Themed collection Fluorine Chemistry

Advances in the field of fluorine chemistry have been applied extensively to the syntheses of ¹⁸F-labelled organic compounds and radiopharmaceuticals.

CF_x-based materials bring significant improvement in terms of gravimetric and volumetric energy densities with respect to other types of primary Li batteries.

A closer look is given to the successful approaches to the C(sp³)–F activation of benzylic, allylic, propargylic and allenylic fluorides.

Over the past few years, we have tackled the synthesis of interesting monofluorinated organic molecules, such as: dihydronaphthalene derivatives, β-fluoro sulfones and related carbonyl compounds, fluorohydrins and allylic alcohols.

The feisty nature of silicon(II) fluorides has been harnessed by two cyclic alkyl amino carbene (cAAC) ligands and (cAAC)₂SiF₂ has been isolated at room temperature and structurally characterized.

This review presents the methods available for the fluorination and radiofluorination of aromatic and aliphatic organoboron compounds.

Di- and mono-fluoromethyl radicals can be easily accessed by photochemical protocols.

This review article provides a summary of the detrifluoroacetylative in situ generation of fluorine-containing enolates and their related reactions.

The use of Zn-phthalocyanine in a red-light-driven process for the perfluoroalkylation reactions of (hetero)arenes and sufides represents a friendlier environmental alternative.

Electrochemical oxidative radical trifluoromethylation/semipinacol rearrangement sequences of alkenyl alcohols were developed in this study.

A combined experimental and computational approach provided insight into the nature and conformational dependence of long-range ⁴J_HF couplings in α-fluoro amides.

The BITE bioisostere of Et and CF₃ allows lipophilicity to be tempered in analogues of the multiple sclerosis drug Gilenya®.

The dodecahedral [WF₄{o-C₆H₄(EMe₂)₂}₂]²⁺ dications (E = P, As) present the highest oxidation state metal fluoride complexes with soft donor ligands.

An original degradable fluorinated surfactant, 3-hydroxy-2-(trifluoromethyl)propanoic acid was applied for the emulsion polymerization of vinylidene difluoride (VDF) to yield a latex of PVDF, consisted of typically 100 nm particle diameters.

A practical one-pot procedure using chlorodifluoroacetic anhydride as a user-friendly chlorodifluoromethyl-source was developed.

An XB-donor amino acid compound F(F₄I) effectively promotes homogeneous catalysis of condensation reactions in water.

A method for the direct C(sp²)–H trifluoromethylation of enamides, including biologically relevant isoindolinones, isoquinolinones and 2-pyridinones using TMSCF₃ under oxidative conditions is presented.

Generating a high yielding but strong fluorinated electrophile by destabilizing a low temperature perfluorocarbanion in non-polar solvent, while avoiding cascading side-reactions.

A new methodology has been developed to access highly enantioenriched α,α-difluoromethyl alcohols by means of sulfoxides as traceless and chiral auxiliaries.

The high-pressure HP2 form of AgF₂ features Ag₂F₇³⁻ units that are theoretically predicted to host extremely strong antiferromagnetic interactions, surpassing those seen in copper(II) oxides.

Reactive [¹⁸F]fluoride was generated from gaseous [¹⁸F]triflyl fluoride and used for a wide range of radiofluorination reactions.

Fluorination of anatase as an effective way to tune Mg²⁺ intercalation properties.

α-Fluoroalkylselenolated sulfones have been readily obtained via a visible-light promoted radical addition of fluoroalkylselenyl and tosyl groups onto unsaturated substrates.

Crossed aldol reactions of the CF₃-containing pseudo C₂ symmetric cyclic imide 3 were performed by way of the corresponding lithium and boron bisenolates to stereoselectively furnish the desired products 4.

A photochemical activation of SF₆ provides access to difluoroimidazolidine derivatives, which can serve as intermediates to shuttle fluorides to alcohols by deoxyfluorination.

Galactose-conjugated fluorinated and non-fluorinated proline oligomers were synthesized and evaluated as antifreeze molecules.

