- Coupling of thiols and aromatic halides promoted by diboron derived super electron donors
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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.
- Franco, Mario,Vargas, Emily L.,Tortosa, Mariola,Cid
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supporting information
p. 11653 - 11656
(2021/11/12)
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- Paired Electrolysis Enabled Ni-Catalyzed Unconventional Cascade Reductive Thiolation Using Sulfinates
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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.
- Kang, Jun-Chen,Li, Zi-Hao,Chen, Chao,Dong, Li-Kun,Zhang, Shu-Yu
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supporting information
p. 15326 - 15334
(2021/10/25)
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- Nickel-Catalyzed Decarbonylative Thioetherification of Acyl Fluorides via C-F Bond Activation
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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.
- You, Jingwen,Chen, Qiang,Nishihara, Yasushi
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supporting information
p. 3045 - 3050
(2021/05/31)
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- Method for preparing 4-benzoyl-4'-methyl-diphenyl sulfide
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The invention relates to a preparation method of a photoinitiator 4-benzoyl-4'-methyl-diphenyl sulfide, in particular to a method for preparing phenyl sulfenyl chloride by taking benzene, sulfur monochloride and chlorine as raw materials, then carrying out thioetherification reaction with toluene, and finally carrying out acylation reaction with benzoyl chloride. According to the preparation method of the 4-benzoyl-4'-methyl-diphenyl sulfide provided by the invention, the shortcomings of an existing method are avoided, the used raw materials are cheap and easy to obtain, the reaction conditions are mild, the method is easy to operate, the yield is high, the cost is low, and the method is suitable for industrial stable production.
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Paragraph 0028; 0035; 0036; 0037; 0040; 0041; 0042; 0045
(2019/05/22)
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- Nickel-Catalyzed Thiolation of Aryl Halides and Heteroaryl Halides through Electrochemistry
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Transition-metal-catalyzed coupling reactions are useful tools for synthesizing aryl sulfur compounds. However, conventional transition-metal-catalyzed thiolation of aryl bromides and chlorides typically requires the use of strong base under elevated reaction temperature. Herein, we report the first examples of nickel-catalyzed electrochemical thiolation of aryl bromides and chlorides in the absence of an external base at room temperature using undivided electrochemical cells.
- Liu, Dong,Ma, Hong-Xing,Fang, Ping,Mei, Tian-Sheng
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supporting information
p. 5033 - 5037
(2019/03/13)
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- Nickel-Catalyzed C?S Bond Formation via Decarbonylative Thioetherification of Esters, Amides and Intramolecular Recombination Fragment Coupling of Thioesters
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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.
- Lee, Shao-Chi,Liao, Hsuan-Hung,Chatupheeraphat, Adisak,Rueping, Magnus
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supporting information
p. 3608 - 3612
(2018/03/13)
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- PHOTOCATALYST-FREE, LIGHT-INDUCED CARBON-SULFUR CROSS-COUPLING METHODS
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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.
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Paragraph 0099; 0153; 0154
(2019/01/10)
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- Visible-light-promoted C-S cross-coupling via intermolecular charge transfer
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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.
- Liu, Bin,Lim, Chern-Hooi,Miyake, Garret M.
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supporting information
p. 13616 - 13619
(2017/11/06)
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- Rhodium-Catalyzed Synthesis of Unsymmetric Di(heteroaryl) Sulfides Using Heteroaryl Ethers and S-Heteroaryl Thioesters via Heteroarylthio Exchange
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Unsymmetric di(heteroaryl) sulfides were synthesized by a rhodium-catalyzed heteroarylthio exchange reaction of heteroaryl aryl ethers and S-(heteroaryl) thioesters. The reaction has broad applicability, giving diverse unsymmetric di(heteroaryl) sulfides containing five- and six-membered heteroarenes. No base is required in this reaction, which has been developed by the judicious design of organic substrates.
- Arisawa, Mieko,Tazawa, Takeru,Tanii, Saori,Horiuchi, Kiyofumi,Yamaguchi, Masahiko
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p. 804 - 810
(2017/04/26)
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- Facile aromatic nucleophilic substitution (SNAr) reactions in ionic liquids: An electrophile-nucleophile dual activation by [Omim]Br for the reaction
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A facile aromatic nucleophilic substitution (SNAr) reaction in recyclable [Omim]Br under relatively mild conditions has been described. An electrophile-nucleophile dual activation by [Omim]Br is also discovered based on control experiments, 1H NMR and IR spectroscopies. This chemistry provides an efficient and metal-free approach for the generation of Caryl-X (XS, N, O) bonds, many of which are significant synthetic intermediates or drugs, making this methodology attractive to both synthetic and medicinal chemistry.
- Zhang, Xiao,Lu, Guo-Ping,Cai, Chun
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p. 5580 - 5585
(2016/10/21)
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