Chiral single-atom-bridged diphosphorus ligands: synthesis, complexation and catalysis†

The synthesis, complexation and main catalytic applications in enantioselective homogeneous catalysis of enantiopure single-atom-bridged diphosphorus ligands ((R¹R²)P–X–P(R³R⁴); X = CR₂, NR, O) is reviewed, covering the literature up to the beginning of 2025. The information is organised by ligand type, with unsubstituted methylene-bridged (–CH₂–) and substituted amino-bridged (–NR–) diphosphorus ligands being by far the most common type of ligands. The perspective review is completed by the analysis of all reported crystal structures of bidentate monometallic complexes with the ligands. The bite angles, metal–phosphorus distances and buried volumes (V_bur) are given in the ESI.