Selective synthesis of erythrulose and 3-pentulose from formaldehyde and dihydroxyacetone catalyzed by phosphates in a neutral aqueous medium

Simonov, Alexandr N.; Matvienko, L. G.; Pestunova, O. P.; Parmon, Valentin N.; Komandrova, Nadezhda A.; Denisenko, V. A.; Vas’kovskii, V. E.

doi:10.1134/s0023158407040118

Cited by 27 publications

(22 citation statements)

References 13 publications

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“…A preliminary identification of the most obvious of these small resonances, occurring between 4.50 and 4.70 ppm, was made by comparison to 1 H NMR shifts reported for erythrulose, a linear tetrose that is analogous to the keto form of fructose at C1–C3. 27,28 This enabled assignment of H1a, H1b and H3 of the linear keto form. The presence of this isomer in the equilibrated mixture was supported by Fourier-transform infrared (FTIR) spectroscopy (see Supplementary data).…”

Section: Resultsmentioning

confidence: 99%

Observation of the keto tautomer of d-fructose in D2O using 1H NMR spectroscopy

Barclay

Ginic‐Markovic

Johnston

et al. 2012

Carbohydrate Research

146

126

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D-Fructose was analysed by NMR spectroscopy and previously unidentified 1H NMR resonances were assigned to the keto and α-pyranose tautomers. The full assignment of shifts for the various fructose tautomers enabled the use of 1H NMR spectroscopy in studies of the mutarotation (5 – 25 °C) and tautomeric composition at equilibrium (5 – 50 °C). The mutarotation of β-pyranose to furanose tautomers in D2O at a concentration of 0.18 M was found to have an activation energy of 62.6 kJ.mol−1. At tautomeric equilibrium (20 °C in D2O) the distribution of the β-pyranose, β-furanose, α-furanose, α-pyranose and the keto tautomers was found to be 68.23%, 22.35%, 6.24%, 2.67% and 0.50%, respectively. This tautomeric composition was not significantly affected by varying concentration between 0.089 and 0.36 M or acidification to pH 3. Upon equilibrating at 6 temperatures between 5 and 50 °C there was a linear relationship between the change in concentration and temperature for all forms.

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Section: Resultsmentioning

confidence: 99%

Observation of the keto tautomer of d-fructose in D2O using 1H NMR spectroscopy

Barclay

Ginic‐Markovic

Johnston

et al. 2012

Carbohydrate Research

146

126

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“…Formula Classification proceeds the more carbohydrates are turned into a water insoluble tar discernable from an intensifying yellowbrown color of the solution [70]. It was shown, however, that the presence of borate [69,76] or phosphorylated carbohydrates [77,78] overcome that selectivity issue.…”

Section: Namementioning

confidence: 99%

Schreibersite: an effective catalyst in the formose reaction network

et al. 2018

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We report on the ability of the meteoritic material schreibersite to catalyze the generation of higher sugars from simple carbohydrates in the formose reaction network. Since the analysis of carbonaceous meteorites like the Murchison meteorite it has become generally accepted that a substantial amount of organic material has been delivered to the early earth and, therefore, ought to be considered in scenarios for the origin(s) of life. Also for the open question of accessible phosphorus sources, an extraterrestrial material called schreibersite has been identified that is capable of releasing soluble and reactive phosphorus oxyanions that would react with organics to form for instance nucleotides and membrane associated molecules. We have reinvestigated this material using capillary electrophoresis to monitor its corrosion process in water and probed its ability to phosphorylate a wide range of organics. Although showing a poor reactivity of schreibersite, we have found that the material catalyzes the aldol reaction of small carbohydrates forming larger sugar molecules. This reaction in the formose reaction network is a prebiotically likely route to biologically relevant sugars. The results of our study present one of the first instances of connecting extraterrestrial material to prebiotic chemistry on the early earth.

