Bis(pyridinium) iodonium(I) tetrafluoroborate (IPy2BF4), a solid and stable reagent, can be used to transform n-pentenyl orthoesters (NPOEs) and n-pentenyl glycosides (NPGs) into glycosyl fluorides. The latter pair constitutes a new set of semiorthogonal glycosyl donors that can be used in glycosylation strategies, alone or in combination with NPOEs.