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Abstract Phosphorus‐containing compounds have a long history of utility in a broad range of fields, including agricultural, pharmaceutical, and metal‐mediated reactions. In recent decades, numerous methods have been developed to streamline the synthesis of organophosphorus reagents based on these numerous applications. This review focuses upon the recent development of phosphorus(III)‐ and phosphorus(V)‐directed C−H borylation reactions. This transformation has evolved significantly in the past two years, resulting in several new methods that provide access to organic substrates containing both phosphorus and boron. Further functionalization of the carbon−boron bond to provide functionalized organophosphorus products is discussed. magnified image 

Abstract Ambiphilic molecules, which contain a Lewis base and Lewis acid, are of great interest based on their unique ability to activate small molecules. Phosphine boronates are one class of these substrates that have interesting catalytic activity. Direct access to these phosphine boronates is described through the iridium‐catalyzed C−H borylation of phosphines. An unconventional cationic iridium catalyst was identified as optimal for a range of phosphines, providing good yields and selectivity across a diverse class of phosphine boronates (isolated as the borane‐protected phosphine). A complimentary catalyst system (quinoline‐based silane ligand with [(COD)IrOMe]₂) was optimal for biphenyl‐based phosphines. Selective polyborylation was also shown providing bis‐ and tris‐borylated phosphines. Deprotection of the phosphine boronate provided free ambiphilic phosphine boronates, which do not have detectable interactions between the phosphorus and boron atoms in solution or the solid state.