Glycosylamines

1 Glycosylamines. - Ai -(p-D-Glucopyranosyl)nicotinic acid was identified as a major metabolite from niacin in cultured tobacco cells.  

Formation of separable, diastereoisomeric JV-glucosyl derivatives (e.g. 3) of racemic 2,2 -indolylindolines, by direct condensation of the bases with free sugar 

Reagents i, BnNHg, MegAI, ii, NaBHaCN, HCHO, AcOH, iii, NaBH4, CF3SO2H. (CH20)  

A sialyl-Lewis conjugate with the tripeptide Arg-Gly-Asp has been prepared by way of a tetrasaccharide glycosylazide using conventional glycosidation reactions, reduction to the glycosamine and coupling with a C-terminal free peptide. In a cell adhesion test, this conjugate was the best competitive inhibitor 

Reagents i, (TmslaNLi then CBr ii, NaNsi iii, H2, Pd/C iv, KOCN, AcOH v, KOBu  

Periodate oxidation of j/V-acetyl-A-)3-D-glycopyranosyl-p-bromoaniline or its /7-anisidine analogue followed by condensation with nitromethane yielded the corresponding iV-acetyl-(3-deoxy-3-nitro-A-j8-D-glucopyranosyl) aniline as the major product in both cases. 

Pinter, J. Kovdcs, A. Messmer, and W. Dietrich, J. Carbohydrates, Nucleosides, Nucleotides, 1978, 5, 225. 

Delpy and A. S. Cerezo, Anales Asoc. Quim. Argentina, 1976, 64, 111. 

A number of 1-pentopyranosyl-isatins (1) have been prepared either from corresponding O-acylated-A -glycosylphenylamines by the Stolle reaction or by chromic acid oxidation of C -acylated-l-pentopyranosyl-indoles.  

The reaction of D-glucuronic acid with proteins has been studied using an L-lysine-containing tripeptide as a model system under physiological conditions, the dimeric glycopeptide (2) was obtained as the major product.  

Sykulski, Acta polon. Pharm 1976,33,295 Chem. Abs., 1977,87,136 277z). 

Kinetic data for the hydrolyses of a number of l-(P-D-galactopyranosyl)-pyridinium salts between pH 2 and 8 have confirmed that the rate-enhancement of 10 °—10 - during enzymic hydrolysis of the salts with E. coli p-D-galactosid-ase is large enough for meaningful conclusions to be drawn about the enzyme mechanism. Thus, it was concluded that the whole of the catalytic effect of the 

Montero, A. Moruzzi, J. Oiry, and J. L. Imbach, European J. Medicin. Chem.-Chim. Ther., 1976, 11, 183 (Chem. Abs., 1977, 86, 30 018e). 

N-Acetyl-2,3,4,6-tetra-O-acetyl-iV-nitroso-P-D-glucopyranosylamine (216) has been synthesized it decomposed to give principally p-D-glucopyranose penta-acetate in dichloromethane or to give a mixture of anomeric o-glucopyranoside 

There have been a number of reports on the Maillard reaction. Oxidation of the melanoidins produced from D-glucose and glycine with potassium permanganate and peracetic acid yielded, among other products, furan-2,5-dicarboxylic acid, suggesting that 5-hydroxymethyl-2-furaldehyde is a precursor of the melanoidic pigments produced in the Maillard reaction. 2-(2-Formyl-5-hydroxymethyl- 

Reagents i, Bn02CCI, PH2NEt ii, NaOH, H2O iii, PivCI, Py iv. Li HMDS, HMPA, R X 

The configuration and solution conformation of various glucosyl amidines 6-8 has been studied by NMR techniques and semi-empirical calculations. Regio-isomeric pseudonucleosides 9 with sulfahydantoins as the base moiety were synthesized by conventional nucleoside synthesis reactions. Glycosylami-nopyrimidines 10 were converted into glycosylaminopyridines 11 by a Diels-Alder - retro-Diels-Alder reaction sequence involving addition of dimethyl 

Carbohydrate Chemistry, Volume 30 The Royal Society of Chemistry, 1998 

A kinetic analysis of the Amadori reaction of glucose with morpholine has been reported, and a study that provides further evidence for the reversibility of the Amadori reaction is covered in Chapter 9 (Section 3.8). 

2 Glycosylamides Includii iV Glycopeptides - The 7V-glycosyl-maleimide 13 was isolated from the leaves of Garania mangostana The positional isomer 14 

The kinetics of the reaction between D-glucose and several alkylamines have been examined by a potentiometric method, and the rate of formation of iV-glyco-sides [e.g. l-JV-(4-aminobenzoyl)-D-xylopyranosylamine] has been measured by determining the decrease of free amino-groups using l,2-naphthoquinone-4-sulphonic acid. Rate constants for the Maillard reaction of glycine with D-xylose, D-glucose, and D-fructose have also been reported.  

The reaction of reducing monosaccharides (e.g. 2,3 5,6-di-0-isopropylidene-a-D-mannofuranose) with an equimolar mixture of phthalimide, dialkyl azodi-carboxylate, and triphenylphosphine yielded both anomeric iV-glycosylphthali-mides, whereas A/ -glycosyl-l,2-dialkoxycarbonylhydrazines [e.g. (160)] were obtained in the absence of phthalimide.  

5-Tri-O-benzoyl-a-D-ribofuranosyl bromide reacted with the metal salts of a series of semicarbazones to give D-ribofuranosylamine derivatives having the general structure (161).  

