95-43-2

Usage

InChI:InChI=1/C4H8O4/c5-2-1-8-4(7)3(2)6/h2-7H,1H2/t2-,3+,4+/m1/s1

Upstream product

• 59-23-4 D-Galactose 
• 95140-39-9 5,5-bis-ethanesulfonyl-D_g-threo-pent-4-ene-1,2,3-triol 
• 533-50-6 D-erythrulose 
• 58-86-6 D-xylose 
• 72599-80-5 D-threofuranose 
• 80877-73-2 β-D-threo-1,4-furanose 
• 80877-72-1 α-D-threo-1,4-furanose 
• 31873-23-1 4,4-bis-acetylamino-D_g-threo-butane-1,2,3-triol 
• 7664-93-9 sulfuric acid 
• 31880-23-6 1,1-bis-ethanesulfonyl-D-1-deoxy-xylitol 
• 64-19-7 acetic acid 
• 50-00-0 formaldehyd 
• 141-46-8 Glycolaldehyde 
• 453-17-8 D-Glyceraldehyde 

Downstream Products

• 2418-52-2 D-threitol 
• 147-71-7 D-tartaric acid 
• 109257-00-3 2-p-toluidino-2-deoxy-D-xylononitrile 
• 128613-52-5 trifluoroacetylated threose anti O-benzyloxime 
• 128613-58-1 trifluoroacetylated threose syn O-benzyloxime 
• 70849-21-7 [1-¹³C₁]-D-xylose 
• 70849-22-8 D-[1-⁽¹³⁾C]-lyxose 
• 533-50-6 D-erythrulose 
• 1518-62-3 2,4-dihydroxybutanoic acid 
• 28119-61-1 4-hydroxy-2-oxobutanal 
• 56-82-6 Glyceraldehyde 
• 128705-39-5 trimethyl silylether of threose anti-O-methyloxime 
• 128706-43-4 trimethyl silylether of threose syn-O-methyloxime 
• 141-46-8 Glycolaldehyde 

Relevant academic research and scientific papers

Selective Reductive Dimerization of CO2into Glycolaldehyde

The selective dimerization of CO2 into glycolaldehyde is achieved in a one-pot two-step process via formaldehyde as a key intermediate. The first step concerns the iron-catalyzed selective reduction of CO2 into formaldehyde via formation and controlled hydrolysis of a bis(boryl)acetal compound. The second step concerns the carbene-catalyzed C-C bond formation to afford glycolaldehyde. Both carbon atoms of glycolaldehyde arise from CO2 as proven by the labeling experiment with 13CO2. This hybrid organometallic/organic catalytic system employs mild conditions (1 atm of CO2, 25 to 80 °C in less than 3 h) and low catalytic loadings (1 and 2.5%, respectively). Glycolaldehyde is obtained in 53% overall yield. The appealing reactivity of glycolaldehyde is exemplified (i) in a dimerization process leading to C4 aldose compounds and (ii) in a tri-component Petasis-Borono-Mannich reaction generating C-N and C-C bonds in one process.

Convergent in situ Generation of Both Transketolase Substrates via Transaminase and Aldolase Reactions for Sequential One-Pot, Three-Step Cascade Synthesis of Ketoses

We describe an efficient three-enzyme, sequential one-pot cascade reaction where both transketolase substrates are generated in situ in a convergent fashion. The nucleophilic donor substrate hydroxypyruvate was obtained from l-serine and pyruvate by a transaminase-catalyzed reaction. In parallel, three different (2S)-α-hydroxylated aldehydes, l-glyceraldehyde, d-threose, and l-erythrose, were generated as electrophilic acceptors from simple achiral compounds glycolaldehyde and formaldehyde by d-fructose-6-phosphate aldolase catalysis. The compatibility of the three enzymes was studied in terms of temperature, enzyme ratio and substrate concentration. The efficiency of the process relied on the irreversibility of the transketolase reaction, driving a shift of the reversible transamination reaction and securing the complete conversion of all substrates. Three valuable (3S,4S)-ketoses, l-ribulose, d-tagatose, and l-psicose were obtained in good yields with high diastereoselectivity.

