Metal-catalyzed enantioselective α-allylation of nitriles

α -Chiral nitriles are key structural motifs found in numerous natural products and pharmaceuticals. Nitriles play a central role in synthetic chemistry and industry as versatile intermediates for diverse functional groups. Considerable research has therefore been devoted to developing efficient strategies for preparing C α -tetrasubstituted and α -quaternary chiral nitriles with varied architectures. This account highlights recent advances in the enantioselective synthesis of homoallylic and allylic nitriles achieved through transition-metal-catalyzed allylation. These catalytic systems deliver high levels of selectivity and accommodate a wide range of substrates, offering practical routes to complex nitrile derivatives. Transition-metal-mediated allylation remains one of the most powerful tools for forging C–C bonds under mild conditions. The discussion also provides key mechanistic insights showing how catalyst design and reaction dynamics control stereochemical outcomes. The synthetic applications presented illustrate how these methods expand access to intricate, stereochemically rich molecules relevant to pharmaceutical and materials chemistry. These advances greatly enrich the synthetic toolkit for the precise and efficient construction of α -chiral nitriles.