The Front Cover shows the introduction of fluorinated groups into molecules, which gives them interesting and sometimes unexpected physicochemical properties and reactivity. In this study, the configurational stability of fluoroalkyl sulfoxides (shown on the flyer) was investigated and the pKa value of the -CHF2 group was determined, which is very important for medicinal and agrochemical research. The picture is reminiscent of “Kinder Surpise”® where the sulfoxide appears as an exciting molecular toy and the surprises are the physical data determined because nothing was known before about this type of compounds (copyright of the illustration by J.-F. Nierengarten). More information can be found in the Full Paper by G. Hanquet, E. Magnier, F. R. Leroux et al.

The enantiomeric separation of aryl trifluoromethyl and difluoromethyl sulfoxides was realized via chiral chromatography. The configurational stability of each set of enantiomers was then studied by thermal enantiomerization. The ΔG≠ values obtained cover a range of 38.2–41.0 kcal mol−1 at 214 °C, thus demonstrating their optical stability at room temperature. However, a shorter half-life time has been observed for difluoromethyl sulfoxides. Furthermore, the acidities of six aryl difluoromethyl sulfoxides were determined in DMSO by an overlapping indicator method using UV-visible spectrophotometric titrations. The pKa values fall in range of 20.3–22.5 and differ by about 10 log units compared to non-fluorinated analogues.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

A simple and efficient protocol for the oxidation of trifluoromethyl, mono- and difluoromethyl sulfides to the corresponding sulfoxides without over-oxidation to sulfones, using TFPAA prepared in situ from trifluoroacetic acid and 15% H2O2 aqueous solution was developed. The methodology is suitable for a wide range of aromatic and aliphatic substrates in milligram and multigram scales.

We describe herein the photoredox-initiated 1,2-difunctionalization of alkene derivatives with N-chloro S-fluoroalkyl sulfoximines yielding novel fluoroalkyl sulfoximine scaffolds. The reaction is proposed to proceed through an atom-transfer radical addition (ATRA) mechanism involving the generation of fluorinated nitrogen-centered sulfoximidoyl radicals.

We report herein the preparation of ortho-vinylaryl S-trifluoromethylated sulfoximines through cross-coupling reactions. Two efficient palladium-catalyzed procedures (Stille and Suzuki) were developed, with use of ortho-iodo aryl sulfoximines as substrates, to give various vinyl derivatives in good yields. The difference in reactivity of the fluorinated derivatives, compared to nonfluorinated counterparts, allowed the use of free NH sulfoximines in the coupling processes, where they proved to be inert to cyclization. Finally, further transformations have been explored, such as metathesis coupling reactions, after post-functionalization of the nitrogen atom by another vinyl group.

The demethylation of lignin in ionic liquids (ILs) was investigated by using pure lignin model monomers and dimers together with dioxane-isolated lignins from poplar, miscanthus, and maize. Different methylimidazolium ILs were compared and the samples were treated with two different heating processes: microwave irradiation and conventional heating in a sealed tube. The conversion yield and influence of the treatment on the lignin structure were assessed by P-31 NMR spectroscopy, size-exclusion chromatography, and thioacidolysis. The acidic methylimidazolium IL [HMIM]Br was shown to be an effective combination of solvent and reagent for the demethylation and depolymerization of lignin. The relatively mild reaction conditions, the clean work-up, and the ability to reuse the IL makes the described procedure an attractive and new green method for the conversion of lignin to produce phenol-rich lignin oligomers.

A general efficient one-pot synthesis of S-perfluoroalkylated NH-sulfoximines from sulfides has been developed using phenyliodine diacetate (PIDA) and ammonium carbamate. Remarkable rate enhancement with trifluoroethanol was observed, presumably due to H-bonding effects. These mild and metal-free conditions are compatible with -CH2 F, -CFCl2 , -CF2 H, -CF2 Br, -C4 F9 , and -CF3 groups, in both the alkyl- and aryl series. Based on a 19 F NMR analysis, a λ6 -acetoxysulfanenitrile intermediate was proposed.

