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Selectfluor, Chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate), F-TEDA-BF4

Recent Literature


A palladium-catalyzed synthesis of aryl fluorides from arylboronic acid derivatives is operationally simple and amenable to multigram-scale synthesis. Evaluation of the reaction mechanism suggests a single-electron-transfer pathway that involves a Pd(III) intermediate.
A. R. Mazzotti, M. G. Campbell, P. Tang, J. M. Murphy, T. Ritter, J. Am. Chem. Soc., 2013, 135, 14012-14015.


A powerful free radical Markovnikov hydrofluorination of unactivated alkenes is mediated by Fe(III)/NaBH4 using Selectfluor reagent as a source of fluorine. In contrast to the traditional radical hydrofluorination of alkenes, the Fe(III)/NaBH4-mediated reaction is conducted under exceptionally mild reaction conditions, tolerates various functional groups, and even runs open to the air and with water as a cosolvent.
T. J. Barker, D. L. Borger, J. Am. Chem. Soc., 2012, 134, 13588-13591.


Visible light activates diarylketone catalysts to abstract a benzylic hydrogen atom selectively, which enables an operationally simple direct fluorination of benzylic C-H groups in the presence of a fluorine radical donor. 9-Fluorenone catalyzes benzylic C-H monofluorination, while xanthone catalyzes benzylic C-H difluorination.
J.-B. Xia, C. Zhu, C. Chen, J. Am. Chem. Soc., 2013, 135, 17494-17500.


J.-B. Xia, C. Zhu, C. Chen, J. Am. Chem. Soc., 2013, 135, 17494-17500.


A continuous-flow protocol for the light-induced fluorination of benzylic compounds in very good isolated yields in residence times below 30 min uses Selectfluor as the fluorine source and xanthone as an inexpensive and commercially available photoorganocatalyst. The flow photoreactor is based on transparent fluorinated ethylene propylene tubing and a household compact fluorescent lamp with black-light irradiation.
D. Cantillo, O. de Frutos, J. A. Rincón, C. Mateos, C. O. Kappe, J. Org. Chem., 2014, 79, 8486-8490.


A mild C-F functionalization of benzylic sp3 C-H bonds allows the synthesis of monofluorinated benzylic substrates in the presence of commercially available iron(II) acetylacetonate and Selectfluor in very good yields and selectivity. A convenient route to β-fluorinated products of 3-aryl ketones provides a synthetic equivalent to the difficult to accomplish conjugate addition of fluoride to α,β-unsaturated ketones.
S. Bloom C. R. Pitts, R. Woltornist, A. Griswold, M. G. Holl, T. Lectka, Org. Lett., 2013, 15, 1722-1724.


In a direct fluorination of C(sp3)-H bonds, a catalytic N-oxyl radical generated from N,N-dihydroxypyromellitimide abstracts the hydrogen followed by trapping of the resulting carbon radical by Selectfluor. This simple metal-free protocol enables the chemoselective introduction of a fluorine atom into various aromatic and aliphatic compounds and serves as a powerful tool for the efficient synthesis of fluorinated molecules.
Y. Amaoka, M. Nagamoto, M. Inoue, Org. Lett., 2013, 15, 2160-2163.


A catalytic amount of AgNO3 enables an efficient decarboxylative fluorination of aliphatic carboxylic acids with Selectfluor in aqueous solution to yield the corresponding alkyl fluorides in good yields under mild conditions. This radical fluorination method is not only efficient and general but also chemoselective and functional-group-compatible, thus making it highly practical in the synthesis of fluorinated molecules.
F. Yin, Z. Wang, Z. Li, C. Li, J. Am. Chem. Soc., 2012, 134, 10401-10404.


Visible light-promoted photoredox catalysis enables a direct conversion of aliphatic carboxylic acids to the corresponding alkyl fluorides. This operationally simple, redox-neutral fluorination method allows the conversion of a broad range of carboxylic acids.
S. Ventre, F. R. Petronijevic, D. W. C. MacMillan, J. Am. Chem. Soc., 2015, 137, 5654-5657.


