Xenon difluoride in synthesis

Tius, Marcus A.

doi:10.1016/0040-4020(95)00362-c

Cited by 167 publications

(89 citation statements)

References 84 publications

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“…Similar results were obtained in quartz and alkali washed quartz. (2) In the absence of alkali XeF 2 is more stable in aqueous solution than might be expected. Satisfactory spectra for covalent XeF 2 were obtained in 3:1 CD 3 CN: D 2 O in Pyrex ® .…”

Section: (C) H 2 O D 2 O and D 2 O/cd 3 Cn (I) Ptfe-fepmentioning

confidence: 91%

“…1,2 In a series of studies we have shown that both solvent and reaction vessel can profoundly influence the mode of reaction of xenon difluoride with organic substrates. [3][4][5][6][7][8][9] Although the instability of xenon difluoride in glassware has been known for some time, Pyrex ® flasks have been widely used, and advocated, 2 for carrying out organic reactions but, apart from our own work, 5 the role of the glass surface in determining the reaction pathway has not been recognised. We have shown, for example, that aryltrimethylsilanes are rapidly fluorinated by xenon difluoride at room temperature (Equation 1) but only in a Pyrex ® flask.…”

Section: Introductionmentioning

confidence: 99%

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19F NMR and UV studies of xenon difluoride solution-vessel stability and its relevance to the fluorination of organic substrates

Shaw¹,

Smith²,

Ramsden³

2011

Arkivoc

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The stability of xenon difluoride in CH 2 Cl 2 , CHCl 3 , CFCl 3 , CH 3 CN, H 2 O and C 6 F 6 , and the corresponding deuterated solvents, in PTFE-FEP, Pyrex ® and quartz tubes has been investigated using 19 F NMR spectroscopy. Stability in tubes lined with PTFE-FEP is good. With the exception of CH 3 CN, decomposition in Pyrex ® tubes occurs within a few hours and this instability is attributable to coordination to Lewis acid sites on the glass surface. In quartz the lifetime of the xenon difluoride is extended by a few hours. The mode of reaction of xenon difluoride with organic substrates depends on the reaction vessel surface and the type of solvent. Pyrex ® catalysis in a suitable solvent such as CH 2 Cl 2 is a convenient way of achieving electrophilic reactions of xenon difluoride. The UV spectra of xenon difluoride in CH 3 CN and CH 3 CN: H 2 O (3:1) have been recorded.

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Section: (C) H 2 O D 2 O and D 2 O/cd 3 Cn (I) Ptfe-fepmentioning

confidence: 91%

Section: Introductionmentioning

confidence: 99%

19F NMR and UV studies of xenon difluoride solution-vessel stability and its relevance to the fluorination of organic substrates

Shaw¹,

Smith²,

Ramsden³

2011

Arkivoc

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“…In this context, the hydrofluorination of alkenes has remained a challenging transformation. The addition of HF/pyridine or HF/SbF 5 across alkenes, [1] and free radical hydrofluorinations [2] have been studied. The harsh reaction conditions offer narrow substrate scope and restrict control over product selectivity.…”

mentioning

confidence: 99%

cis‐Specific Hydrofluorination of Alkenylarenes under Palladium Catalysis through an Ionic Pathway

et al. 2014

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This paper describes the hydrofluorination of alkenes through sequential H À and F + addition under palladium catalysis. The reaction is cis specific, thus providing access to benzylic fluorides. The mechanism of this reaction involves an ionic pathway and is distinct from known hydrofluorinations involving radical intermediates. The first catalytic enantioselective hydrofluorination is also disclosed.

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“…(c) XeF 2 is commercially available in reasonable quantities and is a stable, crystalline solid that is easy to handle. 7,8 This makes it an attractive reagent for introducing fluorine into a molecule, especially at the end of a synthesis. In this context we were aware that late introduction of positron-emitting 18 F (t ½ 110 minutes) into molecules using [ 18 F]-XeF 2 might be useful in Positron Emission Tomography (PET).…”

Section: Introductionmentioning

confidence: 99%

Xenon difluoride in the organic laboratory: a tale of substrates, solvents and vessels

Ramsden¹

2013

Arkivoc

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This Account summarises a series of studies of the reactions of xenon difluoride with organic substrates. It is concluded that xenon difluoride has two initial modes of reaction with organic substrates: single electron transfer (SET) and electrophilic addition. Reactions of aryltrimethylsilanes, carboxylic acids and esters, and trimethylsilyl enol ethers are discussed. The mode of reaction is determined by a combination of the solvent, the reaction vessel material and the presence of an acid catalyst. Pyrex, in the form of a flask surface, is a very effective catalyst for electrophilic reactions but this effect is inhibited by use of acetonitrile as solvent. Trimethylsilyl derivatives are particularly convenient substrates as these avoid the formation of HF, which may catalyse side-reactions. Some studies using [ 18 F]-XeF 2 are described.

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Xenon difluoride in synthesis

Cited by 167 publications

References 84 publications

19F NMR and UV studies of xenon difluoride solution-vessel stability and its relevance to the fluorination of organic substrates

19F NMR and UV studies of xenon difluoride solution-vessel stability and its relevance to the fluorination of organic substrates

cis‐Specific Hydrofluorination of Alkenylarenes under Palladium Catalysis through an Ionic Pathway

Xenon difluoride in the organic laboratory: a tale of substrates, solvents and vessels

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