Forging C−heteroatom bonds by transition-metal-catalyzed enantioselective C–H functionalization

Direct C–H functionalization has recently emerged as one of the most efficient strategies to access structurally complex molecules from readily accessible feedstocks in an atom- and step-economic manner. In particular, enantioselective C–H activation has garnered increasing attention by enabling chemists to efficiently assemble valuable chiral compounds by asymmetrically manipulating C–H bonds into useful functionalities. Apart from the extensively studied C–C bond formation, very few endeavors have been focused on the C–X formation analogs. Motivated by the utility of the latter approach in constructing academically and industrially important heteroatom-containing chiral compounds, we provide herein an overview on C–X forming asymmetric C–H activation reactions proceeding through C–H metalation. The advancements are organized according to the employed catalytic systems, which include Pd(II) catalysis, group-9 CpxM(III) catalysis, monovalent group-9 metal catalysis, and multi-boryl/silyl Ir(III) catalysis, with emphasis on the design philosophy, mechanism, and mode of enantiocontrol.