(4R,5R)-2,2-Dimethyl-α,α,α',α'-tetra-2-naphthalenyl-1,3-dioxolane-4,5-dimethanol, is a privileged ligand analogue of TADDOLs. It can be broadly used in asymmetric synthesis. It is also shown that the titanium TADDOLate catalysts have broad application towards carbonyl addition and cycloaddition.