The Hofer–Moest decarboxylation of d-glucuronic acid and d-glucuronosides

Stapley, Jonathan A.; BeMiller, James N.

doi:10.1016/j.carres.2006.12.011

Cited by 17 publications

(11 citation statements)

References 18 publications

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“…process is called Hofer-Moest reaction. [61] If the electron transfer to the carboxylic acid occurs from atethered moiety with alower oxidation potential, such as electron-rich arenes, the reaction is termed pseudo-Kolbe reaction. [62] Theo utcome of aK olbe electrolysis depends mainly on the reaction conditions.C urrent density,s ubstrate concentration, and pH value are major factors.…”

Section: Kolbe Electrolysismentioning

confidence: 99%

Electrifying Organic Synthesis

et al. 2018

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The direct synthetic organic use of electricity is currently experiencing a renaissance. More synthetically oriented laboratories working in this area are exploiting both novel and more traditional concepts, paving the way to broader applications of this niche technology. As only electrons serve as reagents, the generation of reagent waste is efficiently avoided. Moreover, stoichiometric reagents can be regenerated and allow a transformation to be conducted in an electrocatalytic fashion. However, the application of electroorganic transformations is more than minimizing the waste footprint, it rather gives rise to inherently safe processes, reduces the number of steps of many syntheses, allows for milder reaction conditions, provides alternative means to access desired structural entities, and creates intellectual property (IP) space. When the electricity originates from renewable resources, this surplus might be directly employed as a terminal oxidizing or reducing agent, providing an ultra‐sustainable and therefore highly attractive technique. This Review surveys recent developments in electrochemical synthesis that will influence the future of this area.

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Section: Kolbe Electrolysismentioning

confidence: 99%

Electrifying Organic Synthesis

et al. 2018

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“…96 The group of BeMiller successfully decarboxylated biogenic D-glucuronic acid and D-glucuronosides via the Hofer-Moest mechanism into dialdehydes showing that sugar acids are suitable substrates for Kolbe electrolysis. 103 According to a recent study, the coupling product of levulinic acid 2,7-octanedione (65% yield) can be hydrogenated into 2,7-octanediol (94% yield)a potential monomer for the synthesis of polyesters. 104 The copolyesters poly(2,7-octanediol) terephthalate and poly(2,7-octanediol)-2,5-furanoate were obtained in fair yields (54-63%) with a medium chain length (3978-8531 Da), showing sufficient stability and a low polydispersity index (M w /M N ).…”

Section: Green (Non-)kolbe Electrolysismentioning

confidence: 99%

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

2020

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“…Specifically, they reviewed the so‐called Ruff degradation that involves the decarboxylation of aldonic acids by Fe III and H 2 O 2 in a Fenton‐like system to produce smaller carbohydrates. They also report that Ti IV behaves similarly under the same reaction conditions, which explains the reaction mechanism in the absence of Fe III species 29, 30. Based on this mechanism, we decided to investigate the behaviour of gluconic acid stock solutions under UVA and visible‐light irradiation to assess the resulting product distribution using the 0.5 wt % Ag/TiO 2 catalyst (Figure 5 and Figure S5).…”

Section: Reaction Mechanismmentioning

confidence: 88%

“…As a result of the high oxidising potential, molecules adsorbed on the surface such as gluconic acid can undergo decarboxylation through a mechanism similar to a Ruff degradation (seen typically with Fe III and H 2 O 2 ), but performed here by Ti IV and the photo‐generated radical species 30. This photo‐oxidative pathway does not result in the production of formic acid in each step, so it appears to be the dominant path during the early stages of the photo‐oxidation process (Figure 5).…”

Section: Reaction Mechanismmentioning

confidence: 99%

Visible‐Light‐Controlled Oxidation of Glucose using Titania‐Supported Silver Photocatalysts

et al. 2016

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The visible‐light‐mediated photo‐catalytic selective valorisation of glucose using TiO2‐supported Ag nanoparticles is shown for the first time. The optimisation of the catalyst composition, substrate‐to‐catalyst ratio and reaction medium proved that a near total suppression of the mineralisation pathway could be achieved with a selectivity to partial oxidation products and small‐chain monosaccharides as high as 98 %. The primary products were determined to be gluconic acid, arabinose, erythrose, glyceraldehyde and formic acid. Under UVA light, the selectivity to organics decreases because of the production of CO2 from mineralisation. A reaction mechanism is proposed based on an α‐scission process combined with the Ruff degradation reaction, which explains the presence of the oxidation products, the smaller carbohydrates and formic acid. X‐ray photoelectron spectroscopy, UV/Vis spectroscopy and microscopy studies showed the presence of plasmonic 4 nm particles of silver that were oxidised to silver oxide over the course of the reaction, and recycling studies revealed that this was not detrimental to activity.

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The Hofer–Moest decarboxylation of d-glucuronic acid and d-glucuronosides

Cited by 17 publications

References 18 publications

Electrifying Organic Synthesis

Electrifying Organic Synthesis

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

Visible‐Light‐Controlled Oxidation of Glucose using Titania‐Supported Silver Photocatalysts

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