Catalytic Gels for a Prebiotically Relevant Asymmetric Aldol Reaction in Water: From Organocatalyst Design to Hydrogel Discovery and Back Again

This paper reports an investigation into organocatalytic hydrogels as prebiotically relevant systems. Gels are interesting prebiotic reaction media, combining heterogeneous and homogeneous characteristics with a structurally organized active solid-like catalyst separated from the surrounding environment, yet in intimate contact with the solution phase and readily accessible via liquid-like diffusion. A simple self-assembling glutamine amide derivative 1 was initially found to catalyze a model aldol reaction between cyclohexanone and 4-nitrobenzaldehyde, but it did not maintain its gel structure during reaction. In this study, it was observed that compound 1 could react directly with the benzaldehyde to form a hydrogel in situ based on Schiff base 2 as a low-molecular-weight gelator (LMWG). This new dynamic gel is a rare example of a two-component self-assembled LMWG hydrogel and was fully characterized. It was demonstrated that glutamine amide 1 could select an optimal aldehyde component and preferentially assemble from mixtures. In the hunt for an organocatalyst, reductive conditions were applied to the Schiff base to yield secondary amine 3, which is also a highly effective hydrogelator at very low loadings with a high degree of nanoscale order. Most importantly, the hydrogel based on 3 catalyzed the prebiotically relevant aldol dimerization of glycolaldehyde to give threose and erythrose. In buffered conditions, this reaction gave excellent conversions, good diastereoselectivity, and some enantioselectivity. Catalysis using the hydrogel of 3 was much better than that using non-assembled 3 - demonstrating a clear benefit of self-assembly. The results suggest that hydrogels offer a potential strategy by which prebiotic reactions can be promoted using simple, prebiotically plausible LMWGs that can selectively self-organize from complex mixtures. Such processes may have been of prebiotic importance.

Shape-selective Valorization of Biomass-derived Glycolaldehyde using Tin-containing Zeolites

A highly selective self-condensation of glycolaldehyde to different C4 molecules has been achieved using Lewis acidic stannosilicate catalysts in water at moderate temperatures (40–100 °C). The medium-sized zeolite pores (10-membered ring framework) in Sn-MFI facilitate the formation of tetrose sugars while hindering consecutive aldol reactions leading to hexose sugars. High yields of tetrose sugars (74 %) with minor amounts of vinyl glycolic acid (VGA), an α-hydroxyacid, are obtained using Sn-MFI with selectivities towards C4 products reaching 97 %. Tin catalysts having large pores or no pore structure (Sn-Beta, Sn-MCM-41, Sn-SBA-15, tin chloride) led to lower selectivities for C4 sugars due to formation of hexose sugars. In the case of Sn-Beta, VGA is the main product (30 %), illustrating differences in selectivity of the Sn sites in the different frameworks. Under optimized conditions, GA can undergo further conversion, leading to yields of up to 44 % of VGA using Sn-MFI in water. The use of Sn-MFI offers multiple possibilities for valorization of biomass-derived GA in water under mild conditions selectively producing C4 molecules.

Catalytic effect of aluminium chloride on the example of the conversion of sugar model compounds

Abstract In this work, the catalytic effect of the Bronsted acid hydrochloric acid, the Bronsted base sodium hydroxide and the Lewis acid AlCl3 on the conversion of biomass derived carbohydrates is investigated. On the example of the glycolaldehyde conversion, it is shown that the Lewis acid catalyses the ketol-endiol-tautomerism, the dehydration, the retro-aldol-reaction and the benzilic-acid-rearrangement. The main products are C4- and C6-carbohydrates as well as their secondary products 2-hydroxybut-3-enoic acid 1 and several furans. Under the same reaction conditions hydrochloric acid catalyzes mainly the dehydration and sodium hydroxide the tautomerism and subsequent aldolization.

