Asymmetric Synthesis of P(V) Skeleton via Catalytic Desymmetric Substitution

Abstract Stereogenic‐at‐P(V) skeletons exist ubiquitously in drugs, agrochemicals, organocatalysts, ligands and materials. Conventional synthetic methods mainly rely on chromatographic resolution, chiral auxiliary induction and optically active substrate control. Catalytic asymmetric transformation as an economic pathway has received much progress via racemic substrate resolution and desymmetrization of prochiral precursors. Among them, catalytic desymmetric substitution strategy has recently emerged as a new and powerful route to construct P(V) stereocenter, particularly witnessed a series of achievements in preparing seldom studied fully heteroatom‐substituted P(V) scaffolds in the past one year. This minireview aims to provide a timely summary and highlight on this rapidly developing field, including reaction design, synthesis, mechanism and applications, and also perspective on the potential limitations and future trend.