Aldehydo Sugars Research Articles

A concise approach to .beta.-(1.fwdarw.6)- and .beta.,.beta.-(1.fwdarw.1)-linked C-disaccharides. The synthesis of C-.beta.,.beta.-trehalose peracetate

The fluoride ion mediated condensation of the tetraacetate of β-C-glucopyranosylnitromethane with aldehydo sugars, followed by the elaboration of the resulting nitroaldol, provides and expeditious approach to β-(1→6)-linked (from hexodialdose derivatives) and β,β-(1→1)-linked (from aldehydo-hexoses) C-disaccharides. C-β,β-Trehalose peracetate, the first example of a C-disaccharide related to the trehaloses, was prepared using this methodology

ChemInform Abstract: Silyl Nitronates in Carbohydrate Chemistry. Chain‐Extension Reactions.

AbstractThe aldehydo sugars (I) react with the silyl nitronate (II) to form the nitro alcohols (III).

Synthesis of Blocked Sugars Bearing a Terminal 1-Cyanovinyl Group

Abstract A series of blocked sugar aldehydes treated with the conjugate base of nitromethane afforded the expected nitrosugars 1–7, whose configuration at the new asymmetric centre was assigned by CD. Nitroenoses 8–14, obtained from the corresponding saturated β-hydroxy nitrosugars, reacted with potassium cyanide, afforded the terminal 1-cyanovinyl sugar derivatives 15–23. Another route to 1-cyanovinylic sugars bearing a free hydroxy group (24 and 25) consisted in reacting aldehydo sugars with the conjugate base of acrylonitrile. The 1-cyanovinyl sugars are soft electrophiles which react with hydroxylamines to give the product of a conjugate addition (27 and 28). The interest of these compounds resides in their often selective toxicity towards cells, viruses or bacteria.

Synthesis of 2-deoxy- d- arabino-(6- 13C)hexose

2-Deoxy- d- arabino-[6- 13C]hexose ( 10), to be used to test the stability of 2-deoxy- d- arabino-hexose 6-phosphate in brain tissue, was prepared. 2-Deoxy- d- arabino-hexose was labeled at C-6 because of the large difference in chemical shift between C-6 in the free sugar and C-6 in the 6-phosphate. The synthetic scheme resembled that used for the synthesis of d-[6- 13C]glucose that involved the removal of C-6 from d-glucose followed by its replacement with 13C. The protected derivative methyl 2-deoxy-α- d- arabino-hexofuranoside was prepared, using trifluoroacetic acid in methanol. This was treated with periodate, which cleaves only between C-5 and C-6, to afford an aldehyde which reacted directly with K 13CN to give a mixture of the d- arabino and l- xylo nitriles. The enriched nitriles were reduced with hydrogen in the presence of 5% Pd-carbon catalyst to a mixture of 6- aldehydo sugars. These were reduced with NaBH 4 to a mixture of the two labeled methyl furanosides. Acid hydrolysis followed by ion-exchange chromatography on AG-50(Ca 2+) resin at 65° gave 10 in an overall yield of 16% from K 13CN.

Fragmentation and wittig olefination of glucosamine derivatives-a simple route to open chain amino sugars and chiral glycerols

The Wittig-reaction of 2-acylamino-2-deoxy-4,6-0-ethylidene glucose 1 leads either to the chiral glycerols 6, via a fragmentation of the sugar, or to the chain-elongated derivatives 8, depending on type of the ylide. Compounds 8 can be converted easily to the open-chain aldehydo sugar 10 in two steps.

Loss or transfer of an acetyl group during Knoevenagel reactions of aldehydo sugars with acetylacetone

Loss or transfer of an acetyl group during Knoevenagel reactions of aldehydo sugars with acetylacetone

Antiviral compounds. 1. Structure-activity relationship of some antiviral enediones derived from aldehydo sugars.

A series of aldehydo sugars was subjected to condensation reactions with active methylene compounds. Acetylacetone was condensed with 2,4-O-benzylidene-3,5-O-dibenzoyl-D-ribose (1), 2,4:3,5-O-dibenzylidene-D-ribose (6), 2,3,4,5-tetraacetyl-D-ribose (7), and 2,3,4,5,6-pentaacetyl-D-glucose (9) to yield 3-ylidene-2,4-pentanedione derivatives 2, 11, 12, and 13, respectively. Sugar derivatives 1 and 6 were also condensed with benzoylacetone to give 14 and 18, with acetoacetanilide to give 16 and 19, with malononitrile to give 17 and 20, and with alpha-(gamma-butyrolactonylidene)triphenylphosphorane to give 21 and 22, respectively. Condensation of 1 with dibenzoylmethane gave 15. The double bond in compounds 2 and 11 was saturated by hydrogenation to give 23 and 24. All alpha, beta-unsaturated carbonyl compounds obtained exhibited antiviral activity and cytotoxicity. Compound 11 was found to have the most significant and selective antiviral activity against herpes simplex virus.

