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.
1 February 2018 in Russian Journal of Organic Chemistry
Precise molecular structures resulting from the noncovalent interaction of Br2 with benzene (and toluene) reveal the unusual localized bonding to specific (one or two) carbon centers in prereactive complexes leading directly to the transition states for electrophilic aromatic brominations.
1 April 2017 in Russian Journal of Organic Chemistry
The review analyzes data published in the past decade on the use of trifluoromethanesulfonic acid (triflic acid, CF3SO3H, TfOH) in organic synthesis, in particular in electrophilic aromatic substitution (Friedel–Crafts) reactions, formation of carbon–carbon and carbon–heteroatom bonds, isomerizations, syntheses of carboand heterocyclic structures, and other reactions, as well as in natural and organometallic compounds chemistry. The high protonating power and low nucleophilicity makes trifluoromethanesulfonic acid capable of generating from organic molecules cationic species which can be detected by spectral methods (NMR, IR spectroscopy, etc.), and their transformations can be studied. Experimental simplicity and efficiency of reactions promoted by trifluoromethanesulfonic acid make it a convenient reagent for the synthesis of new organic compounds.