Cyanohydrins are considered to be versatile synthons in organic synthesis because they can be readily converted to a-hydroxycarboxylic acids,1} oc-hydroxyaldehydes2) and ethanolamine derivatives,3) which include a number of physiologically active compounds. Lactic acid, tartaric acid, ephedrine and /?-adrenergic blocking agents are the representative examples of these classes of compounds. Thus, synthesis of chiral cyanohydrins is considered to be an interesting and useful problem, but only a very few reports have been known so far.4>5) Cyanohydrins are knownto be rather unstable compounds because of rapid equilibrium between aldehydes and hydrogen cyanide,6) and this equilibrium will inevitablly be accompanied by racemization of chiral cyanohydrins. Thus, based on the assumption that it would be desirable to prepare chiral
Preparatin of optically pure α-methoxy-α-trifluoromethyl-α-phenylacetic acid via microbial asymmetric hydrolysis of cyanohydrin acetate as the key step is described.
Microorganisms that hydrolyze the one enantiomer of /-phenoxyacetaldehyde cyanohydrin acetate were screened, and Bacillus coagulans isolated from soil was found to be the best. This bacterium was applied to the asymmetric hydrolysis of other aryloxyacetaldehyde derivatives to give satisfactory results. The effect of adding dimethyl sulfoxide to the medium is also described. Cyanide anion is a unique reagent in organic synthesis, because it is the only commercially available carbanion that is stable in water. It can be utilized in Q homologation for carbonyl compounds via cyanohydrins and further transformations.1 } One interesting class of compounds that can be easily obtained from cyanohydrins are ethanolamine derivatives, which include jS-adrenergic blocking agents and physiological amines such as noradrenaline. To synthesize these compounds, chiral cyanohydrins are needed. As only a few routes have been disclosed for the synthesis of chiral cyanohydrins,2) we tried to develop a method for obtaining these compounds with the aid of a microbial enzyme system. In the previous paper,3} it was demonstrated that a geneous Bacillus exhibited high enantioselectivity in the hydrolysis of some aryloxyacetaldehyde cyanohydrin acetates (4). In this paper, a further spectrum of substrate specificity and the effect of adding dimethyl sulfoxide to the incubation mediumare described. Materials and Methods Spectroscopic measurements. IR and^-NMR spectra were taken as reported previously.3) Mass spectra were recorded on a Hitachi M-80 instrument. Medium. The basal medium for screening and cultivation consisted of glucose (1%), K2HPO4 (0.5%), pep-215 tone (0.7%) and yeast extract (0.5%) in distilled water, at pH 7.2. The buffer solution was prepared by mixing a solution of Na2HPO4 and NaH2PO4.
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