99433-27-9

Upstream product

• 13329-40-3 4-Iodoacetophenone 
• 5285-74-5 4-tolyl thiocyanate 
• 403-42-9 1-(4-fluorophenyl)ethanone 
• 106-45-6 para-thiocresol 
• 99-90-1 para-bromoacetophenone 
• 624-31-7 4-tolyl iodide 
• 5720-05-8 4-methylphenylboronic acid 
• 149104-90-5 4-acetylphenylboronic acid 
• 99-91-2 para-chloroacetophenone 
• 10486-08-5 sodium p-thiocresolate 
• 100-19-6 (4-nitrophenyl)ethanone 
• 103-19-5 di(p-tolyl) disulfide 

Relevant academic research and scientific papers

Bimetallic BaMoO4 nanoparticles for the C-S cross-coupling of thiols with haloarenes

We disclosed new bimetallic BaMoO4 nanoparticles for the C-S cross-coupling reaction. The C-S cross-coupling reaction of alkyl/aryl thiols with haloarenes was accomplished with high yields. The reaction has good functional group tolerance and selectivity. This is an efficient protocol for synthesizing the building blocks of pharmaceuticals containing C-S bonds. The catalyst is recyclable. The unactivated bromo- and 4-acetyl fluoro-arenes can well couple to afford thioethers in high yields. The reaction is believed to proceed by oxidative addition and reductive elimination.

Generation of Thiyl Radicals from Air-Stable, Odorless Thiophenol Surrogates: Application to Visible-Light-Promoted C-S Cross-Coupling

The synthetic versatility of thiophenols is offset by their airsensitivity and foul odor. It is demonstrated that S-aryl isothiouronium salts can be used as precursors to thiyl radicals, extending the practical benefits of these air-stable, odorless salts from ionic to single electron manifolds. The isothiouronium salts are accessed via Ni-catalyzed crosscoupling of (hetero)aryl iodides and thiourea and are isolated as freeflowing solids following anion exchange. Judicious choice of a redox-innocent counteranion enables use of these convenient thiophenol surrogates in radical processes, as is exemplified by the synthesis of nonsymmetrical diaryl thioethers via light-promoted S-arylation.

Coupling of thiols and aromatic halides promoted by diboron derived super electron donors

We have proven that pyridine-boryl complexes can be used as superelectron donors to promote the coupling of thiols and aromatic halides through a SRN1 mechanism. The reaction is efficient for a broad substrate scope, tolerating heterocycles including pyridines, enolizable or reducible functional groups. The method has been applied to intermediates in drug synthesis as well as interesting functionalized polythioethers through a controlled and consecutive intramolecular electron transfer process.

Electrochemical Thiolation and Borylation of Arylazo Sulfones with Thiols and B2pin2

An efficient electrochemical synthesis approach of various unsymmetrical thioethers and arylboronates has been developed. Bench stable arylazo sulfones were used as radical precursors for carbon-heteroatom bond formation under electrochemical conditions. Moreover, the scalability of this approach was evaluated by performing the electrochemical thiolation and borylation of arylazo sulfones with thiols and B2pin2 on a gram scale. This protocol not only avoided the use of stoichiometric oxidants, metal catalysts, activating agents and even added bases, but also exhibited favorable functional group tolerance. (Figure presented.).

Redox-active benzimidazolium sulfonamides as cationic thiolating reagents for reductive cross-coupling of organic halides

Redox-active benzimidazolium sulfonamides as thiolating reagents have been developed for reductive C-S bond coupling. The IMDN-SO2R reagent provides a bench-stable cationic precursor to generate a portfolio of highly active N-S intermediates, which can be successfully applied in cross-electrophilic coupling with various organic halides. The employment of an electrophilic sulfur source solved the problem of catalyst deactivation and avoided odorous thiols, featuring practical conditions, broad substrate scope, and excellent tolerance.

