Chiral Lewis Acid‐Catalyzed Asymmetric Radical Transformations

Radical chemistry has long been recognized as a potent and indispensable tool in synthetic chemistry due to its unique ability to cleave and construct chemical bonds. Chiral Lewis acids (CLAs) are essential components of modern organic synthesis, providing strong activation toward substrate molecules and exceptional asymmetric induction in many ionic and concerted reactions. This chapter provides a brief overview of enantioselective radical reactions catalyzed by classic CLAs, such as chiral boranes and complexes of magnesium, lanthanum metals, or other transition metals bearing bidentate, tridentate, or multidentate chiral ligands. Enantioselective hydrogen atom transfer (HAT) reactions, which involve the stereodetermining step in hydrogen atom transfer processes, remain challenging in organic synthesis. Radical-mediated cyclization can form multiple chemical bonds and install several stereogenic centers in a single step, making it a valuable tool for the synthesis of carbocyclic and heterocyclic molecules.