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.

The catalytic properties of 1 wt % Ru catalysts with the same mean Ru cluster size of 1.4–1.5 nm supported on herringbone‐type carbon nanofibers with different N contents were compared for H2 production from formic acid decomposition. The Ru catalyst on the support with 6.8 wt % N gave a 1.5–2 times higher activity for the dehydrogenation reaction (CO2, H2) than the catalyst on the undoped support. The activity in the dehydration reaction (CO, H2O) was the same. As a result, the selectivity to H2 increased significantly from 83 to 92 % with N‐doping, and the activation energies for both reactions were close (55–58 kJ mol−1). The improvement could be explained by the presence of Ru clusters stabilized by pyridinic N located on the open edges of the external surface of the carbon nanofibers. This N may activate formic acid by the formation of an adduct (>NH+HCOO−) followed by its dehydrogenation on the adjacent Ru clusters.

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Selective oxidation of glucose into gluconic acid by molecular oxygen over carbon-supported Pt and Pd catalysts was studied. Under examination were kinetic regularities of the process in respect of the electronic state of the noble metal surface, dispersion of the active component particles as well as substrate:Pt(Pd) ratio. Catalytic activity of the Pt/C catalysts being normalized to the dispersion of the platinum particles appeared independent of the particles mean diameter in the 1-5 nm range. A negative particle size effect for the Pd/C catalysts, caused by feasibility of oxidation of the surface of noble metal particles with the size less than 3 nm, was observed. Pt/C catalysts exhibited lower specific activity and provided poor selectivity of the glucose oxidation in comparison with Pd/C. Deactivation of Pd/C catalysts arising from the formation of surface Pd(II) oxides was retarded when the reaction was carried out under an oxygen-diffusion control.

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