Recent Advances on Fluorine Chemistry.

The purpose of this Special Issue is to showcase the latest findings in fluorine chemistry [...

Monofluoromethylation of -Heterocyclic Compounds.

The review focuses on recent advances in the methodologies for the formation or introduction of the CHF moiety in -heterocyclic substrates over the past 5 years. The monofluoromethyl group is one of the most versatile fluorinated groups used to modify the properties of molecules in synthetic medical chemistry. The review summarizes two strategies for the monofluoromethylation of -containing heterocycles: direct monofluoromethylation with simple XCHF sources (for example, ICHF) and the assembly of -heterocyclic structures from CHF-containing substrates.

The Reactions of Alkenes with Phenyl--triflylimino-λ-iodane: Solvent and Oxidant Impact.

The reactions of alkenes with phenyl--triflylimino-λ-iodane PhI=NTf () have been studied in different conditions. In methylene chloride, in the presence of -halosuccinimides, the products of mono and bis-triflamidation were obtained. In MeCN, the product of bromotriflamidation (with NBS) with solvent interception or of bis-triflamidation (with NIS) is formed.

Sulfonamides with Heterocyclic Periphery as Antiviral Agents.

Sulfonamides are the basic motifs for a whole generation of drugs from a large group of antibiotics. Currently, research in the field of the new sulfonamide synthesis has received a "second wind", due to the increase in the synthetic capabilities of organic chemistry and the study of their medical and biological properties of a wide spectrum of biological activity. New reagents and new reactions make it possible to significantly increase the number of compounds with a sulfonamide fragment in combination with other important pharmacophore groups, such as, for example, a wide class of -containing heterocycles.

Triflamides and Triflimides: Synthesis and Applications.

Among the variety of sulfonamides, triflamides (CFSONHR, TfNHR) occupy a special position in organic chemistry. Triflamides are widely used as reagents, efficient catalysts or additives in numerous reactions. The reasons for the widespread use of these compounds are their high NH-acidity, lipophilicity, catalytic activity and specific chemical properties.

Divergent reactivity of divinylsilanes toward sulfonamides in different oxidative systems.

Oxidative sulfonamidation of divinylsilanes with various sulfonamides in different solvents is reported. With -BuOI as an oxidant, halogenation is the main process, whereas aziridines are the minor products. With NBS in CHCl the products of bromination or bromosulfonamidation were obtained, whereas in MeCN or THF the Ritter-type solvent interception products are formed.

Trifluoromethanesulfonamide vs. Non-Fluorinated Sulfonamides in Oxidative Sulfamidation of the C=C Bond: An In Silico Study.

A theoretical analysis of the reaction of oxidative sulfamidation of several alkenes was performed in order to explain the various experimental observations and different reactivity of triflamide and non-fluorinated sulfonamides. Transformations occurring in the system alkene-sulfonamide in the presence of oxidative system (BuOCl + NaI) were analyzed at the MP2/DGDZVP//B3LYP/DGDZVP level of theory using the IEF-PCM method for taking into account the solvent acetonitrile (MeCN) effect. As the model substrates, styrene, trimethyl(vinyl)silane, dimethyl(divinyl)silane and diphenyl(divinyl)silane were chosen and mesylamide, triflamide, tosylamide and -nosylamide were taken as the reagents.

Solvent interception, heterocyclization and desilylation upon NBS-induced sulfamidation of trimethyl(vinyl)silane.

The reaction of trimethyl(vinyl)silane with sulfonamides in the presence of N-bromosuccinimide was shown to proceed regioselectively in methylene chloride under mild conditions and led to the products of bromosulfamidation in up to 88% yield. The obtained adducts undergo base-promoted dehydrobromination to give 2-trimethylsilyl-N-sulfonyl aziridines in a close to quantitative yield. In the reaction with trifluoromethanesulfonamide in acetonitrile or tetrahydrofuran, the Ritter-type (solvent-interception) products were obtained and converted to 1-triflyl-2-methyl-5-(trimethylsilyl)-2-imidazoline or 4-triflyl-3-(trimethylsilyl)-1,4-oxazocane in almost quantitative yield.

Conformational equilibrium and dynamic behavior of bis-N-triflyl substituted 3,8-diazabicyclo[3.2.1]octane.

Restricted rotation about the N-S partial double bonds in a bis-N-triflyl substituted 3,8-diazabicyclo[3.2.1]octane derivative 1 has been frozen at low temperature (ΔG(≠)  = 11.