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Upstream product

• 99-90-1 para-bromoacetophenone 
• 106-54-7 p-Chlorothiophenol 
• 637-87-6 1-Chloro-4-iodobenzene 
• 149104-90-5 4-acetylphenylboronic acid 
• 403-42-9 1-(4-fluorophenyl)ethanone 
• 13329-40-3 4-Iodoacetophenone 

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• 5002-07-3 4'-(4-chlorophenyl)acetophenone 
• 434941-58-9 1-[4-(4-chlorophenylsulfonyl)phenyl]ethanone 

Relevant academic research and scientific papers

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.

Synthesis of diaryl sulfides based on copper-doped OMS-2

We describe a practical protocol for efficiently preparing diaryl sulfide compounds using Cu–OMS-2 as the catalyst. Cu–OMS-2 originates from manganese oxide octahedral molecular sieves modified with copper ions and catalyzes the C–S coupling reaction of substituted thiophenols and aryl halides. This protocol has the advantages of environmental friendliness, simple operation, high yields, good tolerance of functional groups, and the Cu–OMS-2 catalytic material can be recycled several times.

PHOTOCATALYST-FREE, LIGHT-INDUCED CARBON-SULFUR CROSS-COUPLING METHODS

In one aspect, the invention provides a method of promoting a carbon-sulfur bond forming reaction. In certain embodiments, the reaction comprises cross-coupling of a(n) (hetero)aryl halide with a thiol to form the carbon-sulfur bond, wherein the method is promoted by light irradiation in the absence of a photocatalyst. In other embodiments, the cross-coupling reaction can be promoted through visible light irradiation, including sunlight.

Visible-light-promoted C-S cross-coupling via intermolecular charge transfer

Disclosed is a mild, scalable, visible-lightpromoted cross-coupling reaction between thiols and aryl halides for the construction of C-S bonds in the absence of both transition metal and photoredox catalysts. The scope of aryl halides and thiol partners includes over 60 examples and therefore provides an entry point into various aryl thioether building blocks of pharmaceutical interest. Furthermore, to demonstrate its utility, this C-S coupling protocol was applied in drug synthesis and latestage modifications of active pharmaceutical ingredients. UV-vis spectroscopy and time-dependent density functional theory calculations suggest that visible-lightpromoted intermolecular charge transfer within the thiolate-aryl halide electron donor-acceptor complex permits the reactivity in the absence of catalyst.

Magnetic nanoparticle-supported Pd(II)-cryptand 22 complex: An efficient and reusable heterogeneous precatalyst in the Suzuki-Miyaura coupling and the formation of aryl-sulfur bonds in honor and memory of late Prof. Mathias Mertes

In the present work, silica-coated magnetic nanoparticles [Fe3O4@SiO2@C22-Pd(II)] were prepared and characterized by transmission electron microscopy, Fourier transform infrared spectroscopy, vibrating sample magnetometer, energy dispersive X-ray analysis, X-ray photoelectron spectroscopy, elemental analysis, inductively coupled plasma, thermogravimetric and differential thermal analysis. This heterogeneous catalyst is utilized as an effective catalyst for the Suzuki-Miyaura coupling of arylboronic acids and aryl halides, and the cross-coupling reaction of aryl halides and thiols. The catalyst was easily separated by magnetic decantation and the recovered catalyst was reused for five cycles without any significant loss of the catalytic activity.

Copper mediated formation of carbon-heteroatom bonds using organoboron reagents and ultrasound

This report summarizes research efforts focused on copper acetate mediated reactions to form new carbon-heteroatom bonds using organoboron reagents under ultrasound irradiation. The method involves the application of ultrasound irradiation to the Chan-Evans-Lam reaction to achieve O-arylation of phenols, N-arylation of anilines and indoles, and S-arylation of thiols. Ultrasound irradiation was found to decrease reaction times from 72 hours to 4 hours while improving the product yields an average of 20%.1 Representative C-O, C-N, and C-S coupling reactions were successfully scaled-up from the milligram to gram levels while maintaining good product yields offering potential applications in industrial processes.

Tridentate hydroxy-functionalised MCM-41-immobilised copper(I) complex as an efficient and recyclable catalyst for coupling of aryl iodides with thiols

The C-S coupling reaction of aryl iodides with thiols was achieved at 110 °C in DMF/dioxane (V/V, 1:9) in the presence of a tridentate hydroxy-functionalised MCM-41-immobilised copper(I) complex [MCM-41-3OH-CuI] with Cs2CO3 as base to afford a variety of diaryl sulfides in good to excellent yields. The MCM-41-3OH-CuI catalyst can be easily recovered by a simple filtration and reused for at least six times without significant loss of activity.

The copper-nicotinamide complex: Sustainable applications in coupling and cycloaddition reactions

The crystalline copper(ii)-nicotinamide complex, synthesized via simple mixing of copper chloride and nicotinamide solution at room temperature, catalyzes the C-S, C-N bond forming and cycloaddition reactions under a variety of sustainable reaction conditions.

Organic synthesis via magnetic attraction: Benign and sustainable protocols using magnetic nanoferrites

Magnetic nano-catalysts have been prepared using simple modification of iron ferrites. The nm size range of these particles facilitates the catalysis process, as an increased surface area is available for the reaction; the easy separation of the catalysts by an external magnet and their recovery and reuse are additional beneficial attributes. Glutathione bearing nano-ferrites have been used as organocatalysts for the Paal-Knorr reaction and homocoupling of boronic acids. Nanoferrites, post-synthetically modified by ligands, were used to immobilize nanometals (Cu, Pd, Ru, etc.) which enabled the development of efficient, sustainable and green procedures for azide-alkynes-cycloaddition (AAC) reactions, C-S coupling, O-allylation of phenol, Heck-type reactions and hydration of nitriles.

Ligand-free C-S bond formation catalyzed by copper(I) oxide

An efficient ligand-free Cu2O-catalyzed C-S bond-formation reaction was developed. A large number of diaryl sulfides and alkylaryl sulfides could be rapidly assembled using this new reaction protocol. Georg Thieme Verlag Stuttgart.