Asymmetric Functionalization Harnessing Radical‐Mediated Functional‐Group Migration

Abstract Along with the renaissance of radical chemistry, the past decade has witnessed rapid development in radical‐mediated rearrangement reactions. A wide diversity of radical approaches harnessing functional‐group migration (FGM) have been devised to enhance both synthetic efficiency and molecular complexity. However, the application of FGM reactions to construct stereogenic centers remains underexplored owing to the inherent challenges of asymmetric radical reactions. In this Minireview, we summarize the emerging area of asymmetric functionalization involving radical‐mediated FGM reactions. Enantioselectivity can be regulated by chiral substrates, auxiliaries or reagents, or achieved through asymmetric transition‐metal catalysis. This synthetic strategy demonstrates its superiority in the production of valuable complex molecules that are otherwise difficult to obtain by conventional methods.