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The catalytic asymmetric addition of dimethylzinc to [alpha]-ketoesters in the presence of (-)-MITH and triethyl borate as an additive has given the corresponding chiral [alpha]-hydroxy esters with high enantioselectivities. The advantages of this method are that this ligand can be used for preparing tetrasubstituted [alpha]-hydroxyl esters with good enantioselectivities without the modification of its parent structure and both enantiomers are easily prepared.