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Enantioselective catalysts produce organic compounds in enantiomerically enriched form. They are highly efficient tools for the synthesis of biologically active materials, such as pharmaceuticals and crop-protection chemicals, in which enantiomeric purity can be critical. The design of chiral ligands is the key to developing new enantioselective catalysts. Three unusual families of ligands have been used to develop practical technology for enantioselective hydrocyanation of olefins, ring-opening of epoxides, and hydrogenation of various compounds.