisms. On the basis of these intensive studies, we propose for the first time that the active copper catalyst should be neutral (L)Cu(I)-SAr species (L denotes a neutral ancillary ligand; SAr denotes a thiophenolato type ligand) in nonpolar or less polar solvent and anionic Cu(SAr)2— species in highly polar solvent. These two kinds of species are...