Replacement of BF4− by PF6− makes Selectfluor greener

Jin, Zhuang; Xu, Bo; DiMagno, Stephen G.; Hammond, Gerald B.

doi:10.1016/j.jfluchem.2012.05.010

Cited by 12 publications

(5 citation statements)

References 28 publications

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“…This transient red species rapidly disappeared, resulting in a featureless spectrum. In reactions involving both copper and Selectfluor, several groups have posited the intermediacy of a highly reactive Cu(III) species. ,− We thus hypothesized that this transient red species may in fact be a short-lived Cu(III) intermediate. Despite extensive evaluation of the online ESI-MS data from both the full reaction (Scheme and Figure ) and the simplified mixture (Figure a), however, we were unable to identify a discrete Cu(III) species.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Analysis of the C–H Amination Reaction of Menthol by CuBr₂ and Selectfluor

et al. 2018

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The mechanism of the Ritter-type C-H amination reaction of menthol with acetonitrile using CuBr, Selectfluor, and Zn(OTf), first disclosed by Baran and coworkers in 2012, was studied using a combination of online electrospray ionization mass spectrometry, continuous UV/vis spectrometric monitoring, and density functional theory calculations. In addition to corroborating Baran's original mechanistic proposal, these studies uncovered a second pathway to product formation, which likely only occurs in microdroplets. DFT calculations show that neither pathway has a barrier that is greater than 6.8 kcal/mol, suggesting that both mechanisms are potentially operative under ambient conditions.

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Section: Resultsmentioning

confidence: 99%

Mechanistic Analysis of the C–H Amination Reaction of Menthol by CuBr₂ and Selectfluor

et al. 2018

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“…In this case 1c was isolated as a major product along with minor amounts of 1d . In an effort to enhance the oxidative power of Selectfluor and to promote dihalogenation, CuBr was used as an additive [ 16 – 17 ], but the outcome remained unchanged. In the absence of Selectfluor the same hydrohalogenation products 1c and 1d were isolated but in different ratios ( Scheme 2 ).…”

Section: Resultsmentioning

confidence: 99%

“…Notable examples of oxidative functionalization by Selectfluor include in situ generation of electrophile equivalents Cl + , Br + , SCN + and NO 2 + and their reactions with aromatics [ 12 ], the bromination of representative alkenes with Selectfluor/KBr [ 13 ], and the thiocyanation of representative heteroarenes and ketones with NH 4 SCN [ 14 – 15 ]. Oxidative transformations such as amide to imide mediated by Selectfluor in combination with CuBr have also been shown [ 16 – 17 ].…”

Section: Introductionmentioning

confidence: 99%

Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH₄SCN: Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition

Reddy

Laali

2015

Beilstein J. Org. Chem.

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SummaryReaction of benzyl and ethyl allenoates with TMSX (X = I, Br, Cl) and with NH4SCN were investigated in MeCN, DMF, and in imidazolium ionic liquids [BMIM][NTf2] and [BMIM][PF6] as solvent, in the presence and absence of Selectfluor. Comparative product analysis studies demonstrate that the ability of Selectflour to promote oxidative/electrophilic dihalogenation/dithiocyanation with TMSX/NH4SCN (as observed previously for 1-arylallenes) is diminished in allenoates, most significantly in reactions with TMSCl, and essentially disappearing in reactions with NH4SCN, in favor of nucleophilic/conjugate addition. The study underscores the contrasting reactivity patterns in 1-arylallenes and allenoates toward electrophilic and nucleophilic additions in halofunctionalization with TMSX/Selectfluor and thiocyanation reactions with NH4SCN/Selectfluor. These competing pathways are influenced by the nature of the anion, allene structure, and the choice of solvent.

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“…The advance in reagents that can react via electrophilic fluorination and embody a certain specificity of conditions has not only improved the selectivity of fluorination but has also improved the tolerance of functional groups. 13 The developments of reagents such as N-fluoropyridium salts (FP-T300) 14 , N-fluorobis(phenyl)sulfonimide (NFSI) 15 , 1-chloromethyl-4-fluoro-1,4-diazoniabicyclo-[2.2.2] octane bis(tetrafluoroborate) (Selectfluor®, F-TEDA-BF4), 16 and derivative F-TEDA-PF6 17 have been great innovations to the introduction of a fluorine atom (Figure 3). …”

Section: Scheme 1 Nucleophilic Fluorination Reactionmentioning

confidence: 99%

Selective fluorination of natural products

Luzzio¹,

Monsen²,

Zhdankin³

2017

Arkivoc

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Compounds derived from natural sources including animals, plants, and micro-organisms have been widely used for pharmaceuticals, materials, and agrochemicals. The use of these natural products has grown increasingly over the years and the demand for more improved, biologically active, and safer derivatives of natural products has been investigated by many researchers in the areas of synthetic and medicinal chemistry. Due to the unique characteristics of fluorinated compounds, and the increased or more favorable biological activity which usually accompanies fluorinated analogues of medicinally-important compounds, the fluorination of natural products has gained much attention. This review aims at exploring the range of specific natural product types that have been selectively fluorinated as well as how fluorination was expected to affect their biological activities and physiochemical properties.

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Replacement of BF4− by PF6− makes Selectfluor greener

Cited by 12 publications

References 28 publications

Mechanistic Analysis of the C–H Amination Reaction of Menthol by CuBr₂ and Selectfluor

Mechanistic Analysis of the C–H Amination Reaction of Menthol by CuBr₂ and Selectfluor

Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH₄SCN: Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition

Selective fluorination of natural products

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Replacement of BF4− by PF6− makes Selectfluor greener

Cited by 12 publications

References 28 publications

Mechanistic Analysis of the C–H Amination Reaction of Menthol by CuBr2 and Selectfluor

Mechanistic Analysis of the C–H Amination Reaction of Menthol by CuBr2 and Selectfluor

Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH4SCN: Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition

Selective fluorination of natural products

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Mechanistic Analysis of the C–H Amination Reaction of Menthol by CuBr₂ and Selectfluor

Mechanistic Analysis of the C–H Amination Reaction of Menthol by CuBr₂ and Selectfluor

Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH₄SCN: Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition