Currently, the chemistry of organofluorine compounds is a leading and rapidly developing area of organic chemistry. Fluorine present in a molecule largely determines its specific chemical and biological properties. This thematic issue covers the trends of organofluorine chemistry that have been actively developed in Russia the last 15 – 20 years. The review describes nucleophilic substitution and heterocyclization reactions involving fluorinated arenes and quinones and skeletal cationoid rearrangements in the polyfluoroarene series. The transformations involving CF3-substituted carbocations and radical cations are considered. Heterocyclization and oxidative addition reactions of trifluoroacetamide derivatives and transformations of the organic moiety in polyfluorinated organoboranes and borates with retention of the carbon – boron bond are discussed. Particular attention is devoted to catalytic olefination using freons as an efficient synthetic route to fluorinated compounds. The application of unsymmetrical fluorine-containing N-heterocyclic carbene ligands as catalysts for olefin metathesis is demonstrated. A variety of classes of organofluorine compounds are considered, in particular, polyfluorinated arenes and 1,2-diaminobenzenes, 1-halo-2-trifluoroacetylacetylenes, α-fluoronitro compounds, fluorinated heterocycles, 2-hydrazinylidene-1,3-dicarbonyl derivatives, imines and silanes. The potential practical applications of organofluorine compounds in fundamental organic chemistry, materials science and biomedicine are outlined. The bibliography includes 1019 references.

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Reactions of trifluoromethanesulfonamide with α-methylstyrene, 2-methylpent-1-ene, and cycloocta-1,5-diene in the system t-BuOCl-NaI were studied. In the reaction with α-methylstyrene 1-iodo-2-phenylpropan-2-ol was the only isolated product. The reaction with 2-methylpent-1-ene gave a mixture of N,N′-(2-methylpentane-1,2-diyl)bis(trifluoromethanesulfonamide), trifluoro-N-(2-hydroxy-2-methylpentyl)-methanesulfonamide, and N, N′-[oxybis(2-methylpentan-2,1-diyl)]bis(trifluoromethanesulfonamide). Trifluoromethanesulfonamide reacted with cycloocta-1,5-diene to produce a mixture of 2,5-diiodo-9-(trifluoromethylsulfonyl)-9-azabicyclo[4.2.1]nonane and 2,5-diiodo-9-oxabicyclo[4.2.1]nonane; this reaction may be regarded as the first example of direct assembly of bicyclononane skeleton.We recently showed that aziridination of styrene with trifluoromethanesulfonamide in the oxidative system t-BuOCl-NaI · 2 H 2 O leads to formation of both linear structures I and II and heterocyclization product, 2,5-diphenyl-1,4-bis(trifluoromethylsulfonyl)piperazine (III) [1]. The structure of III was proved by X-ray analysis, and a mechanism involving intermediate formation of 2-phenyl-1-trifluoromethylaziridine was proposed [1]. However, the formation of substituted piperazine instead of expected aziridine contradicted the data reported by Minakata et al. [2], according to which aziridines were obtained in reactions of styrene and other alkenes with sulfonamides under analogous conditions due to strong electron-withdrawing effect of the CF 3 group [1]. We tried to reproduce the conditions described in [2] more accurately and carried out the reaction of styrene with trifluoromethanesulfonamide in the presence of anhydrous sodium iodide. In this case, we isolated compounds I and II and 2,6-diphenyl-1,4-bis(trifluoromethylsulfonyl)piperazine (IV) which is isomeric to III [3].In the present work we studied reactions of trifluoromethanesulfonamide with α-methylstyrene, 2-methylpent-1-ene, and cycloocta-1,5-diene under oxidative conditions (in the presence of t-BuOCl-NaI or t-BuOCl-NaI · 2 H 2 O) and analyzed possible ways of formation of the corresponding products.Taking into account that α-methylstyrene reacted with trifluoromethanesulfonamide in a way similar to styrene [2], i.e., with formation of the corresponding aziridine, and that the reaction direction strongly depends on the composition of the oxidative system, α-methylstyrene (V) was brought into reaction with trifluoromethanesulfonamide in two systems containing NaI · 2H 2 O or anhydrous NaI (as in [2]). In both cases, the only product was 1-iodo-2-phenylpropan-2-ol (VI) (Scheme 1). Compound VI is likely to be formed via iodination of α-methylstyrene with t-BuOI to