Recent Progress in Phosphinamide‐Directed CH Functionalization for the Construction of CX Bonds (XC, N, O)

Abstract

Organophosphorus compounds are widely used in bioactive molecules, catalysts, and ligands. Recent CH functionalization methods—often guided by directing groups—now enable direct formation of CC, CN, and CO bonds on phosphinamide substrates with improved step efficiency. This review highlights key transition‐metal‐catalyzed advances, with emphasis on desymmetrization approaches that deliver enantio‐enriched phosphorus frameworks. The discussed transformations provide direct and atom‐economical pathways for the construction of CC, CN, and CO bonds, offering efficient access to enantio‐enriched phosphorus architectures. While substantial progress has been achieved, this overview also identifies promising future directions, such as the development of greener catalytic systems and the exploration of underdeveloped bond‐forming manifolds.