Idose, 2-amino-2-deoxy

Idopyranoside, methyl 4,6-0-benzyli-dene - 3 - 0 - (ethoxycarbonyl) - 2 - S-methyl-2-thio-a-D-, 120 Idose, 2-amino-2-deoxy-n-, derivatives of, 194... 

A. C. Richardson and H. O. L. Fischer, Cyclization of dialdehydes with nitromethane, Part VI. Preparation of 3- amino-1,6-anhydro-3-deoxy-p-D-gulose, -P-D-altrose and -p-D-idose derivatives and their characterization by means of inversion of mesyloxy groups,./. Am. Chem. Soc., 83 (1961) 1132-1139. 

The difference between the behavior of the 6-amino-6-deoxy-D-glucose and -L-idose derivatives can be rationalized as follows. In the transition states for the formation of the 3,6-anhydro ring from the Tt-gluco isomers, the oxygen (or hetero) atoms attached to C-4 and C-5 are in a sterically unfavorable, cis relationship. The transition states from the h-ido amines involve a trans relationship of these hetero atoms. Thus, for the D-gluco amine, deamination reactions other than 3,6-anhydro ring-formation compete more effectively. 

Another route to 5-amino-5-deoxy-L-idose proceeds from 5-(benzyl-amino)-5-deoxy-l,2-0-isopropylidene-R-L-idurononitrile (56), which is readily obtainable from 1,2-O-isopropylidene-a-D-xj/lo-pentodialdo-1,4-furanose (13) by reaction with benzylamine and hydrogen cy-anide. Partial hydrogenation of the nitrile 56 by the Kuhn procedure, in acid solution, leads to the hexodialdose (57), which is reduced with sodium borohydride to 5-amino-5-deoxy-l,2-0-isopro-pylidene-jS-L-idofuranose. From this compound, tbe acyclic bisulfite adduct (58) is obtained by reaction with sulfiirous acid. Treatment of 58 with barium hydroxide gives crystalline 5-amino-l,6-anhydro-5-deoxy-jS-L-idopyranose (60) in almost quantitative yield. The equilibrium between the pyranose form (61) and its 1,6-anhydride (60) lies far on the side of Ae bicyclic form (60). The equilibrium can be evaluated from the optical rotation of the solution obtained by treat-... 

Derivatives of 5-amino-3,6-anhydro-5-deoxy-L-idose were obtained by C-6-deamination of 5-acetamido-6-amino-l,2-0-cyclohexylidene-... 

Light-induced azrridination of the benzyl acetal of (+)-274 with B0CN3 (Boc = (f-Bu)OCO) gives an aziridine that converted into methyl 3-amino-3-deoxy-a-D-altropyranoside [446], and into 3-amino-3-deoxy-L-idose [447]. 

Synthesis of Amino Sugars by Reduction of Hydrazine Derivatives. 5-Amino-3,6-anhydro-5-deoxy-L-idose Derivatives, M. L. Wolfrom, J. Bernsmann, and D. Horton,/. Org. Chem., 27, 4505-4509 (1962). 

From Achiral Non-carbohydrates. — 3-Deoxy-3-guanidino-D-threose 48 equilibrates with 49. a transition state inhibitor for galactosidase. It was synthesized as shown in Scheme 12 from epoxide 47, which was obtained by porcine pancreatic lipase catalysed enantioselective esterification of the racemic epoxy-alcohol precursor. 6-Deoxy-L-talonolactone 50 was synthesized by an asymmetric aldol condensation - dihydroxylation sequence (Vol.24, p.lS2) in improved diastereoselectivity and was converted into 2-acetamido-2,6-dideoxy-L-fucose (shown as its furanose isomer 51 in Scheme 13), 3-acetamido-3,6Hlideoxy-L-idose and 5-acetamido-S,6-dideoxy-D-allose by S 2 displacements of triflate with azide ion. 4-Amino-4-deoxy-DL-erthrose 53 was obtained from the hetero-Diels-Alder adduct 52 by a sequence of reactions including cis-dihydroxylation (OSO4, NMNO) of the alkene moiety (Scheme 14). The synthesis of a racemic branched-chain lactam is covered in Chapter 16. 

A new route to vicinal amino-dideoxy-sugars has been reported. Thus, catalytic reduction of the keto-hydrazone (135) obtained by treatment of the glycosidulose (134) with alkali gave methyl 3-amino-3,4,6-trideoxy-a -L-n6o-hexopyranoside (Scheme 51). Stevens and his co-workers have extended their work on 4-amino-sugars by synthesizing methyl 4-amino-4,6-dideoxy-a-D-altropyranoside and the isomeric D-idose compound. 3-Amino-3-deoxy-D-altrosides [e.g. (136)] derived from tryptamines have been prepared from methyl... 

Periodate oxidation of suitably protected derivatives of paromomycin and neomycin B, followed by base-catalysed jS-elimination, yielded 5-O-jS-D-ribo-furanosyl- and 5-0-jS-neobiosaminyl-2-deoxystreptamine derivatives, respectively (see also Vol. 8, p. 136). Acidic hydrolysis of penta-A-acetylparomo-mycin liberated 2-amino-2-deoxy-D-glucose, 2-deoxystreptamine, neosamine B (2,6-diamino-2,6-dideoxy-L-idose), and o-ribose, which were separated on a cation-exchange resin. (2-Amino-2-deoxy- and 6-amino-6-deoxy-a-D-gluco-pyranosyl)-2,5-dideoxystreptamine have been synthesized and shown to possess antibacterial activities. ... 

In this manner 3-amino-3-deoxy-D- and -L-ribose, 3-amino-3-deoxy-D-mannose and 3-amino-3-deoxy-D-glucose have been prepared. In an analogous way Richardson and Fischer , starting from laevoglucosan, obtained 3-amino-i,6-anhydro-3-deoxy-D-glucose, -D-altrose and -D-idose. 

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