Chiral phosphorus- and sulfur-stereogenic compounds are widely found in chiral ligands and pharmaceutically active molecules, and their asymmetric construction represents an important research direction in synthetic organic chemistry. Traditional strategies mainly rely on ionic reaction pathways, often requiring stoichiometric chiral auxiliaries, strong bases, or low temperatures. In recent years, radical-mediated strategies have opened new avenues in this field, owing to their mild reaction conditions and distinctive mechanistic profiles. However, the construction of chiral phosphorus and sulfur centers via radical pathways remains challenging due to the lack of effective control strategies, as the configurational inversion barriers of phosphorus- and sulfur-centered radicals are not only substantially different but also unpredictable. This review systematically summarizes advances in the radical-based construction of phosphorus- and sulfur-stereogenic centers over the past five years, organized according to chiral control mechanisms. The construction of phosphorus stereocenters covers strategies including chirality transfer, kinetic resolution and dynamic kinetic resolution, photoenzymatic cooperative catalysis, and cooperative photoredox asymmetric oxidation; the construction of sulfur stereocenters covers chirality transfer, stereoadaptive and deracemization strategies, and chiral induction. By combining representative reaction examples and theoretical calculation analyses, the corresponding stereochemical control mechanisms and their applicable scope are elucidated. Finally, the current challenges and future prospects in this field are discussed.

Key words: radical, P-stereogenic center, S-stereogenic center, asymmetric synthesis, cooperative catalysis