Thioether-enabled palladium-catalyzed atroposelective C-H olefination for N-C and C-C axial chirality.

Thioethers allowed for highly atroposelective C-H olefinations by a palladium/chiral phosphoric acid catalytic system under ambient air. Both N-C and C-C axial chiral (hetero)biaryls were successfully constructed, leading to a broad range of axially chiral N -aryl indoles and biaryls with excellent enantioselectivities up to 99% ee. Experimental and computational studies were conducted to unravel the walking mode for the atroposelective C-H olefination. A plausible chiral induction model for the enantioselectivity-determining step was established by detailed DFT calculations.