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Novelties of solid-liquid phase transfer catalysed synthesis of p-toluenesulfonyl fluoride from p-toluenesulfonyl chloride
Organic sulfonyl fluorides are of interest owing to their insecticidal, germicidal and enzyme inhibitory properties. In the current work synthesis of p-toluenesufonyl fluoride was accomplished by reacting p-toluenesulfonyl chloride with solid potassium fluoride using PEG-400 as a catalyst under solid-liquid phase transfer catalysis (S-L PTC) at 30°C. p-Toulenesulfonyl fluoride is used as peroxygen bleach activator. It also finds use in the treatment of Alzheimer's disease. The mechanism is based on homogeneous solubilization of solid. PEG forms a complex with metal cation which associates with the nucleophile and it participates in SN2 type reaction. The reaction is intrinsically kinetically controlled. A complete theoretical analysis is done to determine both the rate constant and equilibrium constant from the same set of data. The activation energy and Gibbs free energy are also calculated.
Yadav, Ganapati D.,Paranjape, Priyanvada M.
p. 99 - 106
(2005)
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Novelties of solid-liquid phase transfer catalysed synthesis of p-toluenesulfonyl fluoride from p-toluenesulfonyl chloride
Organic sulfonyl fluorides are of interest owing to their insecticidal, germicidal and enzyme inhibitory properties. In the current work, synthesis of p-toluenesufonyl fluoride was accomplished by reacting p-toluenesulfonyl chloride with solid potassium fluoride using PEG-400 as a catalyst under solid-liquid phase transfer catalysis (S-L PTC) at 30°C. p-Toluenesulfonyl fluoride is used as peroxygen bleach activator. It also finds use in the treatment of Alzheimer's disease. The mechanism is based on homogeneous solubilization of solid. PEG forms a complex with metal cation which associates with the nucleophile and it participates in SN2 type reactions. The reaction is intrinsically kinetically controlled. A complete theoretical analysis is done to determine both the rate constant and equilibrium constant from the same set of data. The activation energy and Gibbs free energy are also calculated.
Yadav, Ganapati D.,Paranjape, Priyanvada M.
p. 289 - 295
(2005)
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Synthesis of Symmetrical Thiosulfonates via Cu(OTf)2-Catalyzed Reductive Homocoupling of Arenesulfonyl Chlorides
A variety of symmetrical thiosulfonates are synthesized via Cu-catalyzed reductive homocoupling of aryl sulfonyl chlorides. This protocol uses organic amine acting as a mild reductant and low-cost copper as an effective catalyst. Such a reductive coupling process features a broad substrate scope and good functional group tolerance. Related thiosulfonate products can also be converted into diverse functional molecules.
Liu, Lixia,Luo, Bo,Wang, Chengming
supporting information
p. 5880 - 5883
(2021/11/27)

Fluorination method
In order to overcome the problems of high cost and low stability of the existing fluorination reagents for preparing acyl fluoride, sulfonyl fluoride and phosphoryl fluoride compounds, the invention provides a fluorination method, which comprises the following operation steps of: adding a fluorination reagent into a substrate, wherein the fluorination reagent comprises cations M and anions, the anions are selected from one or more of perfluoropolyether chain carboxylic acid anions as shown in the specification: CF3(OCF2)nCO2, wherein n is selected from 1-10; the substrate comprises a carboxylic acid compound, a sulfonic acid compound, a phosphoric acid compound and a phosphine oxide compound; and carrying out fluorination reaction to obtain acyl fluoride, sulfonyl fluoride and phosphoryl fluoride products. According to the fluorination method provided by the invention, the perfluoropolyether chain carboxylate is used as a fluorination reagent, so that the dehydroxylation fluorination reaction of the carboxylic acid compound, the sulfonic acid compound and the phosphoric acid compound and the fluorination reaction of the phosphine oxide compound are realized, the product yield isrelatively high, and the fluorination method has relatively good universality for different substrates.
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Paragraph 0130-0163

(2021/01/12)

Deoxyfluorination of Carboxylic, Sulfonic, Phosphinic Acids and Phosphine Oxides by Perfluoroalkyl Ether Carboxylic Acids Featuring CF2O Units
The deoxyfluorination of carboxylic, sulfonic, phosphinic acids and phosphine oxides is a fundamentally important approach to access acyl fluorides, sulfonyl fluorides and phosphoric fluorides, thus the development of inexpensive, stable, easy-to-handle, versatile, and efficient deoxyfluorination reagents is highly desired. Herein, we report the use of potassium salts of perfluoroalkyl ether carboxylic acids (PFECA) featuring CF2O units as deoxyfluorination reagents, which are generated mainly as by-products in the manufacture of hexafluoropropene oxide (HFPO). The synthesis of acyl fluorides, sulfonyl fluorides and phosphoric fluorides can be realized via carbonic difluoride (COF2) generated in situ from thermal degradation of the PFECA salt.
Zhao, Shiyu,Guo, Yong,Su, Zhaoben,Wu, Chengying,Chen, Wei,Chen, Qing-Yun
supporting information
p. 1225 - 1232
(2021/05/04)

Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides
A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that the organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within the catalytic cycle without modifying the oxidation state. All steps have been validated, including the catalytic insertion of SO2 into Bi-C bonds, leading to a structurally unique O-bound bismuth sulfinate complex. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.
Cornella, Josep,Magre, Marc
supporting information
p. 21497 - 21502
(2022/01/03)

