Evolution in heterodonor P-N, P-S and P-O chiral ligands for preparing efficient catalysts for asymmetric catalysis. From design to applications

• Helping in the sustainable production of fine chemicals through an appropriate design of M-heterodonor P-N/O/S catalysts. • Efficient metal-containing heterodonor P-N/O/S catalysts for asymmetric reactions. • Modular and readily accessible heterodonor ligands built up with a broad applicability. The success of phosphine-oxazoline ligands (PHOX) inspired the progress in P-oxazoline ligand families by modifying either the ligand backbone, the electronic and/or steric properties of the phosphine group or by exchanging the phosphine to a phosphinite or a phosphite group. In this respect, the structures of chiral P-oxazoline ligands have become more diverse and new families of very efficient ligands have emerged, which have improved catalytic performance in some asymmetric transformations, with an increased versatility, both in the range of reactions and in the range of substrates/reagents. In addition, most of ligands are synthesized from easily accessible chiral amino alcohols, maintaining the short and efficient synthetic route developed for PHOX ligands. New ligands have been developed by replacing the oxazoline functionality with several other N-donor groups, e.g. imidazole, thiazole, oxazole, pyridine, etc., and O- and S-groups. This review offers a critical overview of the utility of these most successful bidentate heterodonor P-N, P-O and P-S ligand families applied in metal-mediated processes. We illustrate how, through proper ligand design, these heterodonor bidentate ligand families can be an excellent source of ligands, with superior catalytic performance in many asymmetric reactions than the best C 2 -symmetric N,N and P,P-ligands reported so far.