Riding the Wave of Monodentate Ligand Revival : from the A/B Concept to Noncovalent Interactions

The rediscovery of chiral monodentate ligands made in the period 1999–2003 had important consequences in enantioselective transition-metal catalysis, such as the introduction of the A/B concept (i.e., use of monodentate ligand mixtures) and, later, a renewed interest in supramolecular ligands capable of ligand–ligand and ligand–substrate interactions. This Personal Account summarizes the contributions made by our research group in this area in the period 2004–2015, which reflect the abovementioned developments. Within this area, we introduced some original concepts, such as 1) the use of chiral tropos ligand mixtures; 2) the development of new strategies to maximize heterocomplex formation from combinations of simple monodentate ligands; 3) the investigation of new ligand–ligand interactions to achieve selective heterocomplex formation; and 4) the development of highly efficient and synthetically accessible supramolecular ligands.