Ni-Catalyzed Enantioselective Reductive Cross- and Homo-Coupling of Aryl Electrophiles: Synthesis of Axially Chiral Diaryl Dicarboxylates

Ni-catalyzed enantioselective cross -coupling naphthyl triflates and aryl bromides and homocoupling of naphthyl triflates have been developed by virtue of a novel spirocyclic pyrrolidine oxazoline ligand. Both coupling reactions provided axially chiral diaryl dicarboxylates, which are useful subunits bioactive molecules and chiral catalysts, with high excellent enantioselectivities. Further control experiments and density functional theory calculations accounted for a possible reason for a successful cross -coupling. A stereocontrol model involving the formation of a dual N-H hydrogen bond between the ligand and naphthyl triflate was also suggested based on the calculation results.