Copper-catalyzed three-component reaction of arylhydrazine hydrochloride, DABSO, and NFSI for the synthesis of arenesulfonyl fluorides
This paper reports a convenient copper-catalyzed three-component conversion of arylhydrazine hydrochlorides to arenesulfonyl fluorides in good yields under mild conditions, using 1,4-diazabicyclo [2.2.2]octane bis(sulfur dioxide) (DABSO) as a sulfonyl source andN-fluorobenzenesulfonimide (NFSI) as a fluorine source based on a radical sulfur dioxide insertion and fluorination strategy. Notably, arylhydrazine hydrochloride is used as a safe precursor of aryl radicals.
Chen, Qing-Yun,Guo, Yong,Hu, Xiaojun,Liu, Chao,Liu, Yongan,Ma, Xiaoyu,Pan, Qijun,Pang, Wan,Wu, Jingjing
supporting information
p. 8999 - 9003
(2021/11/04)

Visible-Light-Mediated Synthesis of Sulfonyl Fluorides from Arylazo Sulfones
Sulfonyl fluorides are useful motifs for a wide range of applications in organic synthesis including sulfur (VI) fluoride exchange-based “click chemistry.” Herein, a visible-light-mediated synthesis of sulfonyl fluorides from arylazo sulfones is described. In the present study, K2S2O5 and N-fluorobenzenesulfonimide (NFSI) were used as the sulfonyl source and fluorinating agent, respectively, for visible-light-mediated fluorosulfonylation of arylazo sulfones to prepare various sulfonyl fluorides in 60–85% yield. This protocol is a synthetic approach to provide useful sulfonyl fluoride structures at room temperature. (Figure presented.).
Bui, Tien Tan,Kim, Hee-Kwon,Tran, Van Hieu
supporting information

(2021/10/14)

Metal-Free Visible-Light Synthesis of Arylsulfonyl Fluorides: Scope and Mechanism
The first metal-free procedure for the synthesis of arylsulfonyl fluorides is reported. Under organo-photoredox conditions, aryl diazonium salts react with a readily available SO2 source (DABSO) to afford the desired product through simple nucleophilic fluorination. The reaction tolerates the presence of both electron-rich and -poor aryls and demonstrated a broad functional group tolerance. To shed the light on the reaction mechanism, several experimental techniques were combined, including fluorescence, NMR, and EPR spectroscopy as well as DFT calculations.
Louvel, Dan,Chelagha, Aida,Rouillon, Jean,Payard, Pierre-Adrien,Khrouz, Lhoussain,Monnereau, Cyrille,Tlili, Anis
supporting information
p. 8704 - 8708
(2021/05/17)

A Unified Strategy for Arylsulfur(VI) Fluorides from Aryl Halides: Access to Ar-SOF3 Compounds
A convenient protocol to selectively access various arylsulfur(VI) fluorides from commercially available aryl halides in a divergent fashion is presented. Firstly, a novel sulfenylation reaction with the electrophilic N-(chlorothio)phthalimide (Cl-S-Phth) and arylzinc reagents afforded the corresponding Ar-S-Phth compounds. Subsequently, the S(II) atom was selectively oxidized to distinct fluorinated sulfur(VI) compounds under mild conditions. Slight modifications on the oxidation protocol permit the chemoselective installation of 1, 3, or 4 fluorine atoms at the S(VI) center, affording the corresponding Ar-SO2F, Ar-SOF3, and Ar-SF4Cl. Of notice, this strategy enables the effective introduction of the rare and underexplored -SOF3 moiety into various (hetero)aryl groups. Reactivity studies demonstrate that such elusive Ar-SOF3 can be utilized as a linchpin for the synthesis of highly coveted aryl sulfonimidoyl fluorides (Ar-SO(NR)F).
Cornella, Josep,Wang, Lin
supporting information
p. 23510 - 23515
(2020/10/29)

Fluorosulfonylation of arenediazonium tetrafluoroborates with Na2S2O5 and N-fluorobenzenesulfonimide
A transition-metal-free Sandmeyer-type fluorosulfonylation reaction has been achieved by the three-component reaction of arenediazonium tetrafluoroborates, Na2S2O5, and N-fluorobenzenesulfonimide (NFSI). The reaction proceeds through a radical tandem process, affording various arenesulfonyl fluorides in moderate to high yields. This protocol not only provides a complement to the previous fluorosulfonylation reactions, but also extends the applications of Sandmeyer reaction.
Huang, Yangen,Liu, Shuai,Qing, Feng-Ling,Xu, Xiu-Hua
(2020/10/18)

Arenesulfonyl Fluoride Synthesis via Copper-free Sandmeyer-type Fluorosulfonylation of Arenediazonium Salts
The limited availability of highly valuable arenesulfonyl fluorides seriously hinders their further application in many research fields including medicinal chemistry and chemical biological, organic synthesis, polymer preparation, etc. We report herein a mild and efficient copper-free Sandmeyer-type fluorosulfonylation reaction of various arenediazonium salts to prepare valuable arenesulfonyl fluorides using K2S2O5 as both a reductant and a practical sulfonyl source in combination with N-fluorobenzenesulfonimide as an effective fluorine source. This methodology provides an attractive route to diverse important arenesulfonyl fluorides given the overall practicality and scope.
Lin, Qiongzhen,Ma, Zhanhu,Zheng, Changge,Hu, Xiao-Jun,Guo, Yong,Chen, Qing-Yun,Liu, Chao
supporting information
p. 1107 - 1110
(2020/07/06)

