Recent advances in the field of organocatalytic asymmetric synthesis have provided several new methods for preparing chiral compounds in an environment-friendly manner. Among them, proline-catalyzed asymmetric aldol reactions gather a considerable attention from synthetic chemists. In our recent work on the synthesis of (5R,6S)-(−)-6-acetoxy-5-hexadecanolide, we found that aldehydes bearing a 1,3-dithiane moiety at the β-position could serve as a useful synthon of straight-chain aliphatic aldehydes. This method has been successfully applied to the enantioselective synthesis of biologically interesting natural products such as (+)-boronolide, D-ribo-C₁₈-phytosphingosine, pachastrissamine, and (+)-prosophylline.