498-83-9

Upstream product

• 98-58-8 4-bromobenzenesulfonyl chloride 
• 108-86-1 bromobenzene 
• 1156-18-9 di(4-bromobenzenesulfonyl)amine 
• 106-53-6 para-bromobenzenethiol 
• 701-34-8 4-bromo-benzenesulfonic acid amide 
• 673-40-5 4-bromobenzenediazonium tetrafluoroborate 
• 14204-32-1 N-((4-bromophenol)thio)phthalimide 
• 622-88-8 4-bromophenylhydrazine hydrochloride 
• 2564-83-2 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical 
• 3376-24-7 N-tert-butyl-α-phenylnitrone 
• 5467-74-3 4-Bromophenylboronic acid 
• 848649-38-7 4-bromobenzenesulfonic acid pentafluorophenyl ester 
• 34176-08-4 sodium 4-bromobenzenesulfinate 

Downstream Products

• 435309-95-8 N-(BOC)-(D,L)-3-(4'-bromophenyl)sulfonyl-nipecotic acid, ethyl ester 
• 6647-76-3 p-bromobenzenesulfonyl azide 
• 16236-44-5 2-Methoxy-1,1′:4′,1′′-terphenyl 
• 312-20-9 1-bromo-4-(trifluoromethylsulfonyl)benzene 

Relevant academic research and scientific papers

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.

Method for preparing aryl sulfonyl fluoride by using aryl hydrazine hydrochloride as raw material

The invention relates to a method for preparing aryl sulfonyl fluoride by using aryl hydrazine hydrochloride as a raw material. According to the method, aryl sulfonyl fluoride is synthesized by taking the aryl hydrazine hydrochloride as a raw material and adding a sulfur dioxide source and a fluorination reagent under the conditions of copper salt catalysis and alkali promotion through a strategy of insertion and fluorination of free radical sulfur dioxide. Compared with the prior art, the aryl sulfonyl fluoride is synthesized under the oxidation condition, and the influence of air on the reaction is not obvious in an experiment; and the reaction synthesis method is simple, good in selectivity, excellent in yield, mild in reaction condition, short in reaction time and universal to various aryl hydrazine hydrochloride substrates, and the method provides a new thought for synthesis of aryl sulfonyl fluoride.

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.

Unbalanced-Ion-Pair-Catalyzed Nucleophilic Fluorination Using Potassium Fluoride

An unbalanced ion pair promoter (e.g., tetrabutylammonium sulfate), consisting of a bulky and charge-delocalized cation and a small and charge-localized anion, greatly accelerates nucleophilic fluorinations using easy handling KF. We also successfully converted an inexpensive and commercially available ion-exchange resin to the polymer-supported ion pair promoter (A26–SO42–), which could be reused after filtration. Moreover, A26–SO42– can be used in continuous flow conditions. In our conditions, water is well-tolerated.

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).

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.

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.

Arylsulfonyl fluoride boronic acids: Preparation and coupling reactivity

We report the efficient and practical syntheses of ortho-, meta, and para-sulfonyl fluoride substituted benzene boronic acids. The syntheses of the para- and meta-isomers commence with the appropriate bromo-substituted benzenesulfonyl chlorides, and the o

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.

Copper-Catalyzed Synthesis of Activated Sulfonate Esters from Boronic Acids, DABSO, and Pentafluorophenol

The synthesis of pentafluorophenyl (PFP) sulfonate esters based on the Pd-catalyzed sulfination of aryl and heteroaryl boronic acids is reported. The sulfinate intermediates are converted in situ to the corresponding sulfonate esters using a copper-catalyzed oxidative process, providing a broad range of PFP esters in good yields.