Arenesulfonyl Fluoride Synthesis via Copper-Catalyzed Fluorosulfonylation of Arenediazonium Salts
We report herein a general and practical copper-catalyzed fluorosulfonylation reaction of a wide range of abundant arenediazonium salts to smoothly prepare various arenesulfonyl fluorides using the 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as a convenient sulfonyl source in combination with KHF2 as an ideal fluorine source and without the need for additional oxidants. Interestingly, the electronic character of the arene ring in the starting arenediazonium salts has a significant impact on the reaction mechanistic pathway.
Liu, Yongan,Yu, Donghai,Guo, Yong,Xiao, Ji-Chang,Chen, Qing-Yun,Liu, Chao
supporting information
p. 2281 - 2286
(2020/03/13)

Copper-free Sandmeyer-type Reaction for the Synthesis of Sulfonyl Fluorides
A copper-free Sandmeyer-type fluorosulfonylation reaction is reported. Utilizing Na2S2O5 and Selectfluor as the sulfur dioxide and fluorine sources, respectively, aryldiazonium salts were transformed into sulfonyl fluorides. The one-pot direct synthesis of sulfonyl fluorides from aromatic amines was also realized via in situ diazotization. The practicality of this method was demonstrated by the broad functional group tolerance, gram-scale synthesis, and late-stage fluorosulfonylation of natural products and pharmaceuticals.
Zhong, Tao,Pang, Meng-Ke,Chen, Zhi-Da,Zhang, Bin,Weng, Jiang,Lu, Gui
supporting information
p. 3072 - 3078
(2020/04/10)

Synthesis of Sulfonyl Fluorides from Sulfonamides
A simple and practical synthesis of sulfonyl fluorides from sulfonamides is reported. The method capitalizes on the formation of the sulfonyl chloride by virtue of the reaction of Pyry-BF4 and MgCl2, and subsequent in situ conversion to the more robust and stable sulfonyl fluoride by the presence of KF. The mild conditions and high chemoselectivity of the protocol enable the late-stage formation of sulfonyl fluorides from densely functionalized molecules.
Pérez-Palau, Marina,Cornella, Josep
supporting information
p. 2497 - 2500
(2020/03/11)

Sulfonyl Fluoride Synthesis through Electrochemical Oxidative Coupling of Thiols and Potassium Fluoride
Sulfonyl fluorides are valuable synthetic motifs for a variety of applications, among which sulfur(VI) fluoride exchange-based "click chemistry" is currently the most prominent. Consequently, the development of novel and efficient synthetic methods to access these functional groups is of great interest. Herein, we report a mild and environmentally benign electrochemical approach to prepare sulfonyl fluorides using thiols or disulfides, as widely available starting materials, in combination with KF, as an inexpensive, abundant and safe fluoride source. No additional oxidants nor additional catalysts are required and, due to mild reaction conditions, the reaction displays a broad substrate scope, including a variety of alkyl, benzyl, aryl and heteroaryl thiols or disulfides.
Laudadio, Gabriele,Bartolomeu, Aloisio De A.,Verwijlen, Lucas M. H. M.,Cao, Yiran,De Oliveira, Kleber T.,No?l, Timothy
supporting information
p. 11832 - 11836
(2019/08/26)

Facile one-pot synthesis of sulfonyl fluorides from sulfonates or sulfonic acids
A facile cascade process for directly transforming the abundant and inexpensive sulfonates (or sulfonic acids) to the highly valuable sulfonyl fluorides was developed. This new protocol features mild reaction conditions using readily available and easy-to-operate reagents. A diverse set of sulfonyl fluorides was prepared facilitating the enrichment of the sulfonyl fluoride library.
Jiang, Ying,Alharbi, Njud S.,Sun, Bing,Qin, Hua-Li
p. 13863 - 13867
(2019/05/17)

One-pot fluorosulfurylation of Grignard reagents using sulfuryl fluoride
Herein, we report a new method for the one-pot syntheses of sulfonyl fluorides. Addition of an alkyl, aryl, or heteroaryl Grignard to a solution of sulfuryl fluoride at ambient temperature affords the desired sulfonyl fluorides in 18-78% yield. Furthermore, this method is applicable for in situ sequential reactions, whereby the Grignard reagent can be converted to the corresponding diarylsulfone, sulfonate ester, or sulfonamide in a one-pot process.
Lee, Cayo,Ball, Nicholas D.,Sammis, Glenn M.
supporting information
p. 14753 - 14756
(2019/12/23)

Copper-Catalyzed Amide Radical-Directed Cyanation of Unactivated Csp3-H Bonds
A method for site-selective intermolecular δ/?-Csp3-H cyanation of aliphatic sulfonamides is developed using TsCN as the cyanating reagent, catalyzed by a Cu(I)/phenanthroline complex. The mild, expeditious, and modular protocol allows efficient remote Csp3-H cyanation with good functional group tolerance and high regioselectivity. Mechanistic studies indicate that the reaction might proceed through a Cu(I)-mediated N-F bond cleavage to generate an amidyl radical, 1,5-HAT, and cyano group transfer of the resulting carbon radical with TsCN.
Zhang, Hongwei,Zhou, Yulu,Tian, Peiyuan,Jiang, Cuiyu
supporting information

(2019/03/19)

