Dithioacetals of Sugars

Wander, Joseph D.; Horton, Derek

doi:10.1016/s0065-2318(08)60336-4

Cited by 53 publications

(9 citation statements)

References 400 publications

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“…Compounds of general structure I belong to a class of intermediates called glycosyl dithioacetals 3. Glycosyl dithioacetals were first prepared by Fischer in the 19th century and, as such, represent some of the oldest known carbohydrate derivatives 4. These compounds are easily prepared in high yield and offer a convenient starting point for preparing other acyclic and also some furanoside derivatives of sugars.…”

Section: Introductionmentioning

confidence: 99%

Effect of metal cationization on the tandem mass spectra of glycosyl dithioacetals

et al. 2004

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The effect of metal cationization on the tandem mass spectra of glycosyl dithioacetals of glucose, mannose, galactose, rhamnose, arabinose and xylose was studied by electrospray ionization mass spectrometry under ammonium and metal (Li, Na, Ag and Cu) ion cationization conditions. The ammonium-cationized glycosyl dithioacetals fragment by loss of ammonia followed by either two molecules of EtSH or one molecule of EtSH and one molecule of H2O. Lithium cationization leads to additional eliminations such as EtSEt and EtSSEt and C-C cleavages. Elimination of EtSH is not observed under sodium cationization. Silver cationization, on the other hand, leads to additional fragmentations involving the elimination of silver as AgOH and AgSEt. Copper cationization results in adducts where copper has undergone a change of oxidation state from II to I. Li+, Ag+ and Cu+ cationization seem to favour cyclization resulting in elimination of EtSH. However, the mechanisms seem to be differently affected by different metal ions. Li+ and Ag+ cationization appear to be non-specific and favour cyclization involving C2-, C4- and C5-hydroxyl hydrogens, whereas Cu+ cationization seems to favour cyclization involving C4-hydroxyl hydrogen.

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Section: Introductionmentioning

confidence: 99%

Effect of metal cationization on the tandem mass spectra of glycosyl dithioacetals

et al. 2004

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“…Wander and Horton (8) have suggested sulfur participation during the methylation step. Haines (I) has suggested methylation on sulfur followed by an intramolecular nucleophilic displacement.…”

Section: Discussionmentioning

confidence: 99%

“…It was recognized at that time (6) that this evidence did not constitute proof of structure. However, it was later considered (8,18) that the most likely structure was 3,4,5,6-tetra-0-acetyl-D-glucose diethyl dithioacetal. Analysis of the lH nmr spectrum at 100 Hz of 8 in chloroform-d as previously with the aid of decoupling experiments unambiguously showed that this product was 2,3,5,6-tetra-0-acetyl-Dglucose diethyl dithioacetal (8).…”

Section: 356-tetra-0-acetyl-d-glucose Diethylmentioning

confidence: 99%

Revision of the structures of partially acylated derivatives of aldose diethyl dithioacetals

Grindley¹,

Ponnampalam²

1980

Can. J. Chem.

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T. BRUCE GRINDLEY and RATHY PONNAMPALAM. Can. J. Chem. 58,1365 (1980. lH nuclear magnetic resonance spectroscopy is used to correct the structures of most of the known partially acylated derivatives of aldose diethyl dithioacetals which contain more than one acyl group. Previous work had suggested that the hydroxyl group on carbon-2 was the least readily acylated secondary hydroxyl group; current work indicates that it is among the most readily acylated. Evidence is presented which shows that the preferential methylation of aldose diethyl dithioacetals at 0-2 is caused by the presence of the sulfur atoms.T. BRUCE GRINDLEY et RATHY PONNAMPALAM. Can. J. Chem. 58, 1365(1980. La spectroscopic de rmn 'H est utilisee pour corriger la structure de la plupart des derives connus, partiellement acyles, des diethyl dithioacetals d'aldose contenant plus d'un groupe acyle. Des travaux anterieurs ont suggere que legroupe hydroxyle sur le carbone 2 Ctait le groupe secondaire le moins facilement acyle. Le present travail indique que ce groupe est un des plus facilement acyles et on y demontre aussi que la methylation preferentielle des diethyl dithioacetals d'aldose a la position 0-2 est due la presence d'atomes de soufre.There has been considerable interest in the to be uncertain. In this publication, we revise the selective acylation of carbohydrates in the last few structures of four of the five known derivatives of years (I). This activity has been directed at this type. evaluating the relative reactivities of the various Results hydroxyl groups and also at generating useful StrLlcturalAssigrzrnent synthetic intermediates. Although little systematic Structural assignments for this series of attention has been given to the partial acylation of pounds were made from the I~ nmr spectra by aldOse d i e t h~l dithiOacetals, a number partially ,sing the observation (13) that converacylated derivatives have been synthesized (2-7). sion of an hydroxyl group to an acetate causes the It is well established that acylation can be per-signal for a geminal secondary proton to appear formed at the terminal primary hy-1.0-1.2 ppm downfield from its position in the und r o x~l position (2). In addition, a number of de-substituted derivative. The effect of a benzoate rivatives which are more fully substituted have group is similar. Since the number of acyl groups been prepared in fair to good yields (3-7). With one present in each derivative was already known, the exception (71, the structures of these derivatives above observation allowed totally unambiguous were considered to have the groups On the structural determination after the individual signals h~d r o x~l group and then progressively up in the IH nmr spectra had been assigned to specific the carbon skeleton. For instance, the tri-0-protons. benzoyl derivative of D-galactose diethyl dithioacetal was considered to be the 4,5,6-tri-0-2,4,5,6-Tetra-0-benzoyl-D-glucose Diethyl benzoyl derivative (6). One of these derivatives, Dithioacetal ( I ) and its Derivatives the tetrabenzoyl deriv...

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“…Sugars react rapidly with alkanethiols in the presence of acid catalysts at room temperature to give acyclic dialkyl dithioacetals as the main products [79], and therefore the reaction is markedly different from the Fischer glycosidation. These open-chain compounds can be used to prepare monosaccharide derivatives with a free carbonyl group, such as 2,3,4,5,6-penta-Oacetyl-D-glucose:…”

Section: Thioacetals and Thioglycosidesmentioning

confidence: 99%

“…Figure 20. Amadori rearrangement of glycosyl amines induced by acid catalysis: D-Glucopyranosylamine is converted into a 1-alkylamino-D-fructose[79] …”

mentioning

confidence: 99%

Carbohydrates: Occurrence, Structures and Chemistry

Lichtenthaler

2010

Ullmann's Encyclopedia of Industrial Chemistry

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Dithioacetals of Sugars

Cited by 53 publications

References 400 publications

Effect of metal cationization on the tandem mass spectra of glycosyl dithioacetals

Effect of metal cationization on the tandem mass spectra of glycosyl dithioacetals

Revision of the structures of partially acylated derivatives of aldose diethyl dithioacetals

Carbohydrates: Occurrence, Structures and Chemistry

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