Chiral Arene Ligand as Stereocontroller for Asymmetric C-H Activation.

Development of chiral ligands is the most fundamental task in metal-catalyzed asymmetric synthesis. In the last 60 years, various kinds of ligands have been sophisticatedly developed. However, it remains a long-standing challenge to develop practically useful chiral η 6 -arene ligands, thereby seriously hampering the asymmetric synthesis promoted by arene-metal catalysts. Herein, we report the design and synthesis of a class of readily tunable, C 2 -symmetric chiral arene ligands derived from [2.2]paracyclophane. Its ruthenium(II) complexes have been prepared and successfully applied in the enantioselective C-H activation to afford a series of axially chiral isoquinolones (up to 99 % yield and 96 % ee). This study not only lays chemists' longstanding doubts about whether it is possible to use chiral arene ligands to stereocontrol ruthenium(II)-catalyzed asymmetric C-H activation, but also opens up a new avenue to achieve asymmetric C-H activation.