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.

Activation of a hydroxyl group by a Ph₂PCH₂CH₂PPh₂/ICH₂CH₂I system enables an efficient dehydroxylative fluorination of tertiary alcohols with Selectfluor. The reaction occurs rapidly to give the desired products in good yields.
W. Zhang, Y.-C. Gu, J.-H. Lin, J.-C. Xiao, Org. Lett., 2020, 22, 6642-6646.

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 divergent strategy for the fluorination of phenylacetic acid derivatives is induced by a charge-transfer complex between Selectfluor and 4-(dimethylamino)pyridine. In the presence of water, decarboxylative fluorination through a single-electron oxidation is dominant. Non-aqueous conditions result in the clean formation of α-fluoro-α-arylcarboxylic acids.
A. Madani, L. Anghileri, M. Heydenreich, H. M. Möller, B. Pieber, Org. Lett., 2022, 24, 5376-5380.

Sulfur mediates a synthesis of acyl fluorides from carboxylic acids using Selectfluor. A broad range of acyl fluorides are accessible from carboxylic acids while avoiding the formation of acid anhydrides. ¹⁹F NMR spectra suggest that a S₈-fluoro-sulfonium cation and a neutral S₈-difluoride are generated in situ as reactive species in this deoxyfluorination reaction.
E. M. Mahmoud, S. Mori, Y. Sumii, N. Shibata, Org. Lett., 2023, 25, 2810-2814.

A decarboxylative fluorination of tertiary β-keto carboxylic acids using an electrophilic fluorinating reagent proceeded in the absence of a catalyst or base to yield the corresponding α-fluoroketones very good yields.
M. Katada, K. Kitahara, S. Iwasa, K. Shibatomi, Synlett, 2018, 29, 2408-2411.

A Ag-catalyzed decarboxylative fluorination reaction provides an unprecedented route to either gem-difluoroalkanes or α-fluorocarboxylic acids from malonic acid derivatives by the judicious selection of base and solvent. This reaction features the use of readily available starting materials, tunable chemoselectivity and good functional group compatibility.
Z. Wang, C.-Y. Guo, C. Yang, J.-P. Chen, J. Am. Chem. Soc., 2019, 141, 5617-5622.

Enantioselective α-fluorination of both cyclic and acyclic β-dicarbonyl compounds with β,β-diaryl serines as primary amine organocatalysts was conducted with only 1.1 equiv of Selectfluor by adding alkali carbonates, such as Na₂CO₃ or Li₂CO₃. The reaction afforded α-fluorinated β-dicarbonyl compounds in good yield with excellent enantioselectivity.
K. Endo, D. Tomon, S. Arimitsu, J. Org. Chem., 2023, 88, 9037-9045.

A β,β-diaryl serine catalyzes an enantioselective fluorination of α-substituted β-diketones to afford the corresponding fluorinated products in very good yields with excellent enantioselectivity. The CO₂H group of the primary amine organocatalyst plays an important role in inducing the high enantioselectivity. Products could be converted into diols, aldols, and allylic fluorides without racemization.
S. Poorsadeghi, K. Endo, S. Arimitsu, Org. Lett., 2022, 24, 420-424.

By altering the amount of Selectfluor, a highly selective mono- and difluorination of 1,3-dicarbonyl compounds provides various 2-fluoro- and 2,2-difluoro-1,3-dicarbonyl compounds in very good yields. This practical and convenient fluorination can be performed in aqueous media without any catalyst and base.
L. Tang, Z. Yang, J. Jiao, Y. Cui, G. Zou, Q. Zhou, Y. Zhou, W. Rao, X. Ma, J. Org. Chem., 2019, 84, 10449-10458.

A radical-based C-C bond scission of 1,1-disubstituted epoxides followed by demethylenation provides ketones. The reaction is accomplished by Selecfluor and its radical dication working in tandem.
E. Holt, N. G. Garrison, R. Rowshanpour, J. J. Kim, N. Henriquez, W. Lam, N. Kiame, J. Williams, S. Zhao, T. Dudding, T. Lectka, J. Org. Chem., 2023, 88, 7597-7600.

A convenient reaction of isoxazoles with an electrophilic fluorinating agent (Selectfluor) provides tertiary fluorinated carbonyl compounds under mild reaction conditions and with good functional group tolerance. Diverse transformations of the resulting α-fluorocyanoketones furnish a broad range of fluorinated compounds.
M. Komatsuda, H. Ohki, H. Kondo Jr., A. Suto, J. Yamaguchi, Org. Lett., 2022, 24, 3270-3274.