Directed ortho-Metalation of Arenesulfonyl Fluorides and Aryl Fluorosulfates
Studies on directed ortho -metalation (DoM) of arenesulfonyl fluorides (ArSO 2 F) with in situ electrophile trapping are presented. Under optimized conditions (LDA, THF, -78 °C), a series of model substrates was mono- and difunctionalized with trimethylsilyl chloride in good yields. The synthetic results reveal powerful directing character of the SO 2 F group, being ahead of bromine and methoxy substituents. Under the same metalation conditions, aryl fluorosulfates (ArOSO 2 F) display fragmentation to arynes and migration of the SO 2 F group to the ortho position (anionic thia-Fries rearrangement).
Talko, Alicja,Antoniak, Damian,Barbasiewicz, Micha?
p. 2278 - 2286
(2019/05/24)

A practical microwave method for the synthesis of fluoromethy 4-methylbenzenesulfonate in tert-amyl alcohol
Fluorine substitution is an established tool in medicinal chemistry to favourably alter the molecular properties of a lead compound of interest. However, gaps still exist in the library of synthetic methods for accessing certain fluorine-substituted motifs. One such area is the fluoromethyl group, particularly when required in a fluoroalkylating capacity. The cold fluorination of methylene ditosylate is under evaluated in the literature, often proceeding with low yields or harsh conditions. This report describes a novel microwave method for the rapid nucleophilic fluorination of methylene ditosylate using inexpensive reagents in good isolated yield (65%).
Brocklesby, Kayleigh L.,Waby, Jennifer S.,Cawthorne, Christopher,Smith, Graham
p. 1635 - 1637
(2018/04/02)

Silver-mediated radical aryltrifluoromethylthiolation of activated alkenes by S-trifluoromethyl 4-methylbenzenesulfonothioate
Herein, we describe the preparation of trifluoromethylthiol-substituted oxindoles by silver-mediated aryltrifluoromethylthiolation of activated alkenes, using S-trifluoromethyl 4-methylbenzenesulfonothioate as a F3CS radical source and showing that the reagent availability, mild conditions, and broad functional group compatibility of this transformation make it a viable alternative strategy of constructing Csp3–SCF3 bonds.
Zhao, Xia,Yang, Bo,Wei, Aoqi,Sheng, Jianqiao,Tian, Miaomiao,Li, Quan,Lu, Kui
p. 1719 - 1722
(2018/04/02)

Regioselective pinacol rearrangement of unsymmetrical cyclobutane-1,2-diols
Hydroxy-sulfone 34b, prepared as a mixture of trans and cis isomers by condensing the O-silyl derivative 18c of 2-hydroxy-2-methyl-cyclobutanone 18b-the Norrish II photocyclisation product of 2,3-pentanedione 21- and methyl phenyl sulfone 33 was found to rearrange selectively either to the cyclo-propanic β-ketosulfone 37 or the isomeric methyl ketone 38 by using, respectively, the tosyl fluoride/DBU and the DAST reagent. The potential of this methodology has been illustrated by a synthesis of phytal 1 from geranylacetone 46, and by the preparation from 3,4-hexanedione 51 and prenol 56-via the cyclopropanic β-ketosulfone 54 (X-ray)-of an advanced fragment of the juvenile hormone molecule 59.
Gembus, Vincent,Karmazin, Lydia,Pira, Sylvain,Uguen, Daniel
p. 319 - 336
(2018/03/21)

METHOD FOR PRODUCING FLUORINATED ALKANE, METHOD FOR SEPARATING AND RECOVERING AMIDINE BASE, AND METHOD FOR USING RECOVERED AMIDINE BASE
The present invention provides: a method for producing a fluorinated alkane represented by the formula (2): R2—F, wherein an alcohol having 3 to 5 carbon atoms is fluorinated by a fluorinating agent represented by the formula (1): R1SO2F in the absence of a solvent, and in the presence of a base selected from the group consisting of an amidine base and a phosphazene base; a method for separating and recovering an amidine base from an amidine base-sulfonate complex represented by the following formula (5); and a method for using a recovered amidine base. In the formula, R1 represents a methyl group, an ethyl group or an aromatic group, R2 represents an alkyl group having 3 to 5 carbon atoms, and n is 0 or 2.
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Paragraph 0179

(2018/05/17)

Sulfonyl halide synthesis by thiol oxyhalogenation using NBS/NCS – iPrOH
A rapid and facile method provides a general route to sulfonyl bromides/chlorides by the oxidation of thiols using NXS – ROH (X?=?Br,Cl, R?=?iPr) as an oxyhalogenation reagent. Control experiments suggest that the alcohol component is the source of oxygen. The proposed method enable the access to structurally diverse sulfonyl bromides and chlorides including challenging examples, inaccessible by other synthetic methods.
Silva-Cuevas, Carolina,Perez-Arrieta, Carlos,Polindara-García, Luis A.,Lujan-Montelongo, J. Armando
p. 2244 - 2247
(2017/05/16)

One-pot palladium-catalyzed synthesis of sulfonyl fluorides from aryl bromides
A mild, efficient synthesis of sulfonyl fluorides from aryl and heteroaryl bromides utilizing palladium catalysis is described. The process involves the initial palladium-catalyzed sulfonylation of aryl bromides using DABSO as an SO2 source, followed by in situ treatment of the resultant sulfinate with the electrophilic fluorine source NFSI. This sequence represents the first general method for the sulfonylation of aryl bromides, and offers a practical, one-pot alternative to previously described syntheses of sulfonyl fluorides, allowing rapid access to these biologically important molecules. Excellent functional group tolerance is demonstrated, with the transformation successfully achieved on a number of active pharmaceutical ingredients, and their precursors. The preparation of peptide-derived sulfonyl fluorides is also demonstrated.
Davies, Alyn T.,Curto, John M.,Bagley, Scott W.,Willis, Michael C.
p. 1233 - 1237
(2017/02/10)

