Cu-Catalyzed Enantioselective Atropisomer Synthesis via Thiolative Ring Opening of Five-Membered Cyclic Diaryliodoniums

Abstract

A Cu-catalyzed asymmetric thiolative ring opening reaction of five-membered diaryliodonium salts and potassium thioates for the synthesis of atropisomeric 2'-iodo-[1,1'-biphenyl]-2-yl thioates was realized. The optimal catalytic system, Cu(CH₃CN)₄PF₆/(Ph)-bis(oxazoline), showed the best performance with respect to both yields and stereocontrol. Finally, the utility of these products was briefly demonstrated by the synthesis of an axially chiral P,S-ligand.