Experimental and Computational Studies on the Directing Ability of Chalcogenoethers in Palladium-Catalyzed Atroposelective C-H Olefination and Allylation.

We present herein our experimental and DFT computational studies on the directing ability of chalcogenoether motifs in Pd-catalyzed atroposelective C-H functionalization. The thioether motif was found to be a superior directing group compared to the corresponding ether and selenoether in terms of reactivity and enantiocontrol. Remarkably, DFT calculation provided a predictive model for the optimization of reaction conditions and the interpretation of the origin of enantioselectivity. Both Pd-catalyzed enantioselective C-H olefination and allylation reactions were successfully developed using chiral phosphoric acids as efficient ligands, providing a broad range of axially chiral biaryls in good yields with excellent enantioselectivities. The highly enantio- and diastereoselective construction of polyaryls bearing multiple stereogenic axes, gram-scale reaction and various chemical transformations make this protocol more attractive and significant.