Mannitol 2-amino-1,5-anhydro-2-deoxy

On deamination, 2-amino-l,5-anhydro-2-deoxy-l>mannitol gave l,5-anhydro-2-deoxy-D-eryf/iro-3-hexulose as the major product.54 The substitution product 1,5-anhydro-D-glucitol was formed to a small extent, and inversion again predominated, as with other axial amines (60, 72, and methyl 4-amino-4-deoxy-a-D-galactopyranoside) this is in accord with the predominant inversion of configuration reported for deamination, in water-rich media, of simple cyclohexyla-mines,154 and aminodecahydronaphthalenes39 in which the amino group is axial. As discussed previously (see p. 15), the extent of inversion can vary considerably with the nature of the solvent, and steric factors appear to be important in deaminations of per-O-acetyl amines (see pp. 37 and 49). 

The isolation of D-aroWno-hexulose phenylosazone from both 1,4-anhydro-D-mannitol and 1,5-anhydro-D-glucitol indicates that o-aroMno-hexosulose is among the reaction products. - Crude methyl D-glucofurano-sides in dilute sulfuric acid yield pyruvaldehyde, and 2-amino-2-deoxy-D-glucose hydrochloride suffers oxidative deamination. ... 

Regioselective epoxide opening in l,2-anhydro-3,4 5,6-di-(9-isopropylidene-D-mannitol (46) to amine or azide constitutes another interesting synthetic pathway to D-fructosamine derivatives." As shown in Scheme 20, this reaction furnishes protected 1-amino-1-deoxy-D-mannitol derivatives 47, which can be subsequently oxidized and deprotected into respective A-substituted 1-amino-1-deoxy-D-fructose. 

Various V-substituted 6-amino-6-deoxy-D-glucose derivatives, e.g. 6-8, were synthesized by reaction of the corresponding 5,6-anhydro-D-glucose derivative with secondary amines, and shown to be useful as non-ionic surfactants capable of forming reverse micelles for solubilization of amino acids in hexane. Reaction of such tertiary amines with methyl iodide provided quaternary ammonium-sugar derivatives. The 6-amino-2,5-anhydro-6-deoxy-D-gluconate derivative 10, a potential dipeptide isostere, was obtained from the C2-symmetric, D-mannitol derived bis-epoxide 9 following silica-assisted azidolysis (Scheme 3). Its enantiomer was obtained similarly from an L-iditol bis-epoxide. ... 

Amino-1,5-anhydro-1 -deoxy-D-mannitol or 1,5-dideoxy-1,5-imino-D-mannitol trivial name deoxymannojirimycin... 

S. Claustre, F. Bringaud, L. Azema, R. Baron, J. Perie, and M. Willson, An easy stereospecific synthesis of l-amino-2,5-anhydro-l-deoxy-D-mannitol and arylamino derivatives, Carbohydr. Res., 315 (1999) 339-344. 

Deamination of 2-amino-l,5-anhydro-2-deoxy-D-mannitol with nitrous acid gave principally l,5-anhydro-2-deoxy-D-e/ yt/fru-hex-3-ulose (68%), by migration of H-3, and some 2-deoxy-D-a/ a6/no-hexose (8%) and 1,5-anhydro-D-glucitol (6%). It was established that 2-deoxy-D-nrai>//in-hexose is formed via a hydride-shift mechanism, rather than by acid-catalysed hydration of D-glucal produced by an elimination pathway. 

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