A fluoride compound of preparation method
The invention relates to a preparation method of a sulfuryl fluoride compound. A sulfonyl hydrazide compound and a fluoride reagent serve as reaction raw materials. The preparation method includes the steps that a, the sulfonyl hydrazide compound with the structure (I) and the fluoride reagent are dispersed in a solvent, wherein the structure (I) is shown in the specification; b; a mixture obtained from the step a is stirred and heated to obtain the sulfuryl fluoride compound with the structure (II), wherein the structure (II) is shown in the specification (II). Compared with existing related technologies in the chemical synthesis field, the method of preparing sulfuryl fluoride from sulfonyl hydrazide is achieved for the first time. In the method, no catalyst needs to be added, reaction conditions are moderate, good compatibility can be achieved for water and air, and large-scale production is easy to achieve. The experimental result indicates that the yield of the obtained sulfuryl fluoride compound can reach up to 98%.
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Paragraph 0070; 0071; 0072; 0073; 0074; 0075-0084

(2017/08/25)

A study of the reactivity of S(VI)-F containing warheads with nucleophilic amino-acid side chains under physiological conditions
Sulfonyl fluorides (SFs) have recently emerged as a promising warhead for the targeted covalent modification of proteins. Despite numerous examples of the successful deployment of SFs as covalent probe compounds, a detailed exploration of the factors influencing the stability and reactivity of SFs has not yet appeared. In this work we present an extensive study on the influence of steric and electronic factors on the reactivity and stability of the SF and related SVI-F groups. While SFs react rapidly with N-acetylcysteine, the resulting adducts were found to be unstable, rendering SFs inappropriate for the durable covalent inhibition of cysteine residues. In contrast, SFs afforded stable adducts with both N-acetyltyrosine and N-acetyllysine; furthermore, we show that the reactivity of arylsulfonyl fluorides towards these nucleophilic amino acids can be predictably modulated by adjusting the electronic properties of the warhead. These trends were largely conserved when the covalent reaction occurred within a protein binding pocket. We have also obtained a crystal structure depicting covalent modification of the catalytic lysine of a tyrosine kinase (FGFR1) by the ATP analog 5′-O-3-((fluorosulfonyl)benzoyl)adenosine (m-FSBA). Highly reactive warheads were demonstrated to be unstable with respect to hydrolysis in buffered aqueous solutions, indicating that warhead reactivity must be carefully tuned to provide optimal rates of protein modification. Our results demonstrate that the reactivity of SFs complements that of more commonly studied acrylamides, and we hope that this work spurs the rational design of novel SF-containing covalent probe compounds and inhibitors, particularly in cases where a suitably positioned cysteine residue is not present.
Mukherjee,Debreczeni,Breed,Tentarelli,Aquila,Dowling,Whitty,Grimster
supporting information
p. 9685 - 9695
(2017/11/30)

Catalyst-free radical fluorination of sulfonyl hydrazides in water
The first catalyst-free fluorination of sulfonyl hydrazides for the synthesis of sulfonyl fluorides has been developed via a free-radical pathway. This protocol presents a broad substrate scope and does not require any metal catalyst and additive. All these transformations proceed smoothly in water under mild conditions, which enables a straightforward, practical and environmentally benign fluorination for S-F bond formation.
Tang, Lin,Yang,Wen, Lixian,Yang, Xingkun,Wang, Zhiyong
p. 1224 - 1228
(2016/03/09)

Synthesis, Bonding, and Reactivity of Vanadium(IV) Oxido-Fluorido Compounds with Neutral Chelate Ligands of the General Formula cis-[VIV(=O)(F)(LN-N)2]+
Reaction of the oxidovanadium(IV)-LN-N species (LN-N is bipy = 2,2′-bipyridine or bipy-like molecules) with either BF4- or HF and/or KF results in the formation of compounds of the general formula cis-[VIV(=O)(F)(LN-N)2]+. Structural and spectroscopic (electron paramagnetic resonance) characterization shows that these compounds are in the tetravalent oxidation state containing a terminal fluorido ligand. Density functional theory calculations reveal that the VIV-F bond is mainly electrostatic, which is reinforced by reactivity studies that demonstrate the nucleophilicity of the fluoride ligand in a halogen exchange reaction and in fluorination of various organic substrates.
Passadis, Stamatis S.,Tsiafoulis, Constantinos,Drouza, Chryssoula,Tsipis, Athanassios C.,Miras, Haralampos N.,Keramidas, Anastasios D.,Kabanos, Themistoklis A.
supporting information
p. 1364 - 1366
(2016/02/27)

Fluoride complexes of cyclometalated iridium(III)
Many electroluminescent devices rely on cyclometalated iridium(III). Their advancement depends on access to reactive starting materials because of the inertness of Ir(III). Notably, fluoride complexes of bis(cyclometalated) Ir(III) are scarce. Syntheses of bridged and terminal fluorides are reported here. New compounds are luminescent and thermally reactive; they are characterized by ground-state and optical methods. Crystal structures were determined for one bridging and one terminal fluoride complex. The terminal fluoride shows intramolecular hydrogen bonding to an adjacent 3,5-dimethylpyrazole ligand; a lesser interaction may occur between F and a nearby aromatic C-H bond. Terminal fluoride complexes react with carbon-, silicon-, and sulfur-based electrophiles. The new complexes phosphoresce with microsecond lifetimes at 77 and 298 K. Density-functional theory calculations indicate triplet states with little contribution from fluoride. The compounds herein are versatile phosphors having the ground-state reactivity of late transition metal fluorides.
Maity, Ayan,Stanek, Robert J.,Anderson, Bryce L.,Zeller, Matthias,Hunter, Allen D.,Moore, Curtis E.,Rheingold, Arnold L.,Gray, Thomas G.
p. 109 - 120
(2015/01/30)

