Themed collection Fluorine Chemistry

Self-assembly of a highly fluorous anion leads to quantitative phase transfer of the photo- and electroactive pristine dicationic Ru(bipy)₃²⁺ into apolar perfluorinated solvent.

The halogen-bonded adduct between DABCO and two molecules of perfluorooctyl iodide (DABCO·(C₈F₁₇I)₂) acts as a recyclable fluorous organocatalyst for the Morita–Baylis–Hillman reaction.

Fluorous benzaldehyde-based synthesis of biaryl-substituted oxazabicyclo[3.3.1]nonanes is accomplished by a three-step synthesis including a multicomponent reaction (MCR) to form tetrahydroquinoline, followed by cycloaddition with coumarin to form oxazabicycles, and then a Suzuki coupling to introduce the biaryl group. Microwave irradiation and fluorous solid-phase extraction (F-SPE) are employed to speed up reactions and simplify product purification.

The synthesis of 8-aminoquinolines and 1,10-phenanthrolines with substituents in α of the nitrogen atoms has been performed through an inverse-demanding aza-Diels–Alder in the fluorinated alcohols TFE or HFIP.

Linear correlation between the measured E_1/2 values and DFT-calculated LUMO energies for ten fullerene(i-C₃F₇)_n compounds with n = 2–6.

An efficient method for highly diastereoselective synthesis of quaternary α-trifluoromethyl α-amino acids and related derivatives was developed via indium-mediated allylation of (R)-phenylglycinol methyl ether based imines of trifluoropyruvate in good yields with high diastereoselectivities.

Fluorous diastereomeric mixture synthesis (FDMS) is introduced and demonstrated in the synthesis of six diastereomers of hydantoin-fused hexahydrochromeno[4,3-b]pyrroles.

Enantiopure (R)- and (S)-trifluoroalaninol were conveniently synthesized in a few steps from fluoral hemiacetal or ethyl trifluoropyruvate.

The 2,3,4-trifluoro-2,3,4-tridehydroxy hexose analogues of D-glucose and D-altrose were prepared and structurally characterised and the novel sugar analogues were explored by 2D-¹⁹F-EXSY NMR for their potential to cross erythrocyte (red blood cell) membranes.

In situ-generated silyl methide species catalyzed the diastereoselective 1,4-addition reaction of silicon dienoates such as 3-bromo-2-silyloxyfuran to α,β-unsaturated aldehydes.

The fluorous resorcin[4]arene immobilized in a fluorous bulk membrane is capable of transporting tetramethylammonium cation from an aqueous source phase into an aqueous receiving phase.

Structurally diverse ¹⁸F-labelled molecular scaffolds are now accessible in one step combining an ¹⁸F-component with two or more additional building blocks. This approach is easy to implement and leads to a series of novel ¹⁸F products difficult to access by known methods.

Silver oxide and catalytic TBAF efficiently promoted the coupling of functional trimethylsilylpyridines with (hetero)aromatic halides.

The perfluoroalkylated pincer palladium complex promotes Heck reactions and can be recycled efficiently by fluorous solid-phase extraction without loss in catalytic activity.

The directing capability of interactions involving ‘organic’ fluorine in aryl biscarbonates and an aryl biscarbamate as a function of acetylenic spacer units has been analyzed to authenticate the influence of such interactions on the conformational features.

From the solid state structures of a series of [AuCl(PR₂R_f)] complexes (R_f = CFCF₂, CFCFH, CClCF₂, CCCF₃, CF₃, i-C₃F₇, s-C₄F₉) the relative importance of Au⋯F, hydrogen bonding, fluorous and aurophilic bonding interactions can be assessed.

The general pathway for a new synthesis of difluoroaryldioxoles.

2-[¹⁸F]Fluoro-L-phenylalanine and 2-[¹⁸F]fluoro-L-tyrosine were synthesized by isotopic exchange on corresponding precursors, followed by removal of the formyl group with Rh(PPh₃)₃Cl and subsequent hydrolysis of the protecting groups.

Ionic liquid is demonstrated to be a tailor-made solvent system for specific chemical reactions.

Unprecedented fluorinated cyclohexane and aromatic derivatives were achieved from pentafluoropropiophenone via its tetrafluoroenol silyl ether and a stepwise Robinson annulation.

A new transition state receptor for selective nucleophilic fluorination has been designed.

Not enough pi to go around! Does the “triple bond” in fluoromethylidyne complexes really have a bond order of three?

In the crystal structure of InF₃·3SbF₅ fluorine atoms bridge In and Sb metals (In–F_b–Sb) with very long Sb–F_b bonds, comparable with that in solid SbF₅ (Sb–F_b–Sb).

No examples of fluoride-trans-NHC arrangements have been observed in a series of the new iridium(III) complexes [IrClF₂(NHC)(COD)], [IrClF₂(CO)₂(NHC)] [IrF₂L(NHC)(COD)][BF₄] and [IrF₂L(CO)₂(NHC)][BF₄].

Structural and spectroscopic characterisation of alkyldiphosphine complexes of TiF₄ are reported, but arylphosphines, arsines and thioethers fail to form similar complexes, although [LigandH₂][Ti₄F₁₈] were minor by-products for some soft-donor ligands.

Treatment of trans-[Pd(F)(4-C₅NF₄)(PiPr₃)₂] with HBpin yields trans-[Pd(H)(4-C₅NF₄)(PiPr₃)₂]. Heating a solution of the latter to 60 °C in the presence of pentafluoropyridine affords 2,3,5,6-tetrafluoropyridine and the C–F activation product trans-[Pd(F)(4-C₅NF₄)(PiPr₃)₂].