A catalytic, vicinal difluorination of olefins displays broad functional group tolerance, using inexpensive p-iodotoluene as the catalyst. Preliminary efforts toward the development of an enantioselective variant are reported.
I. G. Molnár, R. Gilmour, J. Am. Chem. Soc., 2016, 138, 5004-5007.


A micellar system was developed and applied for direct regioselective fluorination of various cyclic and acyclic ketones to α-fluoroketones in water as reaction medium with Selectfluor (F-TEDA-BF4) as fluorinating reagent. The inexpensive ionic amphiphile sodium dodecyl sulfate (SDS) was found to be an excellent promoter.
G. Stavber, M. Zupan, S. Stavber, Synlett, 2009, 589-594.


An efficient and mild fluorination of vinyl azides enables the synthesis of α-fluoroketones via a single-electron transfer (SET) and a subsequent fluorine atom transfer.
S.-W. Wu, F. Liu, Org. Lett., 2016, 18, 3642-3645.


Allylic alcohols are isomerized into enolates (enols) by [Cp*IrCl2]2. A subsequent reaction with Selectfluor present in the reaction media produces α-fluoro ketones as single constitutional isomers in good yields.
N. Ahlsten, A. Bartoszewicz, S. Agrawal, B. Martín-Matute, Synthesis, 2011, 2600-2608.


A metal-free and green catalytic system enables an oxyfluorination of olefins for the synthesis of α-fluoroketones which is an important building block for organic synthesis. Moreover, this reaction system exhibits great functional group tolerance.
Q. Yang, L.-L. Mao, B. Yang, S.-D. Yang, Org. Lett., 2014, 16, 3460-3463.


In an enantioselective fluorination of allylic alcohols under chiral anion phase-transfer conditions, an in situ generation of a directing group proved crucial for achieving effective enantiocontrol. In the presence of such a directing group, a range of acyclic substrates underwent fluorination to afford highly enantioenriched α-fluoro homoallylic alcohols.
W. Zi, Y.-M. Wang, F. D. Toste, J. Am. Chem. Soc., 2014, 136, 12864-12867.


A combination of copper powder and Selectfluor generates a cationic copper species that efficiently catalyze the formation of 1,2-diketones from alkynes under mild conditions with water and dioxygen as inexpensive and environmentally benign sources of oxygen.
W. Zhang, J. Zhang, Y. Liu, Z. Xu, Synlett, 2013, 24, 2709-2714.


A Selectfluor-mediated reaction of α,β-epoxy ketones provides 1,2-diketones in good yields under transition-metal-free oxidative conditions via a ring-opening/benzoyl rearrangement/C-C bond cleavage sequence.
H. Wang, S. Ren, J. Zhang, W. Zhang, Y. Liu, J. Org. Chem., 2015, 80, 6856-6863.


Allenyl carbinol esters isomerize to an E,Z mixture of the corresponding dienes in the presence of a gold catalyst. In a subsequent reaction with Selectfluor, this mixture can be converted to monofluoroalkyl α,β-unsaturated ketones with exclusive E selectivity in high yields.
Z. Jin, R. S. Hidinger, B. Xu, G. B. Hammond, J. Org. Chem., 2012, 77, 7725-7726.


Reactions of enamines with Selectfluor under mild conditions easily led to the corresponding difluorinated carbonyl compounds in high yields.
W. Peng, J. M. Shreeve, J. Org. Chem., 2005, 70, 5760-5763.


Selective introduction of an iodine atom at the α-carbonyl position in various aryl alkyl ketones was effectively achieved by reaction of target molecules with elemental iodine in the presence of N-F reagents such as F-TEDA-BF4 (Selectfluor) as iodination mediators and methanol as the solvent.
M. Jereb, S. Stavber, M. Zupan, Synthesis, 2003, 853-858.


Benzene derivatives bearing at least one bulky alkyl group (i-Pr or t-Bu) were selectively and effectively iodinated using elemental iodine activated by Selectfluor. Up to three iodine atoms were progressively introduced at the most electron-rich and sterically less hindered position on the benzene ring.
S. Stavber, P. Kralj, M. Zupan, Synthesis, 2002, 1513-1518.


