42917-47-5

Upstream product

• 352-34-1 4-fluoro-1-iodobenzene 
• 5285-74-5 4-tolyl thiocyanate 
• 405-31-2 bis(4-fluorophenyl)disulfide 
• 108-88-3 toluene 
• 106-45-6 para-thiocresol 
• 460-00-4 1-Bromo-4-fluorobenzene 
• 352-33-0 1-Chloro-4-fluorobenzene 
• 459-45-0 4-fluorobenzenediazonium tetrafluoroborate 
• 371-42-6 4-Fluorothiophenol 
• 624-31-7 4-tolyl iodide 
• 933-00-6 p-methylbenzenesulfenyl chloride 
• 352-13-6 4-flourophenylmagnesium bromide 
• 824-79-3 sodium 4-methylbenzenesulfinate 
• 1583-56-8 4-fluorobenzoyl fluoride 

Relevant academic research and scientific papers

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.

Paired Electrolysis Enabled Ni-Catalyzed Unconventional Cascade Reductive Thiolation Using Sulfinates

Herein, we have reported a nickel-catalyzed cascade reductive thiolation of aryl halides with sulfinates driven by paired electrolysis. This protocol uses sulfinates as the sulfur source, and various thioethers could be synthesized under mild conditions. By mechanism exploration, we find that a cascade chemical step is allowed on the electrode interface and could alter the reaction pathway in paired electrolysis, whose findings could help the discovery of novel cascade reactions with unique reactivity.

Nickel-Catalyzed Decarbonylative Thioetherification of Acyl Fluorides via C-F Bond Activation

Nickel-catalyzed decarbonylative thioetherification of acyl fluorides has been developed. This transformation allows an array of acyl fluorides to react with thiophenols. A wide range of functional groups are well tolerated and the corresponding sulfides can be obtained in good to excellent yields. This protocol provides the formation of diverse carbon-sulfur bonds via a highly efficient decarbonylative process.

Photoredox Nickel-Catalyzed C-S Cross-Coupling: Mechanism, Kinetics, and Generalization

Photoredox-mediated nickel-catalyzed cross-couplings have evolved as a new effective strategy to forge carbon-heteroatom bonds that are difficult to access with traditional methods. Experimental mechanistic studies are challenging because these reactions involve multiple highly reactive intermediates and perplexing reaction pathways, engendering competing, but unverified, proposals for substrate conversions. Here, we report a comprehensive mechanistic study of photoredox nickel-catalyzed C-S cross-coupling based on time-resolved transient absorption spectroscopy, Stern-Volmer quenching, and quantum yield measurements. We have (i) discovered a self-sustained productive Ni(I/III) cycle leading to a quantum yield φ > 1; (ii) found that pyridinium iodide, formed in situ, serves as the dominant quencher for the excited state photocatalyst and a critical redox mediator to facilitate the formation of the active Ni(I) catalyst; and (iii) observed critical intermediates and determined the rate constants associated with their reactivity. Not only do the findings reveal a complete reaction cycle for C-S cross-coupling, but the mechanistic insights have also allowed for the reaction efficiency to be optimized and the substrate scope to be expanded from aryl iodides to include aryl bromides, thus broadening the applicability of photoredox C-S cross-coupling chemistry.

Concerted aryl-sulfur reductive elimination from PNP pincer-supported Co(iii) and subsequent Co(i)/Co(iii) comproportionation

This report discloses a combined experimental and computational study aimed at understanding C-S reductive elimination from Co(iii) supported by a diarylamido/bis(phosphine) PNP pincer ligand. Divalent (PNP)Co-aryl complexes could be easily oxidized to five-coordinate Co(iii) derivatives, and anion metathesis provided five-coordinate (PNP)Co(Ar)(SAr′) complexes of Co(iii). In contrast to their previously described (POCOP)Co(Ar)(SAr′) analogs, but similarly to the (PNP)Rh(Ar)(SAr′) and (POCOP)Rh(Ar)(SAr′) analogs, (PNP)Co(Ar)(SAr′) undergo C-S reductive elimination with the formation of the desired diarylsulfide product ArSAr′. DFT studies and experimental observations are consistent with a concerted process. However, in contrast to the Rh analogs, the immediate product of such reductive elimination, the unobserved Co(i) complex (PNP)Co, un-dergoes rapid comproportionation with the (PNP)Co(Ar)(SAr′) starting material to give Co(ii) compounds (PNP)Co-Ar and (PNP)Co-SAr′.

DABCO-promoted Diaryl Thioether Formation by Metal-catalyzed Coupling of Sodium Sulfinates and Aryl Iodides

A scalable catalytic synthesis method using commodity chemicals for constructing diaryl thioethers directly from sodium arylsulfinates and iodoarenes is reported in this study. In the presence of CuO or other copper salts such as Cu(OAc)2 as well as palladium catalysts, DABCO demonstrated to be essential to promote this transformation. Various iodoarenes and aryl sulfinates were examined and demonstrated the viability of this method. The mechanistic study showed that radical reactions occurred, while DABCO N-oxide radical can be observed by mass spectrometry. A plausible catalytic mechanism involving DABCO is also discussed, suggesting synergistic reduction of sulfinate by Cu(II) and DABCO is the key step of this coupling reaction. (Figure presented.).

Nickel-Catalyzed C?S Bond Formation via Decarbonylative Thioetherification of Esters, Amides and Intramolecular Recombination Fragment Coupling of Thioesters

A nickel catalyzed cross-coupling protocol for the straightforward C?S bond formation has been developed. Various mercaptans and a wide range of ester and amide substrates bearing various substituents were tolerated in this process which afforded products in good to excellent yields. Furthermore, an intramolecular protocol for the synthesis of thioethers starting from thioesters has been developed. The utility of this protocol has been demonstrated in a new synthetic protocol of benzothiophene.

Iron-catalyzed carbon–sulfur bond formation: Atom-economic construction of thioethers with diaryliodonium salts

Diaryliodonium salts are characterized by poor atom economy with the formation of one equivalent of an iodoarene as waste. We have developed an atom-economic iron-catalyzed protocol for the synthesis of a variety of thioethers with diaryliodonium salts. Not only cyclic diaryliodonium salts but also linear diaryliodonium salts were found to perform well in the reactions.

Visible-light-promoted synthesis of diaryl sulfides under air

A convergent, organocatalytic visible-light-mediated process for the synthesis of diaryl sulfides has been developed. A broad range of aryl thiols reacted with various aryl diazonium salts in the presence of eosin Y under air atmosphere to afford the desired diaryl sulfides in high yields. This novel and environmentally friendly method provides an alternative route to established synthetic approaches.

Room temperature rapid functionalization of E-H bonds (E = O, N, S) via the metal-ligand cooperation mechanism

An arylpalladium PNF-type pincer complex reacts with water and anilines under very mild conditions, providing access to new PNO- and PNN-pincer complexes with concomitant hydrogen transfer to the ligand core. Such a metal-ligand cooperation mode allows for the irreversible double activation of even highly sterically hindered aniline molecules. With thiols, the activation mode depends on the nature of the substituent at the sulfur atom, with thiophenols giving products of C-S elimination.