The challenge of multidimensional optimization is exemplified in catalytic asymmetric reactions, and the most impactful ligand class in this reaction category is undoubtedly bidentate organophosphorus ligands (Fig. ). This is highlighted by the >50-year evolution of chiral bisphosphines as privileged ligands in asymmetric catalysis. This effort has led to an exceptional range of ligand scaffolds that have had a tremendous impact on the synthesis of molecules for the treatment of human disease. Following seminal examples such as DIPAMP and DIOP, diverse structural motifs have been introduced that include axial chirality and ferrocenyl backbones as well as phospholane rings as seen in BINAP, Josiphos, and DuPhos 20 respectively. Additionally, various C2-symmetric biaryl ligands such as MeO-BIPHEP and Segphos have seen widespread application. The evolution of ever more structurally complex motifs has paralleled the vast utilization of these ligands in diverse reactions operating with unique metal-ligand coordination structures. However, the myriad of accessible structures is also a challenge for optimization campaigns where one may find the requisite reactivity but not high stereoselectivity (or vice versa).