Atroposelective Synthesis of Axially Chiral Biaryls by Palladium-Catalyzed Asymmetric C-H Olefination Enabled by a Transient Chiral Auxiliary

Atroposelective synthesis of axially chiral biaryls by palladium-catalyzed C-H olefination, using tert-leucine as an inexpensive, catalytic, and transient chiral auxiliary, has been realized. This strategy provides a highly efficient and straightforward access to a broad range of enantioenriched biaryls in good yields (up to 98%) with excellent enantioselectivities (95 to >99% ee). Kinetic resolution of trisubstituted biaryls bearing sterically more demanding substituents is also operative, thus furnishing the optically active olefinated products with excellent selectivity (95 to >99% ee, s-factor up to 600).