In a remote hydro-oxygenation of alkenes under palladium catalysis, both terminal and internal alkenes are suitable to yield the corresponding linear alcohols efficiently. A compatible SelectFluor/silane redox system plays an essential role for the excellent chemo- and regioselectivities. The reaction features a broad substrate scope and excellent functional group compatibility.
X. Li, X. Yang, P. Chen, G. Liu, J. Am. Chem. Soc., 2022, 144, 22877-22883.

Photoredox catalysis enables a domino-fluorination-protodefluorination decarboxylative cross-coupling of α-keto acids with styrene to provide α,β-unsaturated ketones under mild conditions.
M. Zhang, J. Xi, R. Ruzi, N. Li, Z. Wu, W. Li, C. Zhu, J. Org. Chem., 2017, 82, 9305-9311.

Gold catalysis enables a chemoselective α-methylenation of aromatic ketones using Selectfluor as a methylenating agent to provide various 1,2-disubstituted propenone derivatives in good yields. This reaction offers simple operation, good functional group tolerance, and broad scope of substrates.
H. Zhu, X. Meng, Y. Zhang, G. Chen, Z. Cao, X. Sun, J. You, J. Org. Chem., 2017, 82, 12059-12065.

Selectfluor-promoted cascade cyclizations and cross-coupling reactions provide either 2,5-diacylthiophenes or β-acyl allylic methylsulfones from readily available starting materials by simple solvent modification. The transformations offer excellent chemoselectivity, and good functional group tolerance.
H. Lu, J. Chen, W. Zhou, L. Peng, S.-F. Yin, N. Kambe, R. Qiu, Org. Lett., 2023, 25, 389-394.

A catalytic, regioselective oxidative cyanation of conjugated and nonconjugated alkenes using a homogeneous copper catalyst and Selectfluor as oxidant provides branched alkenyl nitriles that are difficult to prepare.
D.-W. Gao, E. V. Vinogradova, S. K. Nimmagadda, J. M. Medina, Y. Xiao, R. M. Suciu, B. F. Cravatt, K. M. Engle, J. Am. Chem. Soc., 2018, 140, 8069-8073.

Selectfluor mediates an oxidative dehydrogenation of hydrazine derivatives via N-fluorination and elimination processes to provide azo compounds. This reaction offers simple operation, mild conditions, good functional group tolerance, and high efficiency.
Y. Zhao, S. Li, J. Cui, H. Wang, X. King, Y. Wang, L. Tian, Synthesis, 2022, 54, 5245-5252.

A palladium pincer complex catalyzes an allylic C-H borylation of alkenes in high yields. The transformation exhibits high regio- and stereoselectivity with various linear alkenes. Preliminary mechanistic studies indicate that this C-H borylation reaction proceeds via Pd(IV) pincer complex intermediates.
L. Mao, R. Bertermann, K. Emmert, K. J. Szabo, T. B. Marder, Org. Lett., 2017, 19, 6586-6589.

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.

The use of Selectfluor as an oxidant and tetrabutylammonium bromide/chloride salts as a halogen source enables a metal-free and molecular halogen reagent-free dihomohalogenation methodology. This effective strategy provides various fluorine-free halogenated products easily in quantitative yields from alkenes, alkynes, and natural products.
Z. Dağalan, R. Koçak, A. Daştan, B. Nişancı, Org. Lett., 2022, 24, 8261-8264.

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 dianionic phase-transfer catalyst enables an asymmetric fluorofunctionalization of γ,γ-disubstituted allylamine derivatives. Depending on the substituents on the alkene moiety, the reaction afforded chiral allylic fluorides and fluorinated dihydrooxazines in a highly enantioselective manner.
T. Niwa, K. Nishibashi, H. Sato, K. Ujiie, K. Yamashita, H. Egami, Y. Hamashima, J. Am. Chem. Soc., 2021, 143, 16599-16609.

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.

Selectfluor mediates practical and efficient oxidations of sulfides and thiols to provide sulfoxides, sulfones, and thiosulfonates, respectively, at ambient temperature. All these organosulfur compounds can be prepared with nearly quantitative yields by applying eco-friendly H₂O as O-source. The formation of sulfoxides and thiosulfonates takes only a few minutes.
X. Guo, X. Sun, M. Jiang, Y. Zhao, Synthesis, 2022, 54, 1996-2004.

