The stereochemical course of the nonenzymic decarboxylation of the adduct of pyruvate and thiamin was determined. Racemic ethyl 2-(lact-2-yl)thiamin was resolved as the 2,3-dibenzoyltartrate salt under slightly acidic conditions. The specific rotations of the free enantiomers of ethyl 2-(lact-2-yl)thiamin are +8.4 f 0.1' and -8.4 f 0.1'. These were converted to the parent acid, 2-(lact-2-yl)thiamin, by acid hydrolysis. The (+) ethyl ester gave the (-) acid ( [ a ] 2 5 D -4.7 f 0.1") while the (-) ethyl ester gave the (+) acid ([a]25D = +4.7 f 0.1'). The acids were allowed to undergo spontaneous decarboxylation under a variety of conditions: aqueous solution, ethanol solution, dimethylformamide solution, and dimethylformamide solution containing brucine. Under all conditions the product was racemic 2 4 I-hydroxyethy1)thiamin. These results require that the reaction proceed via an achiral intermediate or rapidly equilibrating achirally solvated enantiomeric intermediates. Since it is known that enzymic reactions produce a single enantiomer of 2 4 1-hydroxyethyl)thiamin, the stereospecificity of the enzymic reaction is due to the chirality of the protein and not the intrinsic mechanism of the decarboxylation reaction. ( 5 ) Ullrich, J.; Mannschreck, A. Eur. J . Biochem. 1967, 1 , 110. (6) Kiuger, R.; Karimian, K.; Gish, G.; Pangborn, W. A,; DeTitta, G. T. J. Am. Chem. SOC. 1987, 109, 618. The title and caption to Figure 1 contain a typographical error. The enantiomer of HETI shown has a negatiue (but very weak) specific rotation (circular dichroism is preferred for the assignment), as stated in the rest of the paper. This material results from (+)hydroxyethylthiamin and the configuration at the stereocenter is R as indicated. We thank Professor W. Shin for noting the error.
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