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“…In particular, homogeneous and heterogeneous phosphates and borates exhibit low but sufficient catalytic activity towards the aldol reaction processes, and support the synthesis of erythrulose and 3-pentulose as a result of the in-teraction between CH 2 O and any simple monosaccharide. [52,64,86] The highest selectivity of 45-50 and 35-40 % for pentose and tetrose, respectively, is attained when using dihydroxyacetone as a monosaccharide substrate and a mixture of Na 2 HPO 4 and KH 2 PO 4 as a catalyst at nearly neutral pH. [86] The nature of the lower monosaccharide used as the second substrate does not affect the composition of the final mixture during this synthesis (when formaldehyde is used in a notable excess with respect to the monosaccharde) since the same carbanion corresponding to dihydroxyacetone is formed from glycolaldehyde and glyceraldehyde.…”

Section: Suppression Of Retroaldol Cleavage and Retardation Of Aldol mentioning

confidence: 99%

“…[52,64,86] The highest selectivity of 45-50 and 35-40 % for pentose and tetrose, respectively, is attained when using dihydroxyacetone as a monosaccharide substrate and a mixture of Na 2 HPO 4 and KH 2 PO 4 as a catalyst at nearly neutral pH. [86] The nature of the lower monosaccharide used as the second substrate does not affect the composition of the final mixture during this synthesis (when formaldehyde is used in a notable excess with respect to the monosaccharde) since the same carbanion corresponding to dihydroxyacetone is formed from glycolaldehyde and glyceraldehyde. [52] When nickel phosphate molecular sieves VSB-5 are applied as a heterogeneous catalyst for the addition of CH 2 O to dihydroxyacetone, the aldol reaction proceeds slower and with lower selectivity for erythrulose (31 mol%) and 3-pentulose (24 mol%), and a notable part of the starting monosaccharide is isomerized to yield glyceraldehyde with the selectivity of 24 %.…”

Section: Suppression Of Retroaldol Cleavage and Retardation Of Aldol mentioning

confidence: 99%

“…Aldolization of monosaccharide phosphates. [86,88] threo-3-pentulose, [93] DL-2-C-hydroxymethyl-3-pentulose, [94] and 2,4-bis(hydroxymethyl)-3-pentulose [95] from formaldehyde catalyzed by thiamine hydrochloride (vitamin B1) were elaborated. Generally, the thiazolium-catalyzed synthesis of monosaccharides is performed at temperatures close to 100 8C to provide an appreciable rate of reaction.…”

Section: Thiazolium-catalyzed Oligomerization Of Formaldehydementioning

confidence: 99%

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Catalytic Formation of Monosaccharides: From the Formose Reaction towards Selective Synthesis

et al. 2014

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The formose reaction (FR) has been long the focus of intensive investigations as a simple method for synthesis of complex biologically important monosaccharides and other sugar-like molecules from the simplest organic substrate-formaldehyde. The fundamental importance of the FR is predominantly connected with the ascertainment of plausible scenarios of chemical evolution which could have occurred on the prebiotic Earth to produce the very first molecules of carbohydrates, amino- and nucleic acids, as well as other vitally important substances. The practical importance of studies on the FR is the elaboration of catalytic methods for the synthesis of rare and non-natural monosaccharides and polyols. This Minireview considers the FR from the point of view of chemists working in the field of catalysis with emphasis on the mechanisms of numerous parallel and consequent catalytic transformations that take place during the FR. Based on its kinetics, the FR may be considered as a non-radical chain process with degenerate branching. The Minireview also considers different approaches to the control of selectivity of carbohydrate synthesis from formaldehyde and lower monosaccharides.

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Selective synthesis of erythrulose and 3-pentulose from formaldehyde and dihydroxyacetone catalyzed by phosphates in a neutral aqueous medium

Cited by 27 publications

References 13 publications

Observation of the keto tautomer of d-fructose in D2O using 1H NMR spectroscopy

Observation of the keto tautomer of d-fructose in D2O using 1H NMR spectroscopy

Schreibersite: an effective catalyst in the formose reaction network

Catalytic Formation of Monosaccharides: From the Formose Reaction towards Selective Synthesis

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