A new efficient and expeditious one-pot synthesis of thiiranes and olefins from cyclic sulfates of vic-diols is described. Opening of cyclic sulfates with potassium thioacetate or potassium thiocyanate followed by treatment with sodium methoxide led to episulfides. Olefins were obtained when potassium selenocyanate was used as nucleophile, and the obtained monoesters were treated with sodium borohydride. This method was applied to acyclic polyols derived from chiral glycerine, 1,2-isopropylidenehexofuranoses with different subtituents at C-3, and dimethyl acetals derived from pentoses and hexoses. The methodology is highly versatile, and its applicability has been demonstrated by the synthesis of different 4- and 5-thiosugars by opening of the thiirane ring with sodium acetate or lithium aluminum hydride. Reduction with lithium aluminum hydride of the thiocyanate sulfate potassium salt obtained by the opening of cyclic sulfate with KSCN allowed the direct synthesis of 5-deoxy-4-thio- and 6-deoxy-5-thiosugars. Cyclic thiosugars with the sulfur atom in the ring are obtained by acidic hydrolysis of the 5-thiol derivatives of 1,2-O-isopropylidenehexofuranoses and 4-thiopentose dimethyl acetals. Using this method, an efficient synthesis of 5-thio-l-fucose as well as the synthesis of 2,5-dideoxy-4-thiofuranose is described.

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