N-Acetylation of the Hexosamines

Roseman, Saul; Ludowieg, Julio

doi:10.1021/ja01630a098

Cited by 234 publications

(62 citation statements)

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“…Preparation of N-Acetylgalaaosamine.--N-acetylgalactosamine was prepared from commercial galactosamine hydroehloride (Mann Research Laboratories, New York) by the acetylation method of Roseman and Ludowieg (8). The product was assayed for purity by paper chromatography and gave the expected color value (30 to 35 per cent of N-acetylglucosamine) in the N-acetylhexosamine method of Reissig et al (9).…”

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confidence: 99%

Studies on the Chemical Structure of the Streptococcal Cell Wall

Krause

McCarty

1962

The Journal of Experimental Medicine

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In the preceding paper of this series, the trypsinized cell walls of Groups A and A-variant streptococci were shown to be composed of their respective group-specific polysaccharide antigen and a mucopeptide polymer (1). The data presented here indicate that Group C streptococcal cell walls contain the same two components. The mucopeptide is similar in composition to that of Group A streptococci with N-acetylglucosamine, N-acetylmuramic acid, and alanine, lysine, glutamic acid, and glycine as the principal constituents. The groupspecific polysaccharide also resembles that of Group A in that it is composed of rhamnose and hexosamine. However, in Group C polysaccharide the predominant hexosam~ne is N-acetylgalactosxmlne rather than N-acetylglucosamine. Previous studies have shown that the specificity of Group A carbohydrate is largely determined by terminal/3-N-acetylglucos~mln~de residues (2, 3) and in the present paper evidence is presented which indicates that N-acetylgalactosamine plays a comparable role in determining the serological specificity of group C carbohydrate. Materials and MetkodsThe following organisms were used for the preparation of cell walls and isolation of groupspecific carbohydrate: Group A, strain T12; Group A-variant, strain K43var.; Group C, strains H45A and 28RP95. A large quantity of strain H45A was kindly supplied by Lederle Laboratories. The methods for preparing cell walls and muralytic enzymes, and for extractions of carbohydrate both by enzymatic and chemical procedures have been previously described (1).Analytical Methods.--Analytical methods for rhamnose, glucosamine, muramic acid, and amino acids were the same as previously described (1).Because galactosamine as well as glucosamine is present in the cell wall of Group C streptococci, methods were required to estimate the relative amounts of these two sugars. For the preliminary work which required only an approximate determination of the relative amounts of glucosamine and galactosamine in a preparation the method of Tracey (4) was satisfactory. With this method a borate buffer is employed in the Elson-Morgan procedure which results

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Studies on the Chemical Structure of the Streptococcal Cell Wall

Krause

McCarty

1962

The Journal of Experimental Medicine

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“…Authentic samples of alkyl 2-acetamido-2-deoxy-cc-D-glucopyranoside were prepared by alcoholysis of Nacetyl-D-glucosamine in the presence of alcohol-washed Amberlite IR-120 resin in the proton form (10). After reaction at the reflux temperature was co~llplete, the resin was removed by filtration and washed with the alcohol.…”

Section: Metllods Arid Reference Conzpoundsmentioning

confidence: 99%

“…However, the corresponding experiments starting from the ethyl and n-propyl oximes required purification of the hydrochlorides by colunln chromatography on microcrystalline cellulose (13) followed by N-acetylation (10) to obtain a pure crystalline product. The yields were 25-35% in each case and the products were identified by direct conlparison with authentic samples.…”

Section: Gas-liquid Partition Ci2rot77atographic Analysis Andmentioning

confidence: 99%

Hydrogenation of alkyl 2-oximino-α-D-arabino-hexopyranosides

Lemieux¹,

Gunner²

1968

Can. J. Chem.

