S-Glycosyl thiosulfates have been discovered as a new class of synthetic intermediates in sugar chemistry, named "glycosyl Bunte salts" after 19th-century German chemist, Hans Bunte. The synthesis was achieved by direct condensation of unprotected sugars and sodium thiosulfate using a formamidine-type dehydrating agent in water-acetonitrile mixed solvent. The application of glycosyl Bunte salts is demonstrated with transformation reactions into other glycosyl compounds such as a 1-thio sugar, a glycosyl disulfide, a 1,6-anhydro sugar, and an O-glycoside.