1494-33-3

Upstream product

• 106-45-6 para-thiocresol 
• 459-46-1 4-Fluorobenzyl bromide 
• 106-49-0 p-toluidine 
• 459-56-3 4-fluorobenzylic alcohol 
• 333-45-9 p-fluorobenzyltrimethylammonium bromide 
• 824-79-3 sodium 4-methylbenzenesulfinate 
• 2943-42-2 di(4-methyl)phenylthiosulfonate 
• 51044-11-2 (4-fluorobenzyl)(triphenyl)phosphonium bromide 
• 459-44-9 4-methylbenzenediazonium tetrafluoroborate 
• 624-31-7 4-tolyl iodide 
• 15894-04-9 (4-fluorophenyl)methanethiol 
• 36651-88-4 N-(4-methylphenylazo)pyrrolidine 
• 352-11-4 1-chloromethyl-4-fluorobenzene 
• 10486-08-5 sodium p-thiocresolate 

Downstream Products

• 234080-54-7 C₂₀H₂₄BrFS 
• 1512843-93-4 (E)-methyl 3-(5-fluoro-2-(p-tolylsulfinylmethyl)phenyl)acrylate 
• 1494-29-7 1-fluoro-4-(4-tolylsulfonylmethyl)benzene 
• 1426-53-5 1-fluoro-4-((p-tolylsulfinyl)methyl)benzene 

Relevant academic research and scientific papers

Synthesis of benzyl thioether derivatives via N-heterocyclic carbene palladium(II)-catalyzed cross coupling of benzylammonium salts with thiophenols

A new route to benzyl thioether derivatives has been developed via the N-heterocyclic carbene palladium(II)-catalyzed cross coupling of benzylammonium salts with thiophenols. Under the optimal conditions, different benzylammonium salts could be well toler

Unusual Application for Phosphonium Salts and Phosphoranes: Synthesis of Chalcogenides

A novel strategy for the synthesis of sulfides and selenides from phosphonium salts and thio- or selenesulfonates, commercially available compounds, is described. When phosphoranes were used in the reaction, different products were obtained. The methodology does not require the use of metals, reactive species, or anhydrous conditions to be performed.

Rhodium-Catalyzed C-H/C-H Cross Coupling of Benzylthioethers or Benzylamines with Thiophenes Enabled by Flexible Directing Groups

Reported herein is an efficient synthetic protocol to ortho-functionalized 2-aryl thiophenes via Rh(III)-catalyzed C-H/C-H cross coupling of benzylthioethers or benzylamines with thiophenes. Both ortho- and meta-substituted benzylthioethers give monoheteroarylated products, while ortho-unhindered substrates mainly provide diheteroarylated benzylthioethers. The C-H/C-H cross coupling of benzylamines with thiophenes exclusively generates diheteroarylated benzaldehydes. Mechanistic investigation discloses a three-step tandem process involving the ortho-C-H diheteroarylation of benzylamine, the oxidation of benzylamine to imine, and the hydrolysis of imine to aldehyde.

Efficient dehydrative alkylation of thiols with alcohols catalyzed by alkyl halides

Alcohols can be efficiently converted into the useful thioethers by a transition metal- and base-free dehydrative S-alkylation reaction with thiols or disulfides by employing alkyl halides as the effective catalyst. This simple and efficient method is a green and practical way for the preparation of thioethers, as it tolerates a wide range of substrates such as aryl and alkyl thiols, as well as benzylic, allylic, secondary, tertiary, and even the less reactive aliphatic alcohols.

Aryl alkyl, aryl aryl thioether compound and its synthesis method

The invention discloses a synthesis method of an aryl-alkyl and aryl-aryl thioether compound represented by a formula (III). According to the synthesis method, aryl tetrafluoroboric acid diazonium salt is taken as a reaction raw material in a reaction solvent, aryl and alkyl thiosulfate is taken as a sulfurizing agent, and the materials react under the catalysis action of visible light and a photosensitive agent to obtain the aryl-alkyl and aryl-aryl thioether compound. According to the synthesis method, the raw materials are easy to obtain and are cheap, the reaction operation is simple, the reaction condition is mild and environment-friendly, the yield is higher, the functional group tolerance is excellent, later modification of drugs is successfully realized, and an efficient C-S bond construction method is provided for medicinal chemistry and biological orthogonal chemistry research.

