Reactions of a series of aminodeoxy-pentitols and -hexitols in anhydrous hydrogen fluoride with formic acid as catalyst gave the corresponding 2,5 and 3,6-anhydro-aminodeoxyhexitols respectively in yields of more than 95%. In the analogous reaction of 3-amino-3-deoxy-D-altritol a dianhydride, namely 3-amino-3-deoxy-1,4:2,6-dianhydro-D-altritol, was obtained. The reactions proceed via an intramolecular endo opening of formoxonium intermediates by suitably placed hydroxy groups. A series of further deoxygenated aminodeoxyhexitols was prepared. These compounds, in which the preferred ring-closure was obstructed, were treated with hydrogen fluoride in the presence of a carboxylic acid catalyst. The products from these reactions, including 2,6-anhydrides, were assigned. In case of 1-amino-1,6-dideoxy- or 1-benzylamino-1,3,6-trideoxy-hexitols very efficient and regioselective conversions to the corresponding 2,5-anhydrides were achieved. These compounds can be recognized as muscarine analogues or precursors. The general mechanism of the reactions was evaluated by 13C NMR spectroscopic studies of the acyloxonium ion intermediates.A series of 1-deoxy-1-trifluoroacetamido-hexitols was prepared and treated with anhydrous hydrogen fluoride. Very stereo- and regioselective reactions to the C-2 inverted 2,5-anhydrides were observed in yields of more than 80%. The reactions proceed via 1,2-fused 2-trifluoromethyl-oxazolinium ions which react by an intramolecular attack by HO-5 at C-2 forming a five membered ring with inversion of the configuration at C-2. The intermediate oxazolinium ions of representative reactions were characterized by their 13C NMR spectra.