Theoretical study of Al(iii)-catalyzed conversion of glyoxal to glycolic acid: dual activated 1,2-hydride shift mechanism by protonated Al(OH)3 species

Ohshima, Takashi; Yamamoto, Yoshihiro; Takaki, U.; Inoue, Yoshihisa; Saeki, Takuya; Itou, Katunobu; Maegawa, Yusuke; Iwasaki, Takanori; Mashima, Kazushi

doi:10.1039/b902729g

Cited by 20 publications

(17 citation statements)

References 10 publications

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“…As in the conversion of trioses and tetroses, the mechanism was shown to occur via a 1,2-hydride shift, in agreement with earlier performed theoretical studies; see Fig. 3.17 [ 117 ]. The authors have also investigated this isomerization reaction in continuous fl ow mode.…”

Section: Lewis Acid-catalyzed Conversion Of Glyoxal To Glycolic Acidsupporting

confidence: 74%

Advances in the Conversion of Short-Chain Carbohydrates: A Mechanistic Insight

Clercq

Dusselier

Sels

2016

Green Chemistry and Sustainable Technology

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This chapter discusses recent insights in the conversion of short carbohydrates, viz., sugars containing four or less carbon atoms. Rather than summarizing product yields from such sugars and reported catalysts for the conversions, the focus lies on understanding the underlying mechanisms. These short carbohydrates can lead to a broad spectrum of products, ranging from platform chemicals such as lactic acid and ethylene glycol to high-value chemicals such as α-hydroxy-γ-butyrolactone and even fuels. Different synthesis strategies of these short carbohydrates include (1) a top -down approach from mono-or polysaccharides and (2) a selective bottom -up synthesis route from formaldehyde. Lewis acids play a major role in carbohydrate chemistry, and among these, Sn-based catalysts often show the highest activity. Whether dioses, trioses, or tetroses are used as substrate, Sn is able to convert them effi ciently into α-hydroxy acids or esters, which are useful building blocks for renewable polyesters. Other reaction types such as isomerization, hydrogenation, and cross couplings are discussed briefl y as well. Glycerol and glyoxal are no sugars, but their chemistry shows great resemblance to that of carbohydrates. Therefore, these compounds are also briefl y accounted for in this chapter.

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Section: Lewis Acid-catalyzed Conversion Of Glyoxal To Glycolic Acidsupporting

confidence: 74%

Advances in the Conversion of Short-Chain Carbohydrates: A Mechanistic Insight

Clercq

Dusselier

Sels

2016

Green Chemistry and Sustainable Technology

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“…[23] Figure 7s hows the 13 CNMR spectrum of af resh aqueous solution. [25,26] Ta ble 4l ists all carbon signals,w ith tentative assignments,o bservedf or glyoxal species in D 2 Of or just-dissolved samples and after 10 da tr oom temperature (see also Figures S4.1 and S4.2). [24] Moreover,p olarization experiments (DEPT) point to tertiary carbon atoms,w ith the sole exception of secondary signals at d % 65 ppm, most likely due to impurities (glycolic acid or its esters, glycolaldehyde), either presenti nt he commercials ample [22] or generated in aqueouss olution.…”

Section: Cn Mr Patterns In Cyanamide-glyoxal Mixturesmentioning

confidence: 99%

Formation of Cyanamide–Glyoxal Oligomers in Aqueous Environments Relevant to Primeval and Astrochemical Scenarios: A Spectroscopic and Theoretical Study

Lavado¹,

Concepción²,

Babiano³

et al. 2018

Chemistry A European J

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The condensation of cyanamide and glyoxal, two well-known prebiotic monomers, in an aqueous phase has been investigated in great detail, demonstrating the formation of oligomeric species of varied structure, though consistent with generalizable patterns. This chemistry involving structurally simple substances also illustrates the possibility of building molecular complexity under prebiotically plausible conditions, not only on Earth, but also in extraterrestrial scenarios. We show that cyanamide-glyoxal reactions in water lead to mixtures comprising both acyclic and cyclic fragments, largely based on fused five- and six-membered rings, which can be predicted by computation. Remarkably, such a mixture could be identified using high-resolution electrospray ionization (ESI) mass spectrometry and spectroscopic methods. A few mechanistic pathways can be postulated, most involving the intermediacy of glyoxal cyanoimine and further chain growth, thus increasing the diversity of the observed products. This rationale is supported by theoretical analyses with clear-cut identification of all of the stationary points and transition-state structures. The properties and structural differences of oligomers obtained under thermodynamic conditions in water as opposed to those isolated by precipitation from organic media are also discussed.

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“…19,20 As a result, it cannot be separated in solution by vacuum distillation. 20,21 The solubility of GA is ~2,440 g/kg H 2 O (~71 wt% ) at 25 o C. 22 Its hydrophilicity characteristics is exhibited by its low octanol-water partition coefficient (0.078 at 19 o C). 18,23,24 Note that no supporting data were provided by the authors on the statement that GA cannot be vacuum distilled.…”

Section: Solubilitymentioning

confidence: 99%

“…Ohshima et al 20 formed Al-glycolate complexes in their study o f Al(III)-catalyzed conversion of glyoxal to glycolic acid.…”

Section: Naujalis and Padarauskasmentioning

confidence: 99%

“…This is based on the high solubility of GA and sodium glycolate, their non-volatility characteristics, and more importantly the fact that GA cannot be distilled even under high vacuum. 20,21,28,[31][32][33][34][35][36][37] Also, based on Barney's (Hanford site) solubility s tudies, solubility i ncreases with temperature at least to 50 o C for non-saturated sodium nitrate system. 25,26 Hence, the amount of glycolate that will be in the evaporator overhead and go to the ETF will be small especially when the evaporator's demister is taken into consideration.…”

Section: Volatilizationmentioning

confidence: 99%

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Literature Review on Impact of Glycolate on the 2h Evaporator and the Effluent Treatment Facility

Adu-Wusu¹

2012

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Theoretical study of Al(iii)-catalyzed conversion of glyoxal to glycolic acid: dual activated 1,2-hydride shift mechanism by protonated Al(OH)3 species

Cited by 20 publications

References 10 publications

Advances in the Conversion of Short-Chain Carbohydrates: A Mechanistic Insight

Advances in the Conversion of Short-Chain Carbohydrates: A Mechanistic Insight

Formation of Cyanamide–Glyoxal Oligomers in Aqueous Environments Relevant to Primeval and Astrochemical Scenarios: A Spectroscopic and Theoretical Study

Literature Review on Impact of Glycolate on the 2h Evaporator and the Effluent Treatment Facility

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