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

Abstract Herein, we report a new dehydrative glycosylation protocol mediated by Cp 2 ZrCl 2 ‐AgN(SO 2 F) 2 ·2MeCN combination, which efficiently afforded a diverse array of O ‐ and S ‐glycosides in good to excellent yields (up to 91% yield). A series of armed pyranosyl and furanosyl donors are shown to be suitable donors, and primary, secondary and tertiary alcohols and aliphatic and aromatic thiols are suitable acceptors. In the absence of external acceptors, self‐condensation could occur to provide a convenient approach to symmetrical 1,1'‐disaccharides. 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.