Intramolecular Displacement Reactions Involving Sulfur Leading to the Formation of 3,6‐Thiaanhydro Sugar Derivatives during the Synthesis of 3,5‐Dithio‐glucofuranose

Abstract During a synthesis of 3,5‐dithio‐glucofuranose, we discovered two interesting intramolecular displacement reactions involving thiolate sulfur on the one hand and a thiirane sulfur on the other. Both generated 3,6‐thiaanhydro structures. We solved the intramolecular displacement problem by using a 5‐ S ,6‐ O ‐isopropylidene protecting group and accomplished 3,5‐dithio‐glucofuranose synthesis in 9 % overall yield.