Zeolite-catalyzed isomerization of tetroses in aqueous medium

The isomerization of erythrose (ERO) was studied in water over commercially available large-pore zeolites, e.g. H-Y, H-USY and H-beta. Among the employed zeolites, H-USY(6) was found to efficiently isomerize the sugar, yielding 45% erythrulose (ERU), 42% ERO and 3% of the epimer threose (THO) (corresponding to the equilibrium mixture), i.e. total tetrose yield 90%, after reaction for 5-7 h at 120 °C. Changing the solvent from water to methanol decreased the yield of ERU markedly to 18% and gave only a total yield of tetroses of 27% which is significantly lower than that obtained in water. Hence, the results demonstrate that water is the preferred solvent compared to lower alcohols for zeolite-catalyzed tetrose isomerization, which is opposite to what has been found previously for analogous pentose and hexose isomerization. A reuse study revealed further that H-USY(6) could be applied for at least five reaction runs with essentially unchanged activity and without significant aluminum leaching from the catalyst. The use of benign reaction conditions and an industrially pertinent solid catalyst in combination with water establishes a new, green tetrose isomerization protocol. the Partner Organisations 2014.

Efficient biocatalytic processes for highly valuable terminally phosphorylated C5 to C9 D-ketoses

A green enzymatic strategy for the synthesis of terminally phosphorylated C5 to C9 naturally occurring D-ketose phosphates and analogues was developed using D-fructose-6-phosphate aldolase (FSA) as a catalyst. This enzyme has stereoselectively catalysed aldol reactions between glycolaldehyde phosphate or ribose-5-phosphate as an acceptor substrate and dihydroxyacetone, hydroxyacetone or hydroxybutanone as a donor. Furthermore, D-glycero-d-altro-2-octulose 8-phosphate was obtained using a straightforward one-pot domino biocatalytic system involving FSA, ribulose-5-phosphate epimerase and ribose-5-phosphate isomerase controlling five contiguous asymmetric centres and starting from achiral material.

Asymmetric organocatalytic formation of protected and unprotected tetroses under potentially prebiotic conditions

Esters of proteinogenic amino acids efficiently catalyse the formation of erythrose and threose under potentially prebiotic conditions in the highest yields and enantioselectivities yet reported. Remarkably while esters of (l)-proline yield (l)-tetroses, esters of (l)-leucine, (l)-alanine and (l)-valine generate (d)-tetroses, offering the potential to account for the link between natural (l)-amino acids and natural (d)-sugars. The effect of pH and NaCl on the yields and enantioselectivities was also investigated and was shown to be significant, with the optimal enantioselectivities occurring at pH 7.

Efficient immobilization of fructose-6-phosphate aldolase in layered double hydroxide: Improved stereoselective synthesis of sugar analogues

Fructose-6-phosphate aldolase immobilized on layered double hydroxide (FSA@LDH) has been characterized and evaluated as a biocatalyst in aldol reactions. The versatile FSA@LDH showed a comparable activity to the free FSA and can be reused several times without a notable loss of activity.

A mutant D-fructose-6-phosphate aldolase (Ala129Ser) with improved affinity towards dihydroxyacetone for the synthesis of polyhydroxylated compounds

A mutant of D-fructose-6-phosphate aldo-lase (FSA) of Escherichia coli, FSA A129S, with im-proved catalytic efficiency towards dihydroxyacetone (DHA), the donor substrate in aldol addition reac-tions, was explored for synthetic applications. The Kcat/KM value for DHA was 17-fold higher with FSA A129S than that with FSA wild type (FSA wt). On the other hand, for hydroxyacetone as donor sub-strate FSA A129S was found to be 3.5-fold less effi-cient than FSA wt. Furthermore, FSA A129S also ac-cepted glycolaldehyde (GA) as donor substrate with 3.3-fold lower affinity than FSA wt. This differential selectivity of both FSA wt and FSA A129S for GA makes them complementary biocatalysts allowing a control over donor and acceptor roles, which is par-ticularly useful in carboligation multi-step cascade synthesis of polyhydroxylated complex compounds. Production of the mutant protein was also improved for its convenient use in synthesis. Several carbohy-drates and nitrocyclitols were efficiently prepared, demonstrating the versatile potential of FSA A129S as biocatalyst in organic synthesis.