A Ru(II) catalyzed ortho-hydroxylation of ethyl benzoates with ester as a directing groups enables a facile synthesis of various multifunctionalized arenes from easily accessible substrates. Crucial factors in this transformation are both the TFA/TFAA cosolvent system and the oxidants. The reaction demonstrates excellent reactivity, good functional group tolerance, and high yields.
Y. Yang, Y. Lin, Y. Rao, Org. Lett., 2012, 14, 2874-2877.


Using commercially available Ph3PAuCl and readily prepared, benign arylsilanes, a gold-catalyzed oxyarylation of alkenes proceeds smoothly in air. The oxidant, Selectfluor, not only facilitates entry to the Au(I/III) manifold but also provides a fluoride anion for silane activation, thereby avoiding the need for addition of a stoichiometric base.
L. T. Ball, M. Green G. C. Lloyd-Jones, C. A. Russel, Org. Lett., 2010, 12, 4724-4727.


Oxidative bromination of different types of olefins using Selectfluor/KBr afforded addition, monobromo-substituted, or Hunsdiecker-Borodin reaction products in good yields.
C. Ye, J. M. Shreeve, J. Org. Chem., 2004, 69, 8561-8563.


Oxidative bromination of different types of olefins using Selectfluor/KBr afforded addition, monobromo-substituted, or Hunsdiecker-Borodin reaction products in good yields.
C. Ye, J. M. Shreeve, J. Org. Chem., 2004, 69, 8561-8563.


A catalytic intramolecular cyclization of 2-alkynone O-methyl oximes and subsequent fluorination proceeds smoothly at room temperature in the presence of 5 mol % of (IPr)AuCl, 5 mol % of AgOTs, 2.5 equiv of Selectfluor, and 2 equiv of NaHCO3. This process features an efficient one-pot cascade route to fluoroisoxazoles with high yields and high selectivity under mild reaction conditions.
Y. Jeong, B.-I Kim, J. K. Lee, J.-S. Ryu, J. Org. Chem., 2014, 79, 6444-6455.


A cyclization of N-alkenylamides catalyzed by iodoarenes under oxidative conditions enables the preparation of five-, six-, and seven-membered rings with a range of substitutions. Preliminary data from the use of chiral iodoarenes as precatalysts show that enantiocontrol is feasible.
A. Alhalib, S. Kamouka, W. J. Moran, Org. Lett., 2015, 17, 1453-1456.


A facile method enables the construction of quaternary 3,3-disubstituted 2-oxindoles from 2-substituted indoles without a catalyst under mild conditions via an iminium-intermediate-triggered 1,2-rearrangement.
X. Jiang, J. Yang, F. Zhang, P. Yu, P. Yi, Y. Sun, Y. Wang, Org. Lett., 2016, 18, 3154-3157.


A one-pot Pd-catalyzed reaction of aryl iodides with DABSO and Selectfluor provides aryl sulfonyl fluorides in good yields. Additionally, sulfonyl fluorides can be converted to aryl sulfonamides and sulfonic esters using Cs2CO3 under mild conditions.
A. L. Tribby, I. Rodríguez, S. Shariffudin, N. D. Ball, J. Org. Chem., 2017, 82, 2294-2299.


An efficient electrophilic fluorination of secondary phosphine oxides with Selectfluor provides direct access to phosphoric fluorides in good yield under mild conditions. In addition, one-pot P-O bond construction is achieved in the presence of water or alcohols to provide phosphinic acids or phosphinates.
Q. Chen, J. Zeng, X. Yan, Y. Huang, C. Wen, X. Liu, K. Zhang, J. Org. Chem., 2016, 81, 10043-10048.


An efficient electrophilic fluorination of secondary phosphine oxides with Selectfluor provides direct access to phosphoric fluorides in good yield under mild conditions. In addition, one-pot P-O bond construction is achieved in the presence of water or alcohols to provide phosphinic acids or phosphinates.
Q. Chen, J. Zeng, X. Yan, Y. Huang, C. Wen, X. Liu, K. Zhang, J. Org. Chem., 2016, 81, 10043-10048.