Stereospecific cross-coupling reactions: Programmed assembly of chiral molecules by reaction of chiral reagents

Long recognized as being a challenge in the arena of cross-coupling reactions, the formation of C–C bonds between saturated carbon centers has become simpler because of advances in catalyst design. However, when these processes involve the reaction of chiral carbon centers, the control of reaction stereochemistry remains a pressing concern. One still-emerging strategy for stereocontrol in cross-coupling relies on construction of configurationally defined reactants paired with catalysts that transform these substrates with high stereochemical fidelity. In this review, we survey chiral organometallic reagents that may be formed with enantiocontrol and examine advances in their cross-coupling.