Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Rationally Designed Chiral (P,N)-Ligands

We report, for the first time, the concept of enantioselective Au(I)/Au(III) redox catalysis, enabled by the newly designed hemilabile chiral (P,N)-ligands – ChetPhos. The potential of this concept has been demonstrated by the development of enantioselective 1,2-oxyarylation and 1,2-aminoarylation of alkenes which provided direct access to the medicinally relevant 3-oxy- and 3-aminochromans (up to 88% yield and 99% ee). DFT studies were carried out to underpin the enantioinduction model, which revealed that the greater trans-influence of phosphorus allows precise positioning of the substrate in the C2-symmetric chiral environment present around nitrogen, imparting a high level of enantioselectivity.