hydrocarbon/perfluorocarbon phase-switching of [Ru(bipy)3]2+ driven by supramolecular heteromeric fluorous carboxylate– carboxylic acid H-bond interactions
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.
Fluorous tagging of DABCO through
halogen bonding: recyclable catalyst for the Morita–Baylis–Hillman reaction
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.
benzaldehyde-based synthesis of biaryl-substituted oxazabicyclo[3.3.1]nonanes
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.
Synthesis of substituted 8-aminoquinolines and
phenanthrolines through a Povarov approach
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.
Chemical tailoring of
fullerene acceptors: synthesis, structures and electrochemical properties of perfluoroisopropylfullerenes
Linear correlation between the measured E1/2 values and DFT-calculated LUMO energies for ten fullerene(i-C3F7)n compounds with n = 2–6.
Highly diastereoselective synthesis of quaternary α-trifluoromethyl α-amino acids from chiral
imines of trifluoropyruvate
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) of
Fluorous diastereomeric mixture synthesis (FDMS) is introduced and demonstrated in the synthesis of six diastereomers of hydantoin-fused hexahydrochromeno[4,3-b]pyrroles.
Straightforward synthesis of enantiopure (R)- and
Enantiopure (R)- and (S)-trifluoroalaninol were conveniently synthesized in a few steps from fluoral hemiacetal or ethyl trifluoropyruvate.
Fluorosugars: synthesis of the
2,3,4-trideoxy-2,3,4-trifluoro hexose analogues of D-glucose and D-altrose and assessment of their erythrocyte transmembrane transport
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.
1,4-Addition of silicon dienoates to α,β-unsaturated aldehydes catalyzed by in situ-generated silicon Lewis acid
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.
Synthesis, characterization, and applications of fluorous resorcinarenes
The fluorous resorcinarene immobilized in a fluorous bulk membrane is capable of transporting tetramethylammonium cation from an aqueous source phase into an aqueous receiving phase.
Convergent 18F radiosynthesis: A new dimension for radiolabelling
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-mediated cross-coupling of functional trimethysilylpyridines: access to arylpyridines and bihetaryl compounds
Silver oxide and catalytic TBAF efficiently promoted the coupling of functional trimethylsilylpyridines with (hetero)aromatic halides.
A recyclable perfluoroalkylated PCP pincer palladium complex
The perfluoroalkylated pincer palladium complex promotes Heck reactions and can be recycled efficiently by fluorous solid-phase extraction without loss in catalytic activity.
Crystal structures of fluorinated aryl biscarbonates and a biscarbamate: a counterpoise between weak intermolecular interactions and molecular symmetry
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.
Synthesis of gold(I) fluoroalkyl and fluoroalkenyl-substituted
phosphine complexes and factors affecting their crystal packing
From the solid state structures of a series of [AuCl(PR2Rf)] complexes (Rf = 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.
Synthesis of difluoroaryldioxoles using BrF3
The general pathway for a new synthesis of difluoroaryldioxoles.
Enantiospecific synthesis of 2-[18F]fluoro-L-phenylalanine and 2-[18F]fluoro-L-tyrosine by isotopic exchange
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.
Fluorination reactions in
ionic liquids: a mechanistic study towards solvent engineering
Ionic liquid is demonstrated to be a tailor-made solvent system for specific chemical reactions.
Synthesis of trifluoromethyl cyclohexyl, cyclohexenyl and
aryl compounds via stepwise Robinson annulation
Unprecedented fluorinated cyclohexane and aromatic derivatives were achieved from pentafluoropropiophenone via its tetrafluoroenol silyl ether and a stepwise Robinson annulation.
Chemical reactions inside structured nano-environment:
SN2 vs. E2 reactions for the F− + CH3CH2Cl system
A new transition state receptor for selective nucleophilic fluorination has been designed.
Synthesis and structural characterization of group 6 transition metal complexes with terminal fluoromethylidyne (CF)
ligands; a DFT/NBO/NRT comparison of bonding characteristics of terminal NO, CF and CH ligands
Not enough pi to go around! Does the “triple bond” in fluoromethylidyne complexes really have a bond order of three?
Fluoride ion donor properties of group 13 trifluorides (MF3, M = Al, Ga, In, Tl) and crystal structures of InF3·3SbF5, TlF3·3SbF5 and TlF3·AsF5·2HF
In the crystal structure of InF3·3SbF5 fluorine atoms bridge In and Sb metals (In–Fb–Sb) with very long Sb–Fb bonds, comparable with that in solid SbF5 (Sb–Fb–Sb).
iridium(III) fluoride complexes with NHCs
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].
Taking TiF4 complexes to extremes - the first examples with
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.
Isolation and reactivity of
palladium hydrido complexes: intermediates in the hydrodefluorination of pentafluoropyridine
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].
About this collection
The RSC Fluorine Interest group celebrates its tenth anniversary. To commemorate this, the RSC has published a web themed issue on fluorine chemistry across several journals. For an introduction to this web themed issue by the Chair of the RSC Fluorine Chemistry Group and Guest Editor of this issue See OBC Blog.