Metal‐Catalyzed Enantioselective Hydrophosphorylation Reactions

The catalytic enantioselective addition of hydrophosphoryl compounds (molecules bearing an H─P(O) moiety) to unsaturated chemical bonds—referred to as hydrophosphorylation—has emerged as a powerful strategy for constructing chiral organophosphorus compounds, which are key motifs in asymmetric catalysis, materials science, and medicinal chemistry. Among various methods, metal catalysis offers a versatile platform for achieving high levels of chemo‐, regio‐, and enantioselectivity across a broad range of unsaturated systems, including carbonyl compounds and their derivatives, alkenes, and alkynes. This Concept article highlights recent advances in metal‐catalyzed enantioselective hydrophosphorylation reactions, with particular emphasis on the structural features of products, catalyst design, and mechanistic insights. We also discuss the current scope and limitations of existing methodologies and propose future directions aimed at developing more sustainable, broadly applicable, and stereodivergent catalytic systems.