CuMoO4 Bimetallic Nanoparticles, An Efficient Catalyst for Room Temperature C?S Cross-Coupling of Thiols and Haloarenes

CuII catalyst is less efficient at room temperature for C?S cross-coupling. C?S cross-coupling by CuII catalyst at room temperature is not reported; however, doping of copper with molybdenum metal has been realized here to be more efficient for C?S cross-coupling in comparison to general CuII catalyst. The doped catalyst CuMoO4 nanoparticle is found to be more efficient than copper. The catalyst works under mild conditions without any ligand at room temperature and is recyclable and effective for a wide range of thiols and haloarenes (ArI, ArBr, ArF) from milligram to gram scale. The copper-based bimetallic catalyst is developed and recognized for C?S cross-coupling of haloarenes with alkyl and aryl thiols.

Dechalcogenization of Aryl Dichalcogenides to Synthesize Aryl Chalcogenides via Copper Catalysis

An application for dechalcogenization of aryl dichalcogenides via copper catalysis to synthesize aryl chalcogenides is disclosed. This approach is highlighted by the practical conditions, broad substrate scope, and good functional group tolerance with several sensitive groups such as aldehyde, ketone, ester, amide, cyanide, alkene, nitro, and methylsulfonyl. Furthermore, the robustness of this methodology is depicted by the late-stage modification of estrone and synthesis of vortioxetine. Remarkably, synthesis of more challenging organic materials with large ring tension under milder conditions and synthesis of some halogen contained diaryl sulfides which could not be synthesized using metal-catalyzed coupling reactions of aryl halogen are successfully accomplished with this protocol.

Palladium nanoparticles immobilized on a nano-silica triazine dendritic polymer: a recyclable and sustainable nanoreactor for C-S cross-coupling

Dendrimers are of great interest due to their special structural topology and chemical versatility. Owing to their properties, dendrimers have found practical applications in catalytic processes as efficient nanoreactors. Therefore, we herein report an environmentally attractive strategy and highly efficient route for the synthesis of a wide variety of diaryl sulfides using palladium nanoparticles immobilized on a nano-silica triazine dendritic polymer (Pdnp-nSTDP) as a nanoreactor. In this manner, different diaryl or aryl heteroaryl sulfides and bis(aryl/heteroarylthio)benzene/anthracene/pyridine derivatives were preparedviaC-S cross-coupling reactions of aryl halides with diaryl/diheteroaryl disulfides under thermal conditions and microwave irradiation. The catalyst could be easily recovered and reused several times without any significant loss of its activity.

An efficient protocol for the synthesis of thioethers via iron-catalyzed cross-coupling reaction and its mechanistic investigation

One of the most straightforward methods for the synthesis of diaryl sulfides is the transition metal catalyzed C–S coupling reaction. Herein we report a study on the iron-catalyzed protocol for cross-coupling reaction of aryl halides with thiols. Structurally diverse diaryl sulfides were prepared efficiently by using a catalyst system involving cheap and environment-friendly FeCl3 and non-toxic universal ligand L-proline. The reaction mechanism for the iron-catalyzed C–S coupling reaction was investigated by means of density functional theory (DFT) methods on a model system. The calculations were performed using hybrid PBE1PBE functional in conjugation with the LANL-2DZ basis set. The key step involved in the mechanism is the formation of a reactant complex in which both reactants are electrostatically bound to Fe(III) proline complex catalyst. The elimination of HI occurs with a much lower TS energy (20.0 kcal/mol) than the uncatalyzed reaction (44.7 kcal/mol).

C-S coupling with nitro group as leaving group via simple inorganic salt catalysis

An efficient and practical synthetic protocol to synthesize nonsymmetrical aryl thioethers by nucleophilic aromatic substitution (SNAr) reaction of nitroarenes by thiols with potassium phosphate as the catalyst is described. Various moderate to strong electron-withdrawing functional groups are tolerated by the system to provide thioethers in a good to excellent yields. We also showed that the present method allows access to 3 drug examples in a short reaction time. Finally, mechanistic studies suggest that the reaction may form the classic Meisenheimer complex through a two-step addition-elimination mechanism.