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β-Benzylsulfanyl-β-trifluoromethyl-α-amino acid esters have been synthesized from (Z)-β- substituted-β-trifluoromethyl-α,β-dehydroamino acid esters via Michael addition with moderate diastereoselectivities. The reaction was investigated with various catalysts. Et3N and LiBr gave satisfactory results, which operated synergistically as bifunctional catalyst. However, the other tested chiral catalysts gave no good enantioselectivities.