35007-64-8

Upstream product

• 186581-53-3 diazomethane 
• 73945-73-0 (R)-2,3-o-isopropylidene-D-glyceroyl chloride 
• 583-50-6 D-erythrose 
• 95-43-2 D-threose 
• 50-00-0 formaldehyd 
• 57-04-5 dihydroxyacetone phosphate 
• 210230-59-4 D-erythrofuranose 
• 909878-64-4 meso-erythritol 
• 1927-27-1 β-hydroxypyruvate 
• 141-46-8 Glycolaldehyde 
• 50-99-7 D-glucose 
• 2418-52-2 D-threitol 
• 3369-79-7 Lithium hydroxypyruvate 

Downstream Products

• 95-43-2 D-threose 
• 583-50-6 D-erythrose 
• 57-55-6 propylene glycol 
• 2418-52-2 D-threitol 
• 909878-64-4 meso-erythritol 
• 107-21-1 ethylene glycol 
• 584-03-2 1,2-dihydroxybutane 
• 6968-16-7 rac-threitol 
• 56-81-5 glycerol 

Relevant academic research and scientific papers

Efficient Production of Biomass-Derived C4 Chiral Synthons in Aqueous Solution

Carbohydrates are expected to replace petroleum and to become the base of industrial chemistry. Chirality is one particular area in which carbohydrates have a special potential advantage over petroleum resources. Herein, we report a catalytic approach for the direct production of d-tetroses [i.e., d-(?)-erythrose and d-(+)-erythrulose] from d-hexoses through a fast retro-aldol process at 190 °C that achieves a yield of 46 % and completely retains the chiral centers in the final chiral synthon. The d-tetrose products were further converted into their derivatives, thereby accomplishing transfer of chirality from natural chiral hexoses to high-value-added chiral chemicals. Our results also suggest that the product distribution for the conversion of d-hexoses was determined by their isomerization and epimerization trends that competed with their corresponding retro-aldol condensation processes.

FORMATION OF 3-OCTULOSES BY A SELF-ALDOL REACTION OF D-ERYTHROSE

When kept at 105 deg C for 2.5 h, weakly alkaline, syrupy D-erythrose was readily converted into a mixture containing mainly D-glycero-tetrulose, the previously unknown β-D-altro-L-glycero-3-octulofuranose (2), and α-D-gluco-L-glycero-3-octulopyranose, which were isolated as the corresponding acetates.Treatment of 2 with Dowex 50 (H+) resin yielded 3,8-anhydro-β-D-altro-L-glycero-octulopyranose, identified as its acetate.Previous discrepancies in the D values for D-erythrose appear partly to originate in the self-aldol reaction.The dimerisation of D-erythrose 4-phosphate is also described.

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.

Study of the Specificity of a Spinach Transketolase on Achiral Substrates

The behaviour and the specificity of a spinach transketolase towards achiral aldehydes was studied.We have shown that these aldehydes are accepted by the enzyme and yield the corresponding saccharides with good enantiomeric excess.

Glucose isomerase catalysed isomerisation reactions of (2 R,3 R)- configured aldofuranoses into the corresponding open-chain 2-ketoses

Immobilised glucose isomerase (EC 5.3.1.5) accepted various (2 R,3R)- configured aldofuranoses such as D-erythrose, as well as homologous C-5- modified o-ribose derivatives, as substrates. In the case of D-erythrose, quantitative conversion into D-glycero-tetrulose took place. D-Ribofuranoses were converted into the corresponding open-chain 2-ketoses in isolated yields of 65%. Surprisingly, L-erythrose also turned out to be a substrate of this enzyme.

Modular microfluidic reactor and inline filtration system for the biocatalytic synthesis of chiral metabolites

Biocatalytic synthesis is now well established amongst catalytic methodologies as an extremely useful approach for the industrial synthesis of high-value compounds, due to its many advantages such as high reaction specificity and selectivity. However, engineering a biocatalytic process can be complex and time-consuming. This paper presents a modular microfluidic reactor and in-line filtration system for the rapid and small-scale evaluation of biocatalytic reactions. The system combines a substrate with a biocatalyst in free solution, incubates the two components until full conversion to product has been achieved, before extracting the product. The system has been applied to the transketolase-catalysed reaction of hydroxypyruvate (HPA) and glycolaldehyde (GA) to l-erythrulose, demonstrating complete conversion of substrate to product, complete retention of the enzyme and an overall yield of approximately 65%. The complete conversion of HPA and propanal to (3S)-1,3-dihydroxypentan-2- one with a mutant transketolase further demonstrated the applicability of the microfluidic system for organic synthesis.