Kinetics of oxidation of aldoses by thallium(III) in acid perchlorate medium

The kinetics of oxidation of aldoses by thallium(III) in acid perchlorate medium have been investigated under pseudo-first-order conditions. The oxidation rate of different aldoses, which is in the order d-ribose > d-arabinose > d-xylose > d-galactose > d-mannose > d-glucose, is explained on the basis of its correlation with the percentage of free aldehydo sugar. The rate decreases with increase in the acidity, and is strongly inhibited by chloride and acetate ions. Thermodynamic parameters are reported, and suitable mechanistic steps are proposed on the basis of the kinetic and stoichiometric results.

Synthesis of 4-(Glycosyl)isoxazoline N-Oxides and Related Substances

Abstract 4-(Glycosyl)isoxazoline N-oxides were synthesized directly from aldehydo sugars by one-step cyclization with double mole of methyl nitroacetate in a satisfactory yield. 2,3-O-Isopropylidene-d-glyceraldehyde reacted with methyl nitroacetate to give 4-(1,2-O-isopropylidene-d-glycero-dihydroxyethyl)-3,5-bis(methoxycarbonyl)isoxazoline N-oxide. The same treatment of 2,3 : 4,5-di-O-isopropylidene-aldehydo-l-arabinose and penta-O-acetyl-aldehydo-d-glucose also gave the corresponding homologs. From the corresponding cyclic aldehydo sugars, 4-aldofuranosyl-3,5-bis(methoxycarbonyl)isoxazoline N-oxides, e.g. 4-(2,3-O-isopropylidene-β-d-erythrofuranosyl)-, 4-[(4R)-3-O-benzyl-1,2-O-isopropylidene-β-l-threofuranos-4-yl]-, 4-(2,3,5-tri-O-benzyl-β-d-ribofuranosyl)-, and 4-(2,3,5-tri-O-benzoyl-β-d-ribofuranosyl)-derivatives were synthesized. The latter was converted into 3,5-dicarbamoyl-4-(β-d-ribofuranosyl)isoxazoline by deoxygenation followed by carbamoylation and deprotection.

Enol acetates of aldehydo sugar derivatives. Synthesis and crystallographic determination of double-bond geometry

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTEnol acetates of aldehydo sugar derivatives. Synthesis and crystallographic determination of double-bond geometryArnaud Ducruix, Claudine Pascard-Billy, Stephen J. Eitelman, and Derek HortonCite this: J. Org. Chem. 1976, 41, 15, 2652–2653Publication Date (Print):July 1, 1976Publication History Published online1 May 2002Published inissue 1 July 1976https://doi.org/10.1021/jo00877a036RIGHTS & PERMISSIONSArticle Views41Altmetric-Citations11LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (270 KB) Get e-Alerts Get e-Alerts

ChemInform Abstract: DECARBONYLATION OF ALDEHYDO SUGAR DERIVATIVES WITH CHLOROTRIS(METHYLDIPHENYLPHOSPHINE)RHODIUM(I)

Chemischer InformationsdienstVolume 7, Issue 22 Natural Products ChemInform Abstract: DECARBONYLATION OF ALDEHYDO SUGAR DERIVATIVES WITH CHLOROTRIS(METHYLDIPHENYLPHOSPHINE)RHODIUM(I) D. J. WARD, D. J. WARDSearch for more papers by this authorW. A. SZAREK, W. A. SZAREKSearch for more papers by this authorJ. K. N. JONES, J. K. N. JONESSearch for more papers by this author D. J. WARD, D. J. WARDSearch for more papers by this authorW. A. SZAREK, W. A. SZAREKSearch for more papers by this authorJ. K. N. JONES, J. K. N. JONESSearch for more papers by this author First published: June 1, 1976 https://doi.org/10.1002/chin.197622323Read the full textAboutPDF ToolsRequest permissionExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinkedInRedditWechat No abstract is available for this article. Volume7, Issue22June 1, 1976 RelatedInformation

Étude de la bromation d'hydrazones d'aldéhydo-sucres

p-Nitrophenylhydrazones of aldehydo sugars have been treated with one equivalent of bromine. The presence of gem-bromoazo intermediates, which have been suggested for this type of reaction with an S E2′ mechanism, have been demonstrated, and one of these compounds, 3- O-benzyl-5( R)-bromo-5-deoxy- 1,2- O-isopropylidene- 5( R)- p-nitrophenylazo-α- D-xylofuranose, was isolated in crystalline form. Two gem-bromoazo diastereoisomers were obtained from the same hydrazone. These rather unstable derivatives underwent a prototropic reaction, which led to the formation of the corresponding hydrazonoyl bromide.

Dérivés C-glycosyliques : Partie XI. Étude de la chloration d'oximes d'aldéhydo-sucres

The chlorination of oximes of aldehydo sugars takes place via an S E 2′ mechanism and gives the corresponding gem-chloronitroso derivatives which are in equilibrium with their dimers. The study of the monomer formation from the dimer by n.m.r. spectroscopy at various temperatures indicates a positive difference of standard entropy. The gem-chloronitroso derivatives obtained isomerize into hydroximoyl chlorides.