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Hydrogenation of alkyl 2-oximino-or-D-arnbino-hexopyranosides in the presence of palladium on charcoal and hydrochloric acid gave mixtures of the alkyl 2-amino-2-deoxy-or-D-hexopyranoside hydrochlorides with the gluco and tnniii~o configurations in about 90% yields. The fraction of gl~tco compound varied substantially with the nature of the alkyl group; viz., methyl, 71 %; ethyl or 11-propyl, 62%; isopropyl, 80 %. More of the Inatvzo compound is formed, viz., isopropyl, 50 %, when the 3,4,6-triacetate of the oximinoglycoside is hydrogenated. Hydrogenation of methyl 6-0-(2-oximino-a-Dnrabit~o-hexopyranosy1)-8-D-glucopyranoside gave an about equimolar mixture of the two configurations.Canadian Journal of Chemistry, 46, 397 (1968) The occurrence of 2-amino-2-deoxy-a-glycopyranosyl groups in a wide variety of antibiotics (1) has rendered the synthesis of such glycosides (a-glycosaininides) a leading problem in carbohydrate chemistry. p-Glycosaminides in which the aglycon is either the residue of a simple alcohol or a more complex carbohydrate structure can normally be obtained via the KoenigsKnorr reaction or its modifications (2). The yield depends strongly on the complexity of the potential aglycon. To date there exists no controlled synthesis of complex a-glycosaminides in appreciable yield. Of the various methods employed, alcoholysis of the parent sugar or derivative in the presence of acid proceeds in best yield (3). However this method is inherently limited to simple acid-resistant alcohols. For more coinplex alcohols, for example appropriately blocked carbohydrate structures, only low yields of a-glycosaminides are available usually via Koenigs-Knorr type reactions (4). The reduction of the 2-oximino-a-hexopyranosides, which are formed in high yield on reaction of alcol~ols with the nitrosyl chloride adduct of acetylated glycals (5, 6), offered a new approach to these compounds and is the subject of this paper. The work is concerned mainly with the preparation of alkyl glycopyranosaminides from simple alkyl (methyl, ethyl, iz-propyl, and isopropyl) alcohols which are normally best prepared by alcoholysis of the aminosugars. Nevertheless, the data provide an insight to the factors which affect the stereochemical routes of the reductions. Also, the result obtained in the pre-'Presented at the Symposium on Synthesis, Organic Division, Chemical Institute of Canada, Banff, Alberta, August 31 -September 2, 1966.paration of a mixture of methyl 6-0-(2-amino-2-deoxy-a-D-glucopyran0syl)-p-D-glucopyranoside with the corresponding a-D-manno isomer is described as an illustration of an a-linked disaccharide synthesis.The alkyl 2-amino-2-deoxy-a-D-glucopyranosides formed in the reductions were identified by direct comparisons with authentic samples prepared from D-glucosamine and this comprises proof of the a-D-configuration for the parent oxinzino-glycosides.' The formation of alkyl 2 -amino -2-deoxy -a -D -mannopyranosides was based on this fact together with nuclear magnetic resonance (n.m.r.) data for these compoun...

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“…Hydrolysis of the diacetate 8 with hydrochloric acid afforded crystalline 2-amino-2,6-dideoxy-6-fluoro-a-D-glucose hydrochloride (11) in 90% yield. N-Acetylation of the amine salt 11 was accomplished by deionization of a solution of 11 followed by treatment with acetic anhydride (12) to give crystalline 2-acetamido-2,6-dideoxy-6-fluoro-a-D-glucose (12).…”

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confidence: 99%

“…This latter treatment afforded a crystalline mixture of triacetates of 2-acetamido-2,6-dideoxy-6-fluoro-D-glucose which was mainly the a-pyranose, but which could not be resolved into a pure anomer by recrystallization. The pure a-pyranose tri-0-acetate (10) was, however, obtained from the 2-acetamido sugar (12) by acetylation with acetic anhydride in pyridine.…”

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confidence: 99%

Synthesis of fluoro derivatives of 2-amino-2-deoxy-D-galactose and -D-glucose

Hough¹,

Penglis²,

Richardson³

1981

Can. J. Chem.

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Selective fluoride displacement of the 6-mesyloxy group of methyl 2-benzamido-3-O-benzyl-2-deoxy-4,6-di-O-mesyl-α-D-glucopyranoside 4 gave the 6-fluoride 5. Subsequent removal of the blocking substituents afforded 2-amino-2,6-dideoxy-6-fluoro-D-glucose, isolated as its hydrochloride 11 and its N-acetyl derivative 12. Nucleophilic displacement of the remaining 4-mesyloxy group of the intermediary 6-fluoro-4-mesylate 5, by benzoate anion afforded derivatives of 2-amino-2,6-deoxy-6-fluoro-D-galactose (18). An interplay of similar substitutions on 4 gave, after deprotection, methyl 2-acetamido-4,6-difluoro-2,4,6-trideoxy-α-D-galactopyranoside (22), methyl 2-acetamido-3-O-acetyl-4,6-difluoro-2,4,6-trideoxy-α-D-glucopyranoside (27), and methyl 2-benzamido-3-O-benzyl-6-fluoro-2,4,6-trideoxy-β-L-threo-hex-4-enopyranoside(28).Methyl 2-acetamido-2,4-dideoxy-4-fluoro-α-D-glucopyranoside diacetate (31) was synthesized from the 4-O-mesyl-6-O-trityl-galactopyranoside 29.

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N-Acetylation of the Hexosamines

Cited by 234 publications

References 2 publications

Studies on the Chemical Structure of the Streptococcal Cell Wall

Studies on the Chemical Structure of the Streptococcal Cell Wall

Hydrogenation of alkyl 2-oximino-α-D-arabino-hexopyranosides

Synthesis of fluoro derivatives of 2-amino-2-deoxy-D-galactose and -D-glucose

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