Rearrangement in a Tripodal Nitroxide Ligand to Modulate the Reactivity of a Ti-F Bond
The tripodal nitroxide ligand [(2-tBuNO)C6H4CH2)3N]3- (TriNOx3-) binds the Ti(IV) cation and prevents inner-sphere coordination of chloride in the complex [Ti(TriNOx)]Cl (1). The ligand undergoes an η2-NO to κ1-O rearrangement to enable a fluoride ion to bind in the related complex Ti(TriNOx)F (2). Computational and reactivity studies demonstrated that the ligand rearrangement contributed to the enthalpy change in the transfer of a fluoride anion.
Boreen, Michael A.,Bogart, Justin A.,Carroll, Patrick J.,Schelter, Eric J.
p. 9588 - 9593
(2015/10/12)

Oxidation of disulfides with electrophilic halogenating reagents: Concise methods for preparation of thiosulfonates and sulfonyl halides
The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. Conversely, the reaction of disulfides with 6.5 equiv of Selectfluor or thiosulfonates with 4.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluorides in high yields. Accufluor and FP-T300 are also effective in preparing sulfonyl fluorides from disulfides under the similar reaction conditions. Sulfonyl chlorides or sulfonyl bromides were effectively obtained from the reaction of disulfides with 6 equiv of either N-chlorosuccinimide or N-bromosuccinimide in acetonitrile/water (10:1) at room temperature. Some other electrophilic chlorinating or brominating reagents are also able to be used instead of N-chlorosuccinimide or N-bromosuccinimide for the syntheses of sulfonyl halides from disulfides. These reactions of disulfides with electrophilic halogenating reagents are convenient methods to prepare thiosulfonates and sulfonyl halides.
Kirihara, Masayuki,Naito, Sayuri,Nishimura, Yuki,Ishizuka, Yuki,Iwai, Toshiaki,Takeuchi, Haruka,Ogata, Tomomi,Hanai, Honoka,Kinoshita, Yukari,Kishida, Mari,Yamazaki, Kento,Noguchi, Takuya,Yamashoji, Shiro
p. 2464 - 2471
(2014/04/03)

Mono- and dinitration of pentafluorosulfanylbenzenes with [NO 2][BF4], and substrate selectivity (PhSF5 vs PhCF3 and PhSF5 vs PhNO2) in competitive nitration
PhSF5 1 reacts with NO2+BF 4-/TfOH in CH2Cl2 (DCM) at room temperature to give 1-nitro-3-(pentafluorosulfanyl)benzene 2 in near quantitative yield. The dinitro derivative 4 is synthesized from 2 by reaction with NO2+BF4-/TfOH at 70 °C. The p-MeC6H4SF5 is mononitrated at room temperature with NO2+BF4-/DCM and dinitrated with NO2+BF4-/TfOH. Substrate selectivity (kPhSF5kRPh) in competitive nitration for PhSF5/PhCF3 and PhSF5/PhNO 2 with NO2+BF4- in DCM at room temperature was determined at 21.3 and ～1 respectively. Relative stability of the corresponding benzenium ions were gauged by DFT from the isodesmic proton transfer reaction SF5-C6H 6+ + R-C6H5 → SF 5-C6H5 + R-C6H6 + (R = CF3 and NO2). These studies indicate that reactivity of ArSF5 in SEAr is similar to ArNO 2.
Okazaki, Takao,Laali, Kenneth K.
p. 96 - 100
(2014/08/05)

C-F bond activation with an apparently benign ethynyl dithiocarbamate, and subsequent fluoride transfer reactions
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Ung, Gael,Bertrand, Guy
supporting information
p. 12955 - 12957,3
(2020/09/16)

Oxidation of disulfides with Selectfluor: Concise syntheses of thiosulfonates and sulfonyl fluorides
The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. On the other hand, the reaction of disulfides with 6.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluoride in high yields.
Kirihara, Masayuki,Naito, Sayuri,Ishizuka, Yuki,Hanai, Honoka,Noguchi, Takuya
experimental part
p. 3086 - 3089
(2011/06/26)

Nucleophilic fluorination reactions starting from aqueous fluoride ion solutions
The sulfonium borane 2+ reacts with fluoride anions in MeOH/H2O mixtures to afford the zwitterionic fluoroborate 2-F as an easily isolable nonhygroscopic solid. In dry acetonitrile, 2-F reacts with PhS- to afford the anionic fluoroborate 1-F-. The latter is very labile and acts as a nucleophilic fluorination reagent toward a variety of substrates including alkylhalides and electron-deficient aromatic compounds. This approach may become broadly applicable to nucleophilic fluorination procedures that involve wet fluoride sources.
Zhao, Haiyan,Gabbai, Francois P.
supporting information; experimental part
p. 1444 - 1446
(2011/05/08)

