We have developed a direct and efficient route for the synthesis of ciclamycin 0 using the sulfoxide glycosylation reaction to form the glycosidic linkages. In the course of completing the synthesis of ciclamycin 0, we developed new glycosylation conditions that improve the outcome of the sulfoxide reaction. The conditions involve the addition of agents that scavenge phenylsulfenyl triflate, a highly reactive byproduct that forms following activation of anomeric sulfoxides with triflic anhydride.