Totally Stereoselective Synthesis of 1,3-Disaccharides through Diels-Alder Reactions

A non-classical, totally stereoselective synthesis of orthogonally protected 1,3-disaccharides is reported. Enantiomerically pure b-keto-d-lactones, efficiently obtained from glucal and galactal, are transformed into electron-poor heterodienes and chemo-, regio- and stereoselectively cycloadded to glycals as electron-rich dienophiles, to directly afford 2-thiodisaccharides. The reductive desulfurization of the latter smoothly gave the corresponding 2,2’-dideoxydisaccharides.