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TEMPO mediated oxidation of carbohydrates using electrochemical methods

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Abstract

The oxidation of some readily available carbohydrates was investigated in aqueous medium using a catalytic amount of 2,2,6,6-Tetramethyl-1-piperidinyl-oxy (TEMPO) as redox mediator. The regeneration of oxoammonium (active form) was electrochemically performed in alkaline medium at a glassy carbon anode and at controlled potential (0.5 V vs. AgCl/Ag). The primary alcohol groups of the carbohydrates without free aldehyde group, were selectively oxidized to the corresponding sodium uronate with high Faradaic yields. The presence of free aldehyde or hemiacetal groups leads to a decrease in selectivities towards uronic acids and increases the amount of by-products.

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References

  • Bragd PL, Besemer AC, van Bekkum H (2000) Bromide-free TEMPO-mediated oxidation of primary alcohol groups in starch and methyl α-glucopyranoside. Carbohydr Res 328:355–363

    Article  CAS  Google Scholar 

  • Bragd PL, Besemer AC, van Bekkum H (2001) TEMPO-derivatives as catalysts in the oxidation of primary alcohol groups in carbohydrates. J Mol Catal A Chem 170:35–42

    Article  CAS  Google Scholar 

  • Bragd PL, Besemer AC, van Bekkum H (2002) Selective oxidation of carbohydrates by 4-AcNH-TEMPO/peracid systems. Carbohydr Polym 49:397–406

    Article  CAS  Google Scholar 

  • Bragd PL, van Bekkum H, Besemer AC (2004) TEMPO-mediated oxidation of polysaccharides: survey of methods and applications. Top Catal 27:49–66

    Article  CAS  Google Scholar 

  • De Nooy AEJ, Besemer AC, van Bekkum H (1995) Highly selective nitroxyl radical-mediated oxidation of primary alcohol groups in water-soluble glucans. Carbohydr Res 269:89–98

    Article  Google Scholar 

  • Edye LA, Meehan GV, Richards GN (1991) Platinum catalyzed oxidation of sucrose. J Carbohydr Chem 10:11–23

    Article  CAS  Google Scholar 

  • Isogai A, Kato Y (1998) Preparation of polyuronic acid from cellulose by TEMPO-mediated oxidation. Cellulose 5:153–164

    Article  CAS  Google Scholar 

  • Kato Y, Habu N, Yamaguchi J, Kobayashi Y, Shibata I, Isogai A, Samejima M (2002) Biodegradation of β-1, 4-linked polyglucuronic acid (cellouronic acid). Cellulose 9:75–81

    Article  CAS  Google Scholar 

  • Kerkenaar A, Besemer AC (1991) Polyglucuronic acid, process for preparing polyglucuronic acid and use of polyglucuronic acid. Patent WO 9104988

  • Kokoh KB, Alonso-Vante N (2006) Electrocatalytic oxidation of lactose on gold nanoparticle modified carbon in carbonate buffer. J Appl Electrochem 36:147–151

    Article  CAS  Google Scholar 

  • Liaigre D, Breton T, Belgsir EM (2005) Kinetic and selectivity control of TEMPO electro-mediated oxidation of alcohols. Electrochem Commun 7:312–316

    Article  CAS  Google Scholar 

  • Parpot P, Kokoh KB, Belgsir EM, Leger JM, Beden B, Lamy C (1997) Electrocatalytic oxidation of sucrose: analysis of the reaction products. J Appl Electrochem 27:25–33

    Article  CAS  Google Scholar 

  • Schämann M, Schäfer HJ (2005) Reaction of enamines and mediated anodic oxidation of carbohydrates with the 2, 2, 6, 6-tetramethylpiperidine-1-oxoammonium ion (TEMPO+). Electrochim Acta 50:4956–4972

    Article  Google Scholar 

  • Sweeley CC, Bentley R, Makita M, Wells WW (2002) Gas–Liquid chromatography of trimethylsilyl derivatives of sugars and related substances. J Am Chem Soc 85:2497–2507

    Article  Google Scholar 

Download references

Acknowledgments

This work was mainly conducted within the framework of a collaborative program CNRS/GRICES between France and Portugal under grant no 20159.

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Authors and Affiliations

  1. Departamento de Quimica, Universidade do Minho, Largo do Paço, 4719, Braga Codex, Portugal

    P. Parpot & A. P. Bettencourt

  2. Laboratory of Electrocatalysis, UMR-CNRS 6503, Université de Poitiers, 40, avenue du Recteur Pineau, 86022, Poitiers cedex, France

    K. Servat, H. Huser & K. B. Kokoh

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  1. P. Parpot
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  2. K. Servat
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  3. A. P. Bettencourt
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  4. H. Huser
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  5. K. B. Kokoh
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Correspondence to K. B. Kokoh.

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Parpot, P., Servat, K., Bettencourt, A.P. et al. TEMPO mediated oxidation of carbohydrates using electrochemical methods. Cellulose 17, 815–824 (2010). https://doi.org/10.1007/s10570-010-9417-7

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  • DOI: https://doi.org/10.1007/s10570-010-9417-7

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