Pure and Applied Chemistry

Abstract: Lewis acid catalysis has attracted much attention in organic synthesis because of unique reactivity and selectivity attained under mild conditions. Although various kinds of Lewis acids have been developed and applied in industry, these Lewis acids must be generally used under strictly anhydrous conditions. The presence of even a small amount of water handles the reactions owing to preferential reactions of the Lewis acids with water rather than the substrates. In contrast, rare earth and other metal complexes have been found to be water-compatible. Several catalytic asymmetric reactions in aqueous media, including hydroxymethylation of silicon enolates with an aqueous solution of formaldehyde in the presence of Sc(OTf)₃-chiral bipyridine ligand or Bi(OTf)₃-chiral bipyridine ligand, Sc- or Bi-catalyzed asymmetric meso-epoxide ring-opening reactions with amines, and asymmetric Mannich-type reactions of silicon enolates with N-acylhydrazones in the presence of a chiral Zn catalyst have been developed. Water plays key roles in these asymmetric reactions.