A Dehydrative Glycosylation Protocol Mediated by Cp2ZrCl2‐AgN(SO2F)2∙2MeCN

We developed a new dehydrative glycosylation protocol mediated by Cp2ZrCl2‐AgN(SO2F)2∙2MeCN combination, which efficiently afforded a diverse array of O‐ and S‐glycosides in good to excellent yields (up to 91% yield). An intriguing rearrangement of 3,4,6‐tri‐O‐benzyl‐2‐deoxy‐D‐glucosose under the Zr promoter system was discovered to provide a C2‐branched pyranose derivatives.