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This chapter describes recent advances in the development of chiral vanadium and niobium catalysts for enantioselective carbon–carbon bond-forming transformations. The catalyst prepared from a vanadium salt or a niobium salt with a chiral multidentate ligand is a powerful tool for the efficient synthesis of optically enriched compounds such as cyanohydrins, amino alcohols and 1,1′-bi-2-naphthols, which can be readily transformed to biologically active compounds and chiral ligands.

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