Electroorganic synthesis has become an established, useful, and environmentally benign alternative to classic organic synthesis for the oxidation or the reduction of organic compounds. In this context, the use of redox mediators to achieve indirect processes is attaining increased significance, since it offers many advantages compared to a direct electrolysis. Kinetic inhibitions that are associated with the electron transfer at the electrode/electrolyte interface, for example, can be eliminated and higher or totally different selectivity can be achieved. In many cases, a mediated electron transfer can occur against a potential gradient, meaning that lower potentials are needed, reducing the probability of undesired side-reactions. In addition, the use of electron transfer mediators can help to avoid electrode passivation resulting from polymer film formation on the electrode surface. Although the principle of indirect electrolysis was established many years ago, new, exciting and useful developments continue to be made. In recent years, several new types of redox mediators have been designed and examined, a process that can be accomplished more efficiently and purposefully using modern computational tools. New protocols including, the development of double mediatory systems in biphasic media, enantioselective mediation and heterogeneous electrocatalysis using immobilized mediators have been established. Furthermore, the understanding of mediated electron transfer reaction mechanisms has advanced. This review describes progress in the field of electroorganic synthesis and summarizes recent advances.

Redox catalysis in organic electrosynthesis: basic principles and recent developments.

Recent Advances in Asymmetric Catalytic Metal Carbene Transformations.

Transition metal chemistry of cyclopropenes and cyclopropanes.

http://chemistry-chemists.com/chemister/Warning/Explosives/ExplosiveAbstacts/review-energetic-materials.pdf

A review of energetic materials synthesis

A model for absolute free energies of solvation of organic, small inorganic, and biological molecules in aqueous solution is described. This model has the following features: (i) the solute charge distribution is described by distributed monopoles, and solute screening of dielectric polarization is treated with no restrictions on solute shape; (ii) the energetic effects of cavity formation, dispersion interactions, and solute-induced restructuring of water are included by a semiempirical cavity surface tension; and (iii) both of these effects are included in the solute Hamiltonian operator for self-consistent field (SCF) calculations to allow solvent-induced electronic and geometric distortion of the solute. The model is parameterized for solutes composed of H, C, N, O, F, P, S, Cl, Br, and I against experimental data for 150 neutral solutes and 28 ions, with mean absolute errors of 0.7 and 2.6 kilocalories per mole, respectively.

https://science.sciencemag.org/content/sci/256/5054/213.full.pdf

An SCF Solvation Model for the Hydrophobic Effect and Absolute Free Energies of Aqueous Solvation.

Nitropyrazoles: 1. Synthesis, transformations, and physicochemical properties of nitro derivatives of 1H,4H-pyrazolo[4,3-c]pyrazole

A method of preparation of 5-amino-3,4-dinitropyrazole (1) from 3(5)-methyl-5(3)-nitro- and 3(5)-methyl-4,5(3)-dinitropyrazoles was developed, the key step of which was the Hofmann rearrengement of nitro- and dinitropyrazolecarboxamides. The protonation of 5-amino- 3,4-dinitropyrazole was studied by spectral methods (UV spectroscopy, NMR spectroscopy). In spite of low basicity of the amino group, compound 1 undergoes N-arylation, N-nitration, and annulation reactions with formation of dinitropyrazolo[5,1-a]pyrimidine derivatives and hitherto unknown dinitroimidazo[1,2-b]pyrazole derivatives. Diazotization of 1 leads to 5-diazo-3,4-dinitropyrazole (19), which exists in the form of the internal salt. Some reactions of this compound were studied and the formation of the corresponding 5-halogeno(azido)- 3,4-dinitropyrazoles under the action of the halide and azide ion was shown. Dinitropyrazolo- [5,1-c][1,2,4]triazine and 7-hydroxydinitro-4,7-dihydropyrazolo[5,1-c][1,2,4]triazine deriva- tives were obtained by the action of active methylene compounds on the betaine 19.

Bogdan I. Ugrak

Papers

Nitropyrazoles: 1. Synthesis, transformations, and physicochemical properties of nitro derivatives of 1H,4H-pyrazolo[4,3-c]pyrazole

Nitropyrazoles : 18. Synthesis and transformations of 5-amino-3,4-dinitropyrazole (Full Articles)

Electrochemical transformation of malononitrile and ketones into 3,3-disubstituted-1,1,2,2-tetracyanocyclopropanes

Branched triangulanes: general strategy of synthesis

Synthesis of branched triangulanes