Synthesis of unsaturated aldehydes by hydroboration of propargyl alcohols and from aldehydo sugar precursors

Propargyl acetates obtained by ethynylation of aldehydo sugar derivatives, followed by acetylation, can be converted by hydroboration with bis(isoamyl)borane and subsequent treatment with hydrogen peroxide into α,β-unsaturated aldehydes; the latter may also be obtained by treating the original aldehydo sugar derivative with formylmethylenetriphenylphosphorane. By these two routes the aldehydo sugars 2,3- O-isopropylidene- aldehydo- D-glyceraldehyde ( 1), 2,3,4,5-tetra- O-acetyl- aldehydo- D-arabinose ( 5), and 2,3:4,5-di- O-isopropylidene- aldehydo- D-arabinose ( 9) have been converted with 2-carbon chain-extension into the corresponding trans-unsaturated aldehydes 3, 7, and 11, respectively. Likewise, by the acetylene route, 1,2:3,4-di- O-isopropylidene-6- aldehydo-α- D- galacto-hexodialdo-1,5-pyranose ( 13) was converted into the C 8 unsaturated aldehyde 15, although the Wittig route was unsuccessful in this instance, as it was with methyl 2,3-di- O-acetyl-4-deoxy-6- aldehydo-β- L- threo-hex-4-enodialdo-1,5-pyranoside ( 16).

Synthetic Studies of Amino Acids by the Use of Copper(II) Complex. III. Syntheses of Several 2-Amino-2-deoxyaldonic Acids by the Use of Bisglycinato- and N-Pyruvylideneglycinatoaquocopper(II)

Abstract A comparative study of the relative reactivity of bisglycinatocopper(II) and N-pyruvylideneglycinatoaquocopper(II) in a base-catalyzed condensation reaction with aldehydo sugar derivatives concluded that the latter complex is much more reactive than the former. This reaction was found to proceed with a considerably high stereoselectivity to afford blocked 2-amino-2-deoxyaldonic acids with a threo configurational relationship between C–2 and C–3, and between C–3 and C–4. The resultant products were converted to the corresponding free 2-amino-2-deoxyaldonic acids in good yields by deblocking them with Amberlite IR-12OB(H form).

Stereochemistry of Dehydrogenation by D-Galactose Oxidase

The stereochemistry of dehydrogenation of the primary carbinol group of D-galactose by D-galactose oxidase has been determined. Using D-galactose-6-d and methyl β-D-galactopyranoside-6-d, it has been established that the reaction involves removal of the pro-S 6-hydrogen atom. This conclusion is based on product analysis, and on the relative impact of the deuterium isotope effect on oxidation rates of substrates having different R:S deuteration patterns. The absolute configurations at C-6 of these substrates have been determined by selective chemical transformations to products of known configuration. The rotational conformation of the 6-carbinol group of D-galactose and its possible relationship to the specificity of the enzyme are discussed, as well as the stereochemistry of reductive deuteration of aldehydo sugar derivatives.

Synthetic Studies of Amino Acids by the Use of Copper Complex. II. The Condensation Reaction of N-Pyruvylideneglycinatocopper(II) Complexes with various Aldehydes

Abstract An investigation of the mechanism of the reaction which involves the base-catalyzed condensation of bis(glycinato)copper(II) with aldehydes was carried out with the purpose of improving it so that it can proceed even with lower molar equivalent ratios of aldehydes to the complex and under milder conditions. On the basis of the results reported in the literature and those of this investigation, the reaction has been carried out as expected and has been newly shown to be applicable to p-tolualdehyde and p-chlorobenzaldehyde, and, moreover, to such aldehydo sugar derivatives as 2,3-O-isopropylidene-d-glyceraldehyde by the use of N-pyruvylideneglycinatocopper(II) complexes in the reaction in place of bis(glycinato)copper(II). An attempt at further improvement will also be described in the present communication.

Syn and anti oxime isomers of an aldehydo sugar derivative

syn and anti oxime isomers of an aldehydo sugar derivative

1,2:3,4-di- O-isopropylidene-α- D-galacto-hexodialdo-1,5-pyranose and its 6-aldehydrol

Oxidation of 1,2:3,4-di- O-isopropylidene-α- D-galactopyranose ( 1) with methyl sulfoxide- N,N′-dicyclohexylcarbodiimide-pyridinium phosphate (Pfitzner-Moffatt reagent) furnishes a preparative route to the title aldehyde 2. In aqueous solution, 2 exists entirely in the form of its 6-aldehydrol ( 8). In common with a number of other aldehydo sugar derivatives, compound 2 exhibits zero spin-coupling between the aldehyde proton and the proton vicinal to it. The aldehyde 2 was characterized as the crystalline 6-oxime ( 3) and 6-( p-nitrophenyl)hydrazone ( 7). Compounds 2, 3, and 7 are important as potential intermediates in chain-extension reactions leading to 6-amino-6,8-dideoxy-octoses related to lincomycin.

A New Approach to the Synthesis of Aldehydo Sugars

A New Approach to the Synthesis of Aldehydo Sugars