Stereoselective process for the synthesis of trans-2,5-disubstituted 1,3-dioxane derivatives, which are important liquid-crystal compounds, was developed. The acetalization reaction between aldehydes and 2-substituted 1,3-propanediols in the presence of acids gave the corresponding 2,5-disubstituted 1,3-dioxane derivatives with high trans selectivity (trans/cis = >96:<4), when the reaction was performed with saturated aqueous solutions of inorganic salts having high water solubility, such as CaCl 2 , LiCl, and ZnCl 2 .
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