PROCESSES FOR PREPARING C-4 SUGARS AND KETOSE SUGARS

Various processes for preparing C4 aldoses and/or ketones thereof are described. Various processes are described for preparing C4 aldoses and/or ketones thereof from feed compositions comprising glycolaldehyde. Also, various processes for preparing useful downstream products and intermediates, such as erythritol and erythronic acid, from the C4 aldoses and/or ketones thereof are described.

ISOMERISATION OF C4-C6 ALDOSES WITH ZEOLITES

The present invention relates to isomerization of C4-C6 aldoses to their corresponding C4-C6 ketoses. In particular, the invention concerns isomerization of C4-C6 aldoses over solid zeolite catalysts free of any metals other than aluminum, in the presence of suitable solvent(s) at suitable elevated temperatures. C6 and C5 aldose sugars such as glucose and xylose, which are available in large amounts from biomass precursors, are isomerized to fructose and xylulose respectively, in a one or two-step process over inexpensive commercially available zeolite catalysts, containing aluminum as the only metal in the catalyst. The ketoses obtained are used as sweeteners in the food and/or brewery industry, or treated to obtain downstream platform chemicals such as lactic acid, HMF, levulinic acid, furfural, MMHB, and the like. FIG. 7

Chemoselective Pd-catalyzed oxidation of polyols: Synthetic scope and mechanistic studies

The regio- and chemoselective oxidation of unprotected vicinal polyols with [(neocuproine)Pd(OAc)]2(OTf)2 (1) (neocuproine = 2,9-dimethyl-1,10-phenanthroline) occurs readily under mild reaction conditions to generate α-hydroxy ketones. The oxidation of vicinal diols is both faster and more selective than the oxidation of primary and secondary alcohols; vicinal 1,2-diols are oxidized selectively to hydroxy ketones, whereas primary alcohols are oxidized in preference to secondary alcohols. Oxidative lactonization of 1,5-diols yields cyclic lactones. Catalyst loadings as low as 0.12 mol % in oxidation reactions on a 10 g scale can be used. The exquisite selectivity of this catalyst system is evident in the chemoselective and stereospecific oxidation of the polyol (S,S)-1,2,3,4-tetrahydroxybutane [(S,S)-threitol] to (S)-erythrulose. Mechanistic, kinetic, and theoretical studies revealed that the rate laws for the oxidation of primary and secondary alcohols differ from those of diols. Density functional theory calculations support the conclusion that β-hydride elimination to give hydroxy ketones is product-determining for the oxidation of vicinal diols, whereas for primary and secondary alcohols, pre-equilibria favoring primary alkoxides are product-determining. In situ desorption electrospray ionization mass spectrometry (DESI-MS) revealed several key intermediates in the proposed catalytic cycle.

Chemoselective oxidation of polyols with chiral palladium catalysts

Chiral palladium-based catalysts derived from pyridinyl oxazoline (pyOx) ligands catalyze the oxidation of alcohols, including 1,2-diols, triols, and tetraols, with high regio- and chemoselectivity. Screening of various chiral oxazoline-derived ligands for the oxidation of a model diol, 1,2-propanediol (1,2-PD), revealed that the nature of the ligand had a significant influence on the activity and chemoselectivity for oxidation of vicinal diols. The PyOx ligands containing an α-methyl substituent were the most active for the oxidation of 1,2-PD using benzoquinone as the terminal oxidant. Oxidation of vicinal diols and polyols occurs selectively at the secondary alcohol to afford α-hydroxy ketones in isolated yields of 62-87%. Chemoselective oxidation of meso-erythritol with the chiral [(S)-(α-Me(tert-Bu)PyOx)Pd(OAc)] 2[OTf]2 afforded (S)-erthyrulose in 62% yield and 24% ee.