METHODS FOR PRODUCING ARYLSULFUR PENTAFLUORIDES
Novel methods for preparing arylsulfur pentafluorides are disclosed. Arylsulfur halotetrafluoride is reacted with a fluoride source under hydrous conditions to form an arylsulfur pentafluoride. The purification method is also disclosed.
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Page/Page column 37

(2010/04/03)

A convenient, one-pot procedure for the preparation of acyl and sulfonyl fluorides using Cl3CCN, Ph3P, and TBAF(t -BuOH) 4
Various carboxylic acids were converted into acyl fluorides in excellent yields by treatment with trichloroacetonitrile, triphenylphosphine, and TBAF(t-BuOH)4 at room temperature. The reaction was applicable to the preparation of acid-sensitive amino acid fluorides without deprotection or rearrangement
Kim, Joong-Gon,Jang, Doo Ok
experimental part
p. 3049 - 3052
(2011/02/25)

Orthoamides, LXIV [1]. Formylation of aromatic compounds by tris(dichloromethyl)amine and oligoformylamine derivatives in the presence of superacids
Tris(dichloromethyl)amine (4), triformamide (1) and tris(diformylamino) methane ( formyl-aalen ) (2) can be activated by addition of trifluoromethanesulfonic acid. The formylating systems thus formed transform activated aromatic compounds, such as toluene, anisole or 2,4-dimethoxybenzene to the corresponding aldehydes. The formylating ability of systems from 4 and superacids, such as FSO3H, FSO3H/SbF5, C 4F9SO3H, and mixtures of aluminum chloride with C4F9SO3H and chlorosulfonic acid, respectively, is compared. In general, low reaction temperatures (-20 to -10°C) are necessary to obtain aldehydes with acceptable to good yields. Remarkably, at higher temperatures (～ 100°C) compound 4 can also act as a formylating agent in the presence of suitable zeolites, as e. g. zeolite HBEA. Reaction mechanisms of the new formylation reactions are proposed.
Kantlehner, Willi,Leonhardt, Sylvia,Ziegler, Georg,Scherr, Oliver,Kre?, Ralf,Goeppert, Alain,Sommer, Jean
p. 995 - 1014
(2008/10/09)

NOVEL COMPOUNDS
The present invention relates to novel indole derivatives such as compounds of the formula (I): which possess antagonist potency at the 5-HT6 receptor and the use of such compounds or pharmaceutically acceptable salts or solvates thereof in the treatment of Alzheimer's disease and other CNS disorders.
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Page/Page column 25; 36

(2008/06/13)

Anhydrous flouride salts and reagents and methods for their production
Anhydrous organic fluoride salts and reagents prepared by a method comprising the nucleophilic substitution of a fluorinated aromatic or fluorinated unsaturated organic compound with a salt having the formula: [QnM]x+Ax?in an inert polar, aprotic solvent; wherein M is an atom capable of supporting a formal positive charge, the n groups Q are independently varied organic moieties, n is an integer such that the [QnM] carries at least one formal positive charge, x is an integer defining the number of formal positive charge(s), +, carried by the [QnM], A? is an anionic nucleophile capable of substituting for F in the fluorinated compound and F represents fluorine or a radioisotope thereof.
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Page/Page column 3-6

(2008/06/13)

Anhydrous tetrabutylammonium fluoride
Tetrabutylammonium fluoride (TBAF) is prepared at low temperature by nucleophilic aromatic substitution of hexafluorobenzene with tetrabutylammonium cyanide. Adventitious water is scavenged during this synthesis by the generated hexacyanobenzene, which readily adds water under basic conditions. Contrary to expectations, TBAF is stable to Hofmann elimination in polar aprotic solvents under anhydrous conditions. Added hydroxylic solvents are shown to catalyze the decomposition of TBAF and to catalyze proton exchange with DMSO. The synthetic utility of this salt is described briefly. Copyright
Sun, Haoran,DiMagno, Stephen G.
p. 2050 - 2051
(2007/10/03)

Inorganic anionic oxygen-containing α-nucleophiles - Effective acyl group acceptors: Hydroxylamine ranks first among the α-nucleophile series
Comparative analysis of the nucleophilicity of inorganic oxygen-containing α-nucleophiles (hydroxylamine and ClO-, BrO--, HOO--, NH2O-, and F- ions) covering the pKa range from -2 to 13.81 toward 4-nitrophenyl esters (4-nitrophenyl acetate, 4-nitrophenyl p-toluenesulfonate, diethyl 4-nitrophenyl phosphate, ethyl 4-nitrophenyl ethylphosphonate, and 4-nitrophenyl dimethylcarbamate) in water at 25°C (ionic strength μ 1.0, KCl) was performed in terms of the extrathermodynamic Brosted relation. It was found for the first time that hydroxylamine anion ranks first among the series of α-nucleophiles. It is more reactive than HOO- ion with respect to 4-nitrophenyl acetate (by a factor of ～8), 4-nitrophenyl p-toluenesulfonate (by a factor of ～4) and 4-nitrophenyl dimethylcarbamate (by a factor of ～10). The nucleophilicities of HOO- and NH 2O- ions toward diethyl 4-nitrophenyl phosphate and ethyl 4-nitrophenyl ethylphosphonate are comparable. Taking into account that neutral hydroxylamine exhibits an anomalously high reactivity, as compared to not only common organic but also inorganic α-nucleophiles, it may be regarded as a unique α-nucleophile. Both neutral hydroxylamine and its anion as O-nucleophiles ensure high rates of acyl group transfer throughout a wide range of pH.
Simanenko,Popov,Prokop'eva,Karpichev,Savelova,Suprun,Bunton
p. 1286 - 1298
(2007/10/03)

