14092-00-3Relevant articles and documents
The Aryl Sulfide Synthesis via Sulfide Transfer
Huang, Hui,Li, Xiang,Liang, Xinyu,Lin, Qijie,Ma, Bowei,Pei, Shurui,Shi, Qinqin,Wang, Song,Wang, Zhi-Xiang,Wen, Kaikai,Zhang, Bei-Bei,Zhang, Meng
supporting information, (2022/05/14)
Aryl sulfides are in great demands in drugs and materials sciences. To avoid using nucleophilic and noxious thiols, many efforts have been focused on exploring novel sulfide resources. Herein, a reductive Pd-catalyzed, Ni-mediated method to synthesize aryl sulfides via a sulfide transfer reaction is developed. The utility and scope of this reaction is exemplified by various aryl electrophiles and aryl sulfides. Mechanistic studies reveal two competing catalytic cycles of sulfide transfer and aryl transfer in this reaction, where the former one is favored over the later one because of the large energy barrier difference during the transmetalation. Moreover, two important chemicals are late-stage functionalized by this method, exhibiting the potential applications in drugs and materials science.
Electrochemistry Enabled Nickel-Catalyzed Selective C?S Bond Coupling Reaction
Pan, Yi,Wang, Yang,Wang, Yi,Zhang, Feng
supporting information, (2022/02/16)
This work describes an electrochemical enabled nickel-catalyzed chemoselective C?S bond coupling protocol for the production of aryl sulfides and sulfones. By simply switching the nickel catalysts and electrodes, this electrochemical C?S bond coupling has demonstrated excellent redox activity, scalability and sustainability. Furthermore, the mechanism for this electrochemical cross-coupling reaction has been investigated.
Synthesis of Aryl Methyl Sulfides from Arysulfonyl Chlorides with Dimethyl Carbonate as the Solvent and C1 Source
Miao, Ren-Guan,Qi, Xinxin,Wu, Xiao-Feng
supporting information, p. 5219 - 5221 (2021/10/19)
A new procedure for the synthesis of aryl methyl sulfides from dimethyl carbonate (DMC) and arylsulfonyl chlorides has been achieved. In this strategy, DMC plays a dual role as both, C1 building block and green solvent. Arylsulfonyl chlorides served as the sulfur precursors, and a variety of aryl methyl sulfides were obtained in moderate to excellent yields with good functional group tolerance. Additionally, alkylsulfonyl chloride and dibenzyl carbonate are proven to be suitable substrates as well.
Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
supporting information, p. 3723 - 3728 (2021/04/07)
We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
Iridium-Catalyzed ortho-C-H Borylation of Thioanisole Derivatives Using Bipyridine-Type Ligand
Kuninobu, Yoichiro,Naito, Morio,Torigoe, Takeru,Yamanaka, Masahiro,Zeng, Jialin
supporting information, (2020/05/08)
A simple iridium catalytic system was developed that allows for a variety of 2-borylthioanisoles to be easily synthesized via ortho-selective C-H borylation of thioanisole derivatives. Once introduced, boryl and methylthio groups were converted by palladium-catalyzed transformations. Density functional theory calculations revealed that weak interactions, such as hydrogen bonding between the C-H bond of the SCH3 group and the oxygen atom of the boryl ligand, control the ortho-selectivity.
Reduction of CO2 with NaBH4/I2 for the Conversion of Thiophenols to Aryl Methyl Sulfides
Zhang, Bo,Fan, Zhengning,Guo, Zhiqiang,Xi, Chanjuan
, p. 8661 - 8667 (2019/07/03)
We report a tandem reaction to realize reduction of carbon dioxide with thiophenols to generate aryl methyl sulfides under the NaBH4/I2 system with 18-crown-6 as the solvent. Thiophenols bearing electron-donating and electron-withdrawing groups are feasible in this reaction. Controlled experiment results indicate that 18-crown-6 plays a critical role in six-electron reduction of carbon dioxide.
Palladium-Catalyzed Methylation of Aryl, Heteroaryl, and Vinyl Boronate Esters
Haydl, Alexander M.,Hartwig, John F.
supporting information, p. 1337 - 1341 (2019/02/26)
A method for the direct methylation of aryl, heteroaryl, and vinyl boronate esters is reported, involving the reaction of iodomethane with aryl-, heteroaryl-, and vinylboronate esters catalyzed by palladium and PtBu2Me. This transformation occurs with a remarkably broad scope and is suitable for late-stage derivatization of biologically active compounds via the boronate esters. The unique capabilities of this method are demonstrated by combining carbon-boron bond-forming reactions with palladium-catalyzed methylation in a tandem transformation.
Chemoenzymatic Deracemization of Chiral Sulfoxides
Nosek, Vladimír,Mí?ek, Ji?í
supporting information, p. 9849 - 9852 (2018/07/31)
The highly enantioselective enzyme methionine sulfoxide reductase A was combined with an oxaziridine-type oxidant in a biphasic setup for the deracemization of chiral sulfoxides. Remarkably, high ee values were observed with a wide range of substrates, thus providing a practical route for the synthesis of enantiomerically pure sulfoxides.
Palladium-Catalyzed ipso-Borylation of Aryl Sulfides with Diborons
Bhanuchandra,Baralle, Alexandre,Otsuka, Shinya,Nogi, Keisuke,Yorimitsu, Hideki,Osuka, Atsuhiro
supporting information, p. 2966 - 2969 (2016/07/06)
A catalytic Miyaura-type ipso-borylation of aryl sulfides with diboron reagents has been achieved, providing arylboronate esters of synthetic use. The key conditions to transform inherently reluctant C-S bonds into C-B bonds include a palladium-NHC (N-heterocyclic carbene) precatalyst, bis(pinacolato)diboron, and lithium hexamethyldisilazide. This protocol is applicable to a reasonable range of aryl alkyl sulfides. Twofold borylation was observed in the reaction of diphenyl sulfide.
Studies on the synthesis, stability and conformation of 2-sulfonyl-oxetane fragments
Morgan,Hollingsworth,Bull
supporting information, p. 5265 - 5272 (2015/05/13)
2-(Arylsulfonyl)oxetanes have been prepared as new structural motifs of interest for medicinal chemistry. These are designed to fit within fragment space and be suitable for screening in fragment based drug discovery, as well as being suitable for further elaboration or incorporation into drug-like compounds. The oxetane ring is constructed through an efficient C-C bond forming cyclisation which allows the incorporation of a wide range of aryl-sulfonyl groups. Furthermore, biaryl-containing compounds can be accessed through Suzuki-Miyaura coupling from halogenated derivatives. With a number of oxetane containing fragment compounds available, their pH stability was assessed, indicating good half-life values for mono-substituted aryl sulfonyl oxetanes across the pH range (1 to 10). Solubility and metabolic stability data is also reported. Finally, the conformation of the fragments is assessed computationally, providing an indication of possible binding orientations.
