Scheme 3. Oxidation of HMF to 2,5-Furandicarboxylic Acid (FDCA) a a Intermediates: 5-hydroxymethylfuran-2-carboxylic acid (HMFCA), 2,5-diformylfuran (DFF), and 5-formylfuran-2-carboxylic acid (FFCA).

Selected aldohexoses (d‐glucose, d‐mannose, and d‐galactose) and aldopentoses (d‐xylose, l‐arabinose, and d‐ribose) are readily available components of biopolymers. Isomerization reactions of these substances are very attractive as carbon‐efficient processes to broaden the portfolio of abundant monosaccharides. This review focuses on the chemocatalytic isomerization of aldoses into the corresponding ketoses as well as epimerization of aldoses at C2. Recent advances in the fields of catalysis by bases and Lewis acids are considered. The emphasis is laid on newly uncovered catalytic systems and mechanisms of carbohydrate transformations.

SAFT-VRE, 81 SAFT1-RPM, 82 SAFT2, 83 and ePC-SAFT 84 a,e a Requires system-specic data for parameterization, high accuracy. b Structure interpolating group contribution method, medium to high accuracy. c Based on quantum mechanics applicable to any system, medium accuracy. d Density explicitly taken into account. e Suitable for electrolyte systems.

The increasing concerns regarding exhaust and CO 2 emissions from fossil-based transportation fuels have propelled intensive research aimed at finding alternative fuel candidates to realize a clean and renewable fuel system. In this context, dimethoxymethane and its derivatives oxymethylene ethers, a class of oxygenated synthetic fuel, have recently attracted increasing interest because of their fascinating characteristics as a diesel blend compound to significantly reduce soot and nitrogen oxide formation. At present, dimethoxymethane production primarily relies on an established two-step process comprising methanol oxidation and methanol condensation with formaldehyde. Several new synthetic routes based on methanol or CO 2 /H 2 have been proposed by adopting a reaction coupling strategy, which enables the production of dimethoxymethane in one step. A large variety of bi-and multifunctional catalysts have been developed for each synthetic route. This Review comprehensively summarizes the latest advances in synthetic approaches, catalyst systems, structure−activity relationships, and reaction mechanism for the catalytic synthesis of dimethoxymethane. Comparisons regarding the features and limitations of different synthetic approaches as well as the related catalytic materials are also provided in order to indicate possible directions for future research, especially on the rational design of catalysts, a vital factor for the commercial production of dimethoxymethane.

The aqueous-phase isomerization of glucose into fructose, catalyzed by Mg-Al hydrotalcites, has been investigated under batch and continuous conditions. A commercial hydrotalcite with a hydrophobic surface modification and two hydrophilic hydrotalcites in carbonate form, or with OH − anions in the interlayer space, served as catalysts. With the hydrophobic hydrotalcite a lower conversion but superior selectivity to fructose could be demonstrated, reaching above 92% selectivity at 30% conversion. The observed by-products confirm retroaldolization of glucose and fructose as the main side reactions causing catalyst deactivation via adsorption. Additionally, acidic degradation products such as lactic acid cause neutralization of the hydrotalcites facilitating leaching of the Mg 2+ ions. Fructose contributes a greater extent to by-product formation. Applying continuous operation conditions, fructose is removed from the reaction mixture.Therefore, by-product formation is notably suppressed and catalyst stability increases. During 70 to 100 h time-on-stream a slow deactivation of the hydrophobic hydrotalcite occurs. Regeneration can be achieved via calcination and treatment in an aqueous sodium n-dodecyl sulfate solution to introduce dodecyl sulfate anions to the interlayer space of the hydrotalcite, restoring the hydrophobic material properties.

Fructose presents a highly attractive substrate for future biorefineries for production of biofuels as well as bulk and fine chemicals.

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.

No abstract