Electrophilic bromination or fluorination of homoallylic alcohol O-Bn ethers triggers a diastereoselective hydride transfer to provide diastereomerically enriched haloalkyl alcohols. A subsequent intramolecular nucleophilic substitution affords tetrahydrofurans.
B. Wang, D. A. Gandamana, D. F. L. Rayo, F. Gagosz, S. Chiba, Org. Lett., 2019, 21, 9179-9182.

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.

Iodine catalyzes a cascade reaction between enaminones, hydrazines, and DMSO in the presence of Selectfluor to provide 1,4-disubstituted pyrazoles. DMSO plays a dual role as the C₁ source and the reaction medium. In addition, the synthesis of 1,3,4-trisubstituted pyrazoles using aldehydes as alternative C₁ building blocks has also been achieved.
H. Guo, L. Tian, Y. Liu, J.-P. Wan, Org. Lett., 2022, 24, 228-233.

Organoiodine(I/III) chemistry enables a metal-free, catalytic enantioselective intermolecular oxyamination of aryl- and alkyl-substituted alkenes with N-(fluorosulfonyl)carbamate as a bifunctional N,O-nucleophile with high enantioselectivity and electronically controlled regioselectivity. The oxyaminated products can be easily deprotected in one step to reveal free amino alcohols in high yields.
C. Wata, T. Hashimoto, J. Am. Chem. Soc., 2021, 143, 1745-1751.

A chiral triazole-substituted iodoarene catalyzes an enantioselective oxidative cyclization of N-allyl carboxamides to provide highly enantioenriched oxazolines and oxazines. Quaternary stereocenters can be constructed and, besides N-allyl amides, the corresponding thioamides and imideamides are well tolerated as substrates.
A. H. Abazid, T.-N. Hollwedel, B. J. Nachtsheim, Org. Lett., 2021, 23, 5076-5080.

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.

Treatment of several 3-substituted indoles, including derivatives of tryptophan and serotonin, with Selectfluor in acetonitrile/water provides 3-substiuted 3-fluorooxindoles in very good yields.
Y. Takeuchi, T. Tarui, N. Shibata, Org. Lett., 2000, 2, 639-642.

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.

An efficient cyclization of enamino ketones in the presence of Selectfluor provides various 3-fluorochromones (3-fluoro-4H-chromene-4-ones) in good yields. This method offers simple operational procedures, a high purity of the product, and excellent regioselectivity.
V. Kandula, P. K. Thota, P. Mallesham, K. Raghavulu, A. Chatterjee, S. Yennam, M. Behera, Synlett, 2019, 30, 2295-2299.

Selectfluor promotes an oxidative coupling of quinoxalin-2(1H)-ones with alcohols, amines, thiols at the C3-position under metal- and photocatalyst-free conditions. The method offers a broad substrate scope including bioactive molecules, mild reaction conditions, readily available coupling partners, high yields, scalability and step-economy.
Sonam, V. N. Shinde, K. Rangan, A. Kumar, J. Org. Chem., 2023, 88, 2344-2357.

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 organobismuth(III) complex bearing a bis-aryl sulfone ligand backbone catalyzes a synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids in the presence of SO₂ and Selectfluor. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.
M. Magre, J. Cornella, J. Am. Chem. Soc., 2021, 143, 21497-21502.

In a copper-free Sandmeyer-type fluorosulfonylation reaction with Na₂S₂O₅ as the sulfur dioxide source and Selectfluor as fluorine source, aryldiazonium salts are transformed into sulfonyl fluorides. In situ diazotization enables the use of aromatic amines as substrates. The method offers broad functional group tolerance, gram-scale synthesis and late-stage fluorosulfonylation.
T. Zhong, M.-K. Pang, Z.-D. Chen, B. Zhang, J. Weng, G. Lu, Org. Lett., 2020, 22, 2941-2945.

Thioethers can be converted to thiocyanates via fluorium-initiated dealkylative cyanation in the presence of selectfluor as the oxidant and trimethylsilyl cyanide as the cyanation reagent. This method is user-friendly, operationally simple, and step-economical.
Y. Chen, H. Qi, N. Chen, D. Ren, J. Xu, Z. Yang, J. Org. Chem., 2019, 84, 9044-9050.

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.

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

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