Synthetic studies on oligosaccharides composed of 5-thioglucopyranose units

An efficient glycosylation reaction of 5-thioglucopyranose was developed and was applied for the preparation of oligosaccharides composed of 5-thioglucopyranose units. Glycosylation reactions of 5-thioglucopyranosyl trichloroacetimidates bearing ethereal protective groups at the 2- O-position 14– 15, and 37 proceed smoothly to give α-glycosides stereoselectively by using a catalytic amount of silyl triflate. This methodology allowed us to achieve syntheses of sulfur-substituted isomaltotetraoside 2 and maltotetraoside 3. These studies also revealed that benzoyl-protected 5-thioglucopyranosyl trichloroacetimidate 12 underwent β-selective glycosylation with C6-OH glucopyranosyl acceptors upon activation by BF 3OEt 2. This was applied for preparation of sulfur-substituted gentiobiosides 1 and 46.