Assembling a Hybrid Pd Catalyst from a Chiral Anionic Co III Complex and Ligand for Asymmetric C(sp 3 )–H Functionalization

An unusual hybrid palladium catalyst containing an anionic chiral Co III complex and a chiral phosphoramidite ligand shows a high capacity for catalyzing asymmetric thioamide‐directed C(sp 3 )−H arylation and delivers excellent yield and enantioselectivity (up to 99 % yield, 99 % ee ). Significant synergy between the chiral ligand and the anion in terms of stereochemical control was observed. Mechanistic investigations have revealed both the nature of the C−H activation and the origin of the enantioselectivity.