Convergent Synthesis of α‐Branched Amines by Transition‐Metal‐Catalyzed C−H Bond Additions to Imines

α‐Branched amines are ubiquitous in drugs and natural products, and consequently, synthetic methods that provide convergent and efficient entry to these structures are of considerable value. Transition‐metal‐catalyzed C−H bond additions to imines have the potential to be highly practical and atom‐economic approaches for the synthesis of a diverse and complex array of α‐branched amine products. These strategies typically employ readily available starting inputs, display high functional group compatibility, and often avoid the production of stoichiometric waste byproducts. A number of C−H functionalization methods have also been developed that incorporate cascade cyclization pathways to give amine‐substituted carbocycles, and in many cases, proceed with the formation of multiple stereogenic centers. Advances in the area of asymmetric C−H bond additions to imines have also been achieved through the use of chiral imine N‐substituents as well as by enantioselective catalysis.