The diastereoselectivity in a bakers' yeast reduction of various alkyl 2-alkyl-3-oxoalkanoates can be controlled by a thermal treatment of the yeast in the presence of methyl vinyl ketone. Pretreated bakers' yeast gives the corresponding (2R,3S)-hydroxy esters selectively. Two beta-keto ester reductases, named L-enzyme-1 and L-enzyme-2, are actual reductants of intact bakers' yeast reduction. The thermal stability and inhibition constants of the purified enzymes can dictate the sterochemical outcome of pretreated bakers' yeast reductions.