Abstract

This chapter reviews asymmetric C–H functionalization reactions in which the newly defined stereochemistry is controlled by the carbon–hydrogen bond cleavage step. Various carbon–carbon bonds are constructed by enantioselective, transition-metal-catalyzed, C(sp²)–H and C(sp³)–H activation reactions. The utility of this transformation is demonstrated by its use in the synthesis of biologically active compounds, natural products, and chiral ligand scaffolds for asymmetric catalysis.