Flash vacuum pyrolysis of stabilised phosphorus ylides. Part 12. Extrusion of Ph3P from sulfonyl ylides and reactivity of the resulting sulfonyl carbenes
Twelve sulfonyl stabilised phosphorus ylides have been prepared and their behaviour upon flash vacuum pyrolysis at 600°C has been examined. Examples with an arylsulfonyl substituent undergo loss of Ph3PO to give intractable products but those with an arylmethylsulfonyl substituent separately lose Ph3P and SO2 to give products consistent with the intermediacy of sulfonyl carbenes. X-Ray structure determinations of one ylide from each series show a more significant P-O non-bonding interaction in the first case, providing some explanation for the different thermal reactivity.
Aitken, R. Alan,Drysdale, Martin J.,Ferguson, George,Lough, Alan J.
p. 875 - 880
(2007/10/03)

Synthesis of p-Toluenesulfonyl Fluoride under Phase-Transfer Conditions. Comparison of Phase-Transfer Catalysts
The example of the synthesis of p-toluenesulfonyl fluoride in acetone from p-toluenesulfonyl chloride and potassium dufluoride under heterogeneous phase-transfer conditions was used to compare the catalytic activity of polyethylene glycols and quaternary ammonium salts. The plot of apparent rate constant on relative catalyst concentration is a peaked curve for ammonium salts and a straight line for polymeric catalysts. At equal relative concentrations, polyethylene glycols are more efficient. The reaction order in polymeric catalyst is close to unity, which corresponds to the concept "one catalyst molecule - one catalytic (coordination) center". The water in acetone undoes the catalytic effect of polyethylene glycol, while in the absence of polyethylene glycol small amounts of water accelerate the reaction.
Krylov,Oleinik
p. 94 - 97
(2007/10/03)

Reaction of p-Toluenesulfonyl Chloride with Metal Fluorides in Bipolar Aprotic Solvents: Phase-Transfer Catalysis of the Reaction with Polyethylene Glycols
Nucleophilic substitution of chlorine by fluorine at the four-coordinate hexavalent sulfur atom under conditions of phase-transfer catalysis in the solid-liquid system is studied with a model reaction of p-toluenesulfonyl chloride with metal fluorides as example. Effective rate costanst are found, and the determining role of crystal lattice is demonstrated. The activation parameters are comparable with those of a homogeneous reaction. The solvent nucleophilically assists the phase transfer and electrophilically assists elimination of the leaving group. Abnormal behavior of nitromethane is caused by its relatively high acidity as compared to other solvents and binding of fluoride ion in the complex F-...HON(O)=CH2. The reaction studied may be described in terms of the Amis electrostatic model with exclusion of nitromethane.
Krylov,Buslaeva
p. 106 - 110
(2007/10/03)

INTERACTION OF p-TOLUENESULFOCHLORIDE WITH METAL FLUORIDES: INTERFACIAL CATALYSIS OF REACTION BY POLYETHYLENE GLYCOLS
Polyethylene glycols with various molecular weights, in bipolar aprotic solvents, can act as effective catalysts for the synthesis of p-toluenesulfofluoride from the corresponding acid chloride by the action of alkali metal fluorides under conditions of interfacial catalysis of the heterogeneous reaction.The activity of the alkali metal fluorides in this process increases from lithium fluoride to cesium fluoride.Potassium bifluoride is the most convenient, because of its ready availability and nonhygroscopicity.It is possible to use N,N-dialkylamides of carboxylic acids as solvents; but even in acetone, interfacial catalysis gives a high yield of the desired product.Polyethylene glycol with an intermediate molecular weight (about 1000) gives the best results.
Krylov, E. N.,Buslaeva, T. A.
p. 884 - 888
(2007/10/02)

Polymer-Supported Potassium Fluoride - A Versatile Fluorination Reagent
The nucleophilic reactivity of potassium fluoride was found to be appreciably enhanced via the despersion of KF onto an inert polymeric support.This crosslinked polystyrene was conveniently synthesized with high surface area and porosity.
Liu, Hanfan,Wang, Ping,Sun, Pengnian
p. 429 - 434
(2007/10/02)

Cross-interaction Constants as a Measure of the Transition-state Structure. Part 1. The Degree of Bond Formation in Nucleophilic Substitution Reactions
The kinetic of seven reaction series in methanol involving halides as leaving groups and aromatic amines as nucleophiles are reported.Analyses of various Hammett ρ values, especially the cross-interaction constants ρXY between substituents X in the nucleophile and Y in the substrate, are used to characterize the transition-state structure for the nucleophilic substitution reactions.The degree of bond formation in the transition state as measured by /ρXY/ indicated that the reactions can be classified into two groups according to the magnitude of the cross-interaction constants; the fluoride series gave larger /ρXY/ values indicating a greater degree of bond formation, under the same reactants condition, compared with other series with relatively good leaving groups, e.g.Cl-, Br-, and -OSO2C6H5.When, however, a non-conjugative intervening group such as CO or CH2 is present between the reaction centre and the benzene ring of a reactant, the cross-interaction constant is reduced by a factor of ca. 2, demonstrating the fall-off of the susceptibility of the reaction centres to substituent changes.
Lee, Ikchoon,Shim, Chang Sub,Chung, Soo Young,Kim, Hyung Yoon,Lee, Hai Whang
p. 1919 - 1924
(2007/10/02)