Aryl Chloride-Directed Enantioselective C(sp 2 )-H Borylation Enabled by Iridium Catalysis.

We herein report the iridium-catalyzed enantioselective C-H borylation of aryl chlorides. A variety of prochiral biaryl compounds could be well-tolerated, affording a vast array of axially chiral biaryls with high enantioselectivities. The current method exhibits a high turnover number (TON) of 7000, which represents the highest in functional-group-directed asymmetric C-H activation. The high TON was attributed to a weak catalyst-substrate interaction that was caused by mismatched chirality between catalyst and substrate. We also demonstrated the synthetic application of the current method by C-B, ortho- C-H, and C-Cl bond functionalization, including programmed Suzuki-Miyaura coupling for the synthesis of axially chiral polyarenes.