Reported herein is the use of S-perfluoroalkyl sulfilimino iminiums as a new source of RF radicals under visible-light photoredox catalysis (RF =CF3 , C4 F9 , CF2 Br, CFCl2 ). These shelf-stable perfluoroalkyl reagents, readily prepared on gram scale from the corresponding sulfoxide using a one-pot procedure, allow the efficient photoredox-induced oxyperfluoroalkylation of various alkenes using fac-Ir(ppy)3 as the photocatalyst. Importantly, spin-trapping/electron paramagnetic resonance experiments were carried out to characterize all the radical intermediates involved in this radical/cationic process.

We describe the first gram scale preparation of the reagent dichlorotrifluoromethoxyacetic acid. This stable compound is obtained in five steps starting from the cheap diethylene glycol. The reactivity of the sodium salt of this fluorinated acid was also tested and allowed the preparation of new amides.

The introduction of a double or triple bond to the nitrogen atom of S-perfluoroalkyl sulfoximines is described. We propose a simple catalytic system based on copper iodide for the reaction with bromoalkenes and bromoalkynes, and based on copper dichloride for the coupling with terminal alkynes. The fluorinated chain was varied from perfluorobutyl to monofluoromethyl. The reaction proceeds efficiently when the unsaturated system is substituted by an aryl or alkyl group. In particular, aliphatic terminal alkynes are efficient substrates for this transformation.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The first use of the NH S-trifluoromethyl sulfoximine as an ortho directing group is described for the functionalization of the aryl group bonded to the sulfur atom. Various electrophiles (halogen, carbon, oxygen, sulfur, boron, etc.) are introduced on the aromatic ring. Cyclic S-trifluoromethyl sulfoximines are synthesized either with properly chosen electrophiles or by structural adjustment of o-azido sulfoximines. Fluorinated analogues of prazosin are also prepared.

N-substituted S-perfluoroalkylated sulfoximines were synthesized from the NH sulfoximines either by a copper coupling reaction with aryl halides or by a reaction with electrophilic substrates. The procedure allowed the preparation of N,N′-bridged bis sulfoximines and of thioureas. The potential of these new sulfoximines was evaluated in different catalytic processes.

An efficient and convenient method is described that allows the synthesis of a set of difluoromethyl sulfoximines, as well as chlorofluoromethyl sulfoxides, sulfones, and sulfoximines. Our procedure does not require metals or nonrecommended freons, and it gives rise to an original route to Hu's reagent. Unprecedented chlorofluoromethyl sulfoximines have been also isolated, and these compounds have been shown to act as an electrophilic source of this original bis-halogenated moiety. The mechanism of the electrophilic chlorofluoromethylation is also discussed.

A new ionic liquid [bdmim][F] has been prepared and fully characterized. Its potential as a fluoride source for the desulfurization–fluorination process has been evaluated with success. The carbon–sulfur double bond of xanthates and thiocarbonates has been difluorinated to give rise to small libraries of halogenated ketals and thioketals.

Mono-, di- and trifluoromethyl sulfilimines and sulfoximines have been isolated for the first time in enantiopure form by separation of the racemate by supercritical fluid chromatography. The electrophilic trifluoromethylating Shibata reagent has been prepared as a single enantiomer.

Our synthetic methodology, which was previously developed for the preparation of perfluoroalkyl sulfilimines by a reaction between fluorinated sulfoxides and nitriles, has been successfully extended to dinitriles. According to the reaction conditions, we can preferentially produce a cyano monosulfilimine or a bis(sulfilimine). New cyano thioethers have been synthesized through a rearrangement process. Mono- and bis(sulfilimine)s were also oxidized to afford the corresponding sulfoximines, which provide a direct route to potential new ligands for catalysis and new electrophilic perfluoroalkylating reagents.

The title reaction is carried out with acid chlorides as reactants in the presence of base to give the corresponding functionalized amides.