New straightforward synthetic approach to hitherto unknown cis-/trans-CF₃-prolines and other 3-polyfluoroalkyl proline analogues.

A simple and general procedure for the preparation of Diels–Alder adducts of perfluorinated thioketones and various dienes is reported.

A route to [Au^IIIClF₂(SIMes)] and [Au^IIIF₂(OTeF₅)(SIMes)] including structural characterization to tune the ligand arrangement and Lewis acidity of gold(III) centres was developed.

The thermally unstable α-fluoroalcohol undecafluorocyclohexanol (c-C₆F₁₁OH) was prepared by addition of hydrogen fluoride to the corresponding ketone.

An oximinotrifluoromethylation of unactivated alkenes was developed via trifluoromethyl radical-induced intramolecular remote oximino migration under mild reaction conditions.

The first highly C-selective difluoromethylation of β-ketoesters was achieved by combining TMSCF₂Br/LiOH/(CH₃(CH₂)₁₅(CH₃)₃NBr).

CF₃-DAST-induced deacylative trifluoromethylthiolation of cyclic 1,3-diketones lactams, and lactones that provides cyclic trifluoromethylthioketones, lactams and lactones is reported.

A copper-mediated intramolecular aminofluorination of 1,3-dienes is disclosed, in which both AgF and Et₃N·3HF can be used as the fluorine source.

A general route to aryl α,β,β-trifluorocyclopropanes is reported and aryl oxidation gave the corresponding α,β,β-trifluorocyclopropane carboxylic acid.

A Stille cross-coupling reaction was developed for the first time by secondary (trifluoromethyl)benzyl chlorides and allylstannanes.

The Pd-catalyzed asymmetric decarboxylative allylic alkylation of trifluoromethoxy allyl enol carbonates is disclosed.

Combining the 4S-fluoro and 3R-fluoromotifs, which each instill an opposing conformational bias, leads to a fluorinated proline with a similar conformational profile to proline.

The first stereodivergent trifluoromethylation of N-sulfinylimines by fluoroform is reported.

An efficient rhodium-catalyzed microwave-assisted transannulation of N-(per)fluoroalkyl-1,2,3-triazoles to previously inaccessible N-(per)fluoroalkyl five-membered heterocycles was developed.

A trifluoromethyl radical is generated by single electron reduction of CF₃-substituted borate complexes.

1,1-Difluoroallenes underwent β-selective C–C bond formation (insertion) via π-allylpalladium(II) to facilitate aromatic ring construction, leading to biologically promising (difluoromethyl)naphthalenes.

A fluoroalkenylation of boronic acids with fluoroalkyl alkenes has been developed.

Visible-light-mediated trifluoromethylthiolation of N-(o-cyanobiaryl)acrylamides with N-trifluoromethylthiosaccharin as the source of SCF₃ radicals provided an efficient route to SCF₃-containing ring-fused phenanthridine derivatives.

Lewis acid promoted substitution of fluorine yields novel 5-alkoxylated 4,4-difluoroisoxazolines via S_N1 type processes.

Herein we introduce tetrafluoropyridyl (TFP) as a new general protecting group for phenols. The TFP protecting group is readily cleaved under mild conditions.

Fluorination alters a cyclic peptide's synthetic efficiency, its molecular conformation, and its biological activity.

An efficient Brønsted base-catalyzed Pechmann-type reaction of cyclic 1,3-diones with ethyl 4,4,4-trifluoroacetoacetate to afford 4-trifluoromethyl 2-pyrones and pyridones was developed.

Hexafluoroisopropan-2-ol is an excellent solvent for promoting fluorinations with the stable hypervalent fluoroiodane reagent without any transition metals or TREAT-HF activators.

The aerobic oxidation took place after the visible light-mediated ring-opening reaction of gem-difluorocyclopropane in the presence of an organic dye and amine to furnish 2,2-difluoro-homoallylic alcohols in good yields.