Direct Synthesis of Glycosyl Fluorides from Hemiacetals Using Diphenylchlorophosphate–KHF ₂

Herein, we report a highly efficient and mild deoxyfluorination strategy for the synthesis of glycosyl fluorides directly from glycosyl hemiacetals using diphenylchlorophosphate in combination with the fluorinating reagent KHF₂. This protocol employs bench-stable and readily available substrates, exhibits excellent functional group tolerance, and affords both armed and disarmed glycosyl fluorides. The synthesized fluoroglycosides exhibited broad synthetic utility in O- and C-glycosylation. Notably, time-resolved NMR analysis revealed direct evidence for a glycosyl phosphate-mediated pathway for the deoxyfluorination of hemiacetals.