Determination of the side-products formed during the nitroxide-mediated bleach oxidation of glucose to glucaric acid

Ibert, Mathias; Marsais, Francis; Merbouh, Nabyl; Brückner, Christian

doi:10.1016/s0008-6215(02)00072-1

Cited by 57 publications

(49 citation statements)

References 33 publications

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“…Glucarate is the end product of nucleotide sugar metabolism and is found naturally in mammals and plants (21,39). Glucarate and its derivatives, such as glucaro-1,4-lactone, have been studied previously as detoxifying and natural anticarcinogenic compounds (8,21,36,39), as well as building blocks for polymer synthesis (16). Glucarate has also been designated as a potential "top value-added" chemical to be produced from biomass (40).…”

Section: Discussionmentioning

confidence: 99%

Cloning and Characterization of Uronate Dehydrogenases from Two Pseudomonads andAgrobacterium tumefaciensStrain C58

et al. 2009

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Uronate dehydrogenase has been cloned from Pseudomonas syringae pv. tomato strain DC3000, Pseudomonas putida KT2440, and Agrobacterium tumefaciens strain C58. The genes were identified by using a novel complementation assay employing an Escherichia coli mutant incapable of consuming glucuronate as the sole carbon source but capable of growth on glucarate. A shotgun library of P. syringae was screened in the mutant E. coli by growing transformed cells on minimal medium containing glucuronic acid. Colonies that survived were evaluated for uronate dehydrogenase, which is capable of converting glucuronic acid to glucaric acid. In this manner, a 0.8-kb open reading frame was identified and subsequently verified to be udh. Homologous enzymes in P. putida and A. tumefaciens were identified based on a similarity search of the sequenced genomes. Recombinant proteins from each of the three organisms expressed in E. coli were purified and characterized. For all three enzymes, the turnover number (k cat ) with glucuronate as a substrate was higher than that with galacturonate; however, the Michaelis constant (K m ) for galacturonate was lower than that for glucuronate. The A. tumefaciens enzyme was found to have the highest rate constant (k cat ‫؍‬ 1.9 ؋ 10 2 s ؊1 on glucuronate), which was more than twofold higher than those of both of the pseudomonad enzymes.

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Section: Discussionmentioning

confidence: 99%

Cloning and Characterization of Uronate Dehydrogenases from Two Pseudomonads andAgrobacterium tumefaciensStrain C58

et al. 2009

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“…During carbohydrate oxidations the secondary alcohols are rarely oxidized, and particularly when strict pH and temperature controls are employed, carbon-carbon bond cleavage is not observed. 316,317 Thus, under suitable conditions, the oxoammonium-mediated oxidations of carbohydrates and nucleosides are quite selective and mild, with little to no over-oxidation. Carbohydrates.…”

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“…77 for D-glucose. 257,316,317,329 In this work, the secondary oxidants used are sodium hypochlorite, chlorine, or bromine. The substrates are D-glucose, D-mannose, and D-galactose, and the yields of sodium salts (from Dglucose and D-mannose) or free acid (from D-galactose) vary between 70 and 80%.…”

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confidence: 99%

“…257,329 It is suggested that these conversions take place in three steps. 316,330 The first is the oxidation of C-1 to an acid salt as is normal with bromine and chlorine oxidations even without a catalyst. The second reaction, the oxidation of C-6 to an aldehyde is nitroxide-catalyzed and is the slow step.…”

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confidence: 99%

“…When the pH drops below 11.5, appreciable carbon-carbon cleavage is observed. 316,317 It is interesting that in these cleavage reactions, no five-carbon fragments are observed during a careful kinetic study of the reaction; that is, no C-1/C-2 or C-5/C-6 cleavage products are observed.…”

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Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

2009

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The discovery in 1959 of stable nitroxide‐based free radicals such as the prototypical 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) led to their use as electron spin resonance (ESR) spin labels in chemistry, biomedicine, and materials science. These nitroxides are prepared by the oxidation of secondary amines that contain no hydrogen atoms on the alpha‐carbons. The unique redox properties of nitroxides enable their use as oxidants in organic synthesis. The varied preparation and uses of oxoammonium salts as stoichiometric oxidants for alcohols are one subject of this review. Oxoammonium ions as oxidants for alcohols have a number of advantages, for example, the method is heavy‐metal free and some of the reactions can be performed in water or aqueous mixtures. A few side reactions are associated with these oxidations. The most serious is the fast reaction of the oxoammonium ion with free amines The several ways these oxidation reactions can be carried out are discussed in detail. They are: Oxidations using stoichimetric quantities of preformed oxoammonium salts carried out in either acidic, neutral, or basic conditions; reactions in which stoichiometric quantities of oxoammonium salts are generated in situ by disproportionation of a nitroxide in the presence of a strong acid; nitroxide‐catalyzed oxidations using a secondary oxidant; efficient nitroxide‐catalyzed oxidations of primary alcohols to carboxylic acids; and oxidations of primary alcohols or hemiacetals that can lead to lactones.

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Nitroxide‐Catalyzed Alcohol Oxidations in Organic Synthesis

Brückner

2010

Stable Radicals

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Determination of the side-products formed during the nitroxide-mediated bleach oxidation of glucose to glucaric acid

Cited by 57 publications

References 33 publications

Cloning and Characterization of Uronate Dehydrogenases from Two Pseudomonads andAgrobacterium tumefaciensStrain C58

Cloning and Characterization of Uronate Dehydrogenases from Two Pseudomonads andAgrobacterium tumefaciensStrain C58

Oxoammonium‐ and Nitroxide‐Catalyzed Oxidations of Alcohols

Nitroxide‐Catalyzed Alcohol Oxidations in Organic Synthesis

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