Lead Tetraacetate Oxidations in the Sugar Group. IV.<sup>1</sup> The Rates of Oxidation of Trehalose, Levoglucosan, α-Methyl-L-sorbopyranoside, Polygalitol and Styracitol in Glacial Acetic Acid<sup>2</sup>

Hockett, Robert C.; Dienes, Margaret T.; Ramsden, Hugh E.

doi:10.1021/ja01248a012

Cited by 21 publications

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“…In dilute solution, its behavior is more akin to that of the 0-ethylidene derivative. I t is probable that the more rapid phases of these reactions involve cyclic forms of the sugars, and that the slower oxidations involve acyclic products (16). Thus, D-mannose and 4-0-formyl-D-arabinose (X) could together account for the rapid uptake of 2 moles per mole, whereas the resulting a-hydroxy aldehyde 3,4-di-0-formyl-D-erythrose (XI)s would be oxidized in the slow step.…”

Section: T Was Concluded Earlier That 4-0-formyl-d-arabinose ( X ) mentioning

confidence: 99%

Ring Contraction During the Lead Tetraacetate Oxidation of Reducing Sugars

Perlin¹

1964

Can. J. Chem.

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The rate of oxidation of D-glucose by lead tetraacetate in acetic acid is affected little by a large change in concentration of reactants, showing that the glycol cleavage step is not ratecontrolling. Oxidation of 3-0-methyl-6-0-trityl-D-glucose yields 3-0-formyl-2-0-methyl-5-0-trityl-D-arabinose; the latter is not derived by production initially of a 4-0-fori11yl derivative that undergoesacyl migration. I t is probable that theoxidation of D-glucoSe proceeds with conversion of the pyranose sugar into a furanose intermediate. By contrast, D-mannose appears t o be oxidized mainly in the pyranose form, a s shown by the oxidation patterns of D-mannose-1-and -2-14C and 5-0-methyl-D-mannofuranose, and the effects of concentration change on the reaction of D-mannose and derivatives. The proximity of the ring oxygen atom t o the 1,2-diol group may contribute t o the unusually high reactivity of D-mannopyranose as compared with other types of monocyclic six-membered ring vic-diols.Intermediate proportions of furanose and pyranose pathways characterize the lead tetraacetate oxidation of the other six aldohexoses. Similarities in the behavior of glucose and idose, gulose and mannose, and allose and talose may originate in steric similarities between these pairs of sugars.T h e lead tetraacetate oxidation (1, 2) of reducing sugars in acetic acid involves primarily the cleavage of a-hydroxy hemiacetal glycol groups, and results in a stepwise shortening of the carbon chain (3,4,5). However, the uptake of oxidant in these reactions is lower than might be anticipated. For example, D-glucose (I) consumes only 2 inoles of lead tetraacetate per mole rather than the 3 moles theoretically possible for the 1,2,3,4-tetrol grouping of the pyranose sugar (I), yielding a diformate ester of D-erythrose rather than of D-glycerose. A possible explanation for these results is t o assume that a complex (6) between the tetravalent lead and the 1,2-diol group of a-D-glucofuranose (11) is a n intermediate in the reaction. This complex could be formed directly from the pyranose sugar, by analogy with the formation of D-glucofuranose 1,2-acetals and borate complexes (7,8), or from the furanose sugar if present in solution even as a minor constituent.Dissociation of the con~plex would give 3-0-formyl-D-arabinose, which, oxidized as a furanose sugar (111), would yield 2,3-di-0-formyl-D-erythrose (IV). Thus, involve~llent of a reactive structure such as I1 accounts for the high rate of the reaction (5, 9), as well as the consuinption of only 2 moles of oxidant per mole. Consistent with these possibilities is the fact that derivatives of D-glucose that are prevented from going over t o a furanose form by substituents a t C-4 are oxidized much more slowly than D-glucose itself, whereas the rate is essentially unaltered by a substituent a t C-3 or C-6 (10).

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Section: T Was Concluded Earlier That 4-0-formyl-d-arabinose ( X ) mentioning

confidence: 99%

Ring Contraction During the Lead Tetraacetate Oxidation of Reducing Sugars

Perlin¹

1964

Can. J. Chem.

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Criegee Glycol Oxidation

2010

Comprehensive Organic Name Reactions and Reagents

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The oxidation of 1,2‐diols (or glycols) to aldehydes or ketones with lead tetraacetate [Pb(OAc) 4 , LTA] via the cleavage of C‐C bond between the hydroxyl‐carrying carbon atoms is generally known as Criegee Glycol oxidation. This reaction has been reported to occur only in anhydrous organic solvent and the oxidation rate depends greatly on the structure of glycol and corresponding solvent. The study finds that the oxidation of cis ‐diol is faster than trans ‐diol on a six‐membered ring for this oxidation. During the oxidation of most of the sugars have been found to get oxidized readily in aqueous solution except sucrose. The oxidation from excess lead tetraacetate gives aldehydes or ketones and carbon dioxide and the decomposition of lead tetraacetate holds an ionic mechanism. This reaction has been applied for the analysis of carbohydrate structures.

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Derivate der Zucker‐mercaptale, III. Mitteil.: Synthesen von D‐Lyxose‐tetraacetaten aus D‐Lyxose‐mercaptalen

Zinner

Brandner

1956

Chem. Ber.

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Lead Tetraacetate Oxidations in the Sugar Group. IV.¹ The Rates of Oxidation of Trehalose, Levoglucosan, α-Methyl-L-sorbopyranoside, Polygalitol and Styracitol in Glacial Acetic Acid²

Abstract: Vol. 65 under reduced pressure to dryness. The friable solid so produced was further dried in ail Abderhalden pistol over potassium hydroxide; yield 17.2 g., m. p. 161°( sinters).

Cited by 21 publications

References 2 publications

Ring Contraction During the Lead Tetraacetate Oxidation of Reducing Sugars

Ring Contraction During the Lead Tetraacetate Oxidation of Reducing Sugars

Criegee Glycol Oxidation

Derivate der Zucker‐mercaptale, III. Mitteil.: Synthesen von D‐Lyxose‐tetraacetaten aus D‐Lyxose‐mercaptalen

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Lead Tetraacetate Oxidations in the Sugar Group. IV.1 The Rates of Oxidation of Trehalose, Levoglucosan, α-Methyl-L-sorbopyranoside, Polygalitol and Styracitol in Glacial Acetic Acid2

Abstract: Vol. 65 under reduced pressure to dryness. The friable solid so produced was further dried in ail Abderhalden pistol over potassium hydroxide; yield 17.2 g., m. p. 161°( sinters).

Cited by 21 publications

References 2 publications

Ring Contraction During the Lead Tetraacetate Oxidation of Reducing Sugars

Ring Contraction During the Lead Tetraacetate Oxidation of Reducing Sugars

Criegee Glycol Oxidation

Derivate der Zucker‐mercaptale, III. Mitteil.: Synthesen von D‐Lyxose‐tetraacetaten aus D‐Lyxose‐mercaptalen

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Lead Tetraacetate Oxidations in the Sugar Group. IV.¹ The Rates of Oxidation of Trehalose, Levoglucosan, α-Methyl-L-sorbopyranoside, Polygalitol and Styracitol in Glacial Acetic Acid²