Photoredox Mediated Nickel Catalyzed Cross-Coupling of Thiols with Aryl and Heteroaryl Iodides via Thiyl Radicals

Ni-catalyzed cross-couplings of aryl, benzyl, and alkyl thiols with aryl and heteroaryl iodides were accomplished in the presence of an Ir-photoredox catalyst. Highly chemoselective C-S cross-coupling was achieved versus competitive C-O and C-N cross-couplings. This C-S cross-coupling method exhibits remarkable functional group tolerance, and the reactions can be carried out in the presence of molecular oxygen. Mechanistic investigations indicated that the reaction proceeded through transient Ni(I)-species and thiyl radicals. Distinct from nickel-catalyzed cross-coupling reactions involving carbon-centered radicals, control experiments and spectroscopic studies suggest that this C-S cross-coupling reaction does not involve a Ni(0)-species.

Mechanistic Study of a Photocatalyzed C-S Bond Formation Involving Alkyl/Aryl Thiosulfate

This study presents thioether construction involving alkyl/aryl thiosulfates and diazonium salt catalyzed by visible-light-excited [Ru(bpy)3Cl2] at room temperature in 44-86 % yield. Electron paramagnetic resonance studies found that thiosulfate radical formation was promoted by K2CO3. Conversely, radicals generated from BnSH or BnSSBn (Bn=benzyl) were clearly suppressed, demonstrating the special property of thiosulfate in this system. Transient absorption spectra confirmed the electron-transfer process between [Ru(bpy)3Cl2] and 4-MeO-phenyl diazonium salt, which occurred with a rate constant of 1.69×109 M-1 s-1. The corresponding radical trapping product was confirmed by X-ray diffraction. The full reaction mechanism was determined together with emission quenching data. Furthermore, this system efficiently avoided the over-oxidation of sulfide caused by H2O in the photoexcited system containing Ru2+. Both aryl and heteroaryl diazonium salts with various electronic properties were investigated for synthetic compatibility. Both alkyl- and aryl-substituted thiosulfates could be used as substrates. Notably, pharmaceutical derivatives afforded late-stage sulfuration smoothly under mild conditions.

Sulfide synthesis through copper-catalyzed C-S bond formation under biomolecule-compatible conditions

We report here an efficient and mild method for constructing C-S bonds. The reactions were carried out with Na2S2O3 as a sulfurating reagent, CuSO4 as a catalyst, and water as solvent without any surfactant. The products were achieved in moderate to excellent yields at room temperature under air. Notably, this reaction is compatible with various biomolecules including amino acids, oligosaccharides, nucleosides, proteins, and cell lysates. This journal is

Palladium(II)-catalyzed ortho -olefination of arenes applying sulfoxides as remote directing groups

A novel palladium-catalyzed ortho-C(sp2)-H olefination protocol has been developed by the use of sulfoxide as the directing group. Importantly, relatively remote coordination can be accessed to achieve the ortho olefination of benzyl, 2-arylethyl, and 3-arylpropenyl sulfoxide substrates, and the olefinated sulfoxide can be easily transformed to other functionalities.

Synthesis of sulfur-bridged polycycles via Pd-catalyzed dehydrogenative cyclization

A general approach to sulfur-bridged polycycles by palladium-catalyzed double C(sp2)-H bond oxidative cyclization is presented. This protocol afforded diverse sulfur-bridged five-, six-, and seven-membered polycycles in moderate to good yields with a tolerance for a wide variety of functional groups. A sulfide-bridged six-membered pyrene-thienoacene compound was synthesized readily using this method, and excellent performance for photoluminescence quantum yield was observed.