Glucosyl 2-amino-2-deoxy

Isomeric glucosylated amino-alditol derivatives, 17, derived from reaction of 2-amino-2-deoxy-mannit-6-yl and -glucit-6-yl a-D-glucopyranosides with methyl methacrylate, were co-polymerized and the physical properties of the resulting polymers were examined in water. 

The amino sugar counterparts of D-glucuronic acid and nonsulfated L-iduronic acid in heparin are either N-acetylated, or nonsulfated at C-6, or both. 2-Acetamido-2-deoxy-D-glucosyl residues account for only a minor proportion of the total hexosamine in heparin, and are especially low in beef-lung preparations (see Table II).8,138,147 -149 In contrast, they... 

FIG. 25.—(A) 13C-N.m.r. Spectrum of Heparin in D20 at Ambient Temperature. (I-Signals are ascribed to a-L-idosyluronic acid residues, and G-signals to 2-amino-2-deoxy-a-D-glucosyl residues chemical shifts are expressed as 8C, relative to external tetramethylsilane.) (B) 13C-N.m.r. Spectrum of Dermatan Sulfate in D20 at 70°. (The horizontal axis is based on 8C, relative to external CS2.)... 

KDO appears to be unique to Gram-negative bacteria. In the LPS that have been studied, KDO residues are situated at the reducing ends of the polysaccharide domains, linking them, by ketosidic bonds, to the fatty-acid-substituted 2-amino-2-deoxy-D-glucosyl disaccharides referred to as lipid A. Fig. 2 is a block diagram indicating the location of KDO in the LPS from Salmonella. 

The 2-amino-2-deoxy-D-glucosyl phosphate linkage is very labile to acid consequently, the teichoic acid is hydrolyzed under mild conditions to a fragment which is apparently44 (43) or (44). Study of this compound should establish which hydroxyl group of the 2-acetamido-2- deoxy-D-glucose residue bears the phosphodiester group. The alanine ester residues (84a) Unpublished work of the authors with Mr. D. Button. 

The resistance of Bacillus cereus cell-wall peptidoglycan to lysozyme action200 is due to the majority of the 2-amino-2-deoxy-D-glucosyl residues having free (nonsubstituted) amino groups. Polysaccharide and peptide components of the cell walls were converted into material susceptible to lysozyme by N-acetylation with acetic anhydride. 

When the structure of a compound is known, the current British-Ameri-can practice42 will be followed. No specific recommendation was made for naming Amadori rearrangement products, but, under Rule 8, the systematic name for the Amadori product of JV-i>-glucosyl-DL-leucine could be 1-(dl-l-carboxy-3-methylbutyl)amino-l-deoxy-D-fructose (I or II), and this name conflicts with the requirement that the carboxyl function takes precedence and that the name should end in acid. Consequently, this compound should be named as N- (n-ara zno-tetrahydroxy-2-oxohexyl)-DL-leucine. A shorter and equally unambiguous name would be l-(DL-leucino)-l-deoxy-D-fructose. (This is sometimes shortened to DL-leucino-deoxyfructose. Such compounds have also been called fructose-leucine, but this is not recommended since it may be confused with such expressions as the fructose-leucine system.11)... 

Chemical synthesis of 1-phosphate esters of 2-amino-2-deoxy-n-glucose has been described.37 127 Reaction of 3,4,6-tri-0-acetyl-2-amino-2-deoxy-a-D-glucosyl bromide hydrobromide (XLII) with triethylammonium diphenyl phosphate gave the l-(diphenyl phosphate) ester, isolated as its hydrochloride (XLIII). Cleavage of the phenyl groups and subsequent deacetylation gave 2-amino-2-deoxy-D-glucosyl phosphate as the crystalline, dipolar-ionic, monopotassium salt (XLV). 

The calcium salt of 2-amino-2-deoxy-D-glucosyl phosphate has been synthesized37 by the interaction of 2-acetamido-3,4,6-tri-0-acetyI-2-deoxy-a-D-glucosyl chloride with silver orthophosphate, with subsequent partial saponification. On the basis of optical rotation, the derivative has been assigned to the a-n series. 2-Amino-2-deoxy-D-glucosyl phosphate is much less stable than the 6-phosphate toward acidic hydrolysis, but it is markedly more... 

A number of very useful indirect methods are available for the preparation of /3-D-glycosides. Polyacetate esters of 2-amino-2-deoxy-D-glucosyl bromide can be used,146 but, for general use, the more stable chlorides are to be preferred, since there is then little tendency for acyl migration147 and they can yield a wider range of glycosides.148,149 Under certain circum-... 

Numerous derivatives of 2-amino-2-deoxy-D-glucosyl halides have been reported recently, especially by Micheel and coworkers.112 113 150 163 168 Methods of synthesis are similar to those for the analogous non-nitrogeneous sugars, namely, treatment of acylated derivatives with acyl halides,169 hydrogen halides,106 1U-112 147 149 or titanic halide.106... 

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