LAUSR

The employment of metal salts is quite limited in asymmetric catalysis, although it would provide an additional arsenal of safe and inexpensive reagents to create molecular functions with high optical purity. Cation chelation by polyethers increases the salts’ solubility in conventional organic solvents, thus increasing their applicability in synthesis. The expansion of this concept to chiral polyethers led to the emergence of asymmetric cation‐binding catalysis, where chiral counter anions are generated from metal salts, particularly using BINOL‐based polyethers. Alkali metal salts, namely KF and KCN, are selectively bound to the catalyst, providing exceptionally high enantioselectivities for kinetic resolutions, elimination reactions (fluoride base), and Strecker synthesis (cyanide nucleophile). Asymmetric cation‐binding catalysis was recently expanded to silicon‐based reagents, enabling highly enantioselective silylation reactions in polyether‐generated chiral environments, and leading to a record‐high turnover in asymmetric organocatalysis. This can lead to further applications by the asymmetric use of other inorganic salts in various organic transformations.