3S0 Fiedler, M. Hfebabecky, and J. Berdnek, Coll. Czech. Chem. Comm., 1975,40,2378. 

6- tri-0-acetyl-4-0-(2,3,4,6-tetra-0-acetyl-j8-D-galactopyranosyl)- -D-gluco-pyranosylamine with 7V-(benzyloxycarbonyl)-L-aspartic anhydride, and several free and protected glycodipeptides and one glycotripeptide containing the 2-acetamido-A -(L-aspart-4-oyl)-2-deoxy-jS-D-glucopyanosylamine residue.  

D-Glucose reacted with diaminomaleonitrile in acetic acid to yield the A -(2-amino-l, 2-dicyanoethenyl)-)8-D-glucopyranosylamine derivative (149). jS-D-GIucopyranosylamine and 2 amino-2-deoxy-D-glucose (isolated as the fully acetylated derivatives) were produced in low yield on u.v.-irradiation of aqueous solutions of D-glucose and glycine or L-lysine.  

Treatment of per-O-acetylated glycosylamines with 2-chloroethyl isocyanate, followed by nitrosation (sodium nitrite in formic acid) and deacetylation, yielded a series of (2-chloroethyl)nitrosourea derivatives [e.g. l-(2-chloroethyl)-3-(j3-D-gIucopyranosyl)-l-nitrosourea (150)], which showed remarkable anti- 

Machinami, S. Nishiyama, K. Kikuchi, and T. Suami, Bull. Chem. Soc. Japan, 1975, 

Mdssbauer spectra of the ferric chloride complexes of several anomeric A -aryl-D-glucopyranosylamines have been reported.  

The 4-pyridone (151), an analogue of maltol, has been isolated from the reaction of lactose or maltose with a hot aqueous solution of methylammonium acetate. The heterocyclic derivative (152) and the 1,2,4-triazine derivatives (153) have been obtained from 2,3,4,6-tetra-O-acetyl-a-D-glucopyranosyl bromide by standard routes. Bischler-Napieralski cyclization of the corresponding iV-acetyl-tryptamines and dehydrogenation (Pd-BaSO ) gave the )S-D-glucopyranosyl-carboline (154) and the related a-L-arabinopyranosylcarboline. The spin-labelled nitroxide derivative (155) has been prepared by reaction of the nicotinamide derivative with 2,3,5-tri-0-benzoyl-j8-D-ribofuranosyl bromide.  

---

Under conditions, the reaction of tetra-o-acetyl-o-glucopyranosyl bromide with A-4-thiazoline-2-thione provides the glycosylamine (76) (N-alkylation) (Scheme 36) (163). However, treatment of 5-... 

Stereoselective Strecker reactions with galactosylamine 1 can also be achieved with sodium cyanide and acetic acid in 2-propanol. The reactions, however, proceed slowly and with a lower stereoselectivity, giving diastereomeric ratios of the products between 3 1 and 7 1. The scope of the method can be extended to other glycosylamines, e.g., 2,3,4-tri-O-pivaloyl-a-D-arabinosyl-amine which allows the stereoselective synthesis of (A )-amino nitriles61,62. 

Monosaccharides in which an alcoholic hydroxy group has been replaced by an amino group are called amino sugars (see 2-Carb-14). When the hemiacetal hydroxy group is replaced, the compounds are called glycosylamines. 

When the amino group is at the anomeric position, the compound is normally named as a glycosylamine (see 2-Carb-33.6). 

N-Glycosyl derivatives are conveniently named as glycosylamines. In the case of complex heterocyclic amines, such as nucleosides, the same approach is used. 

Carba-glycosylamines [2,3,4-trihydroxy-5-(hydroxymethyl)-1 -cyclohex-ylamine] and related compounds are well known to exist as components of the antibiotic validamycin complex and carba-oligosaccharidic alpha amylase inhibitors. ... 

Microbial degradation of validamycin A (8) with a cell suspension of Pseudomonas dentrificans afforded validamine (202) and valienamine (203). Hydrogenolysis of validamycin B, followed by acid hydrolysis, yielded hydroxy validamine (204). Valiolamine (205) was isolated and shown to be a component of validamycin G. ° Biosynthesis of these carba-glycosylamines was extensively studied, and the intramolecular aldol addition of the... 

Inhibitory Activity of Some Carba-glycosylamines against Three Enzymes... 

Results of inhibition studies with nojirimycin and its analogs published up to 1988, and additional data from the author s laboratory, are summarized in Table VI. It should be noted that the inhibition constants are given in pM instead of mM (as in Tables II - V). Data for glycosylamines are included, in order to facilitate an estimation of the effects caused by the different positions of the basic group in the two types of basic sugar derivative. Not included are the data of Reese and coworkers and of Grover and Cushley on nojirimycin, because these authors were apparently unaware of the slow and only partial dissociation of the nojirimycin hydrogensulfite adduct which had been used instead of free nojirimycin. 

Inhibition of a- and Glycosidases by the Respective 5-Amino-5-deoxyhexopyranoses, 1,5-Dideoxy-],5-iminohexitoIs, and Glycosylamines... 

Enzyme and source 5-Amino-S-deoxy- hexopyranose 1,5-Dideoxy- 1,5-iminohexitol Glycosylamine References... 

Ferndndez-Bolanos JG, Lopez 6 (2007) Synthesis of Heterocycles from Glycosylamines and Glycosyl Azides. 7 31-66... 

---