cas 5181-10-2, 4,4'-DICHLORO DIPHENYL SULFIDE

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Palladium Complex Immobilized on Magnetic Nanoparticles Modified with 2-Aminopyridine Ligand: A Novel and Efficient Recoverable Nanocatalyst for C–S and C–Se Coupling Reactions
A novel, versatile and efficient magnetically recoverable palladium nanocatalyst [Fe3O4@SiO2/2-aminopyridine-Pd(II)] was fabricated via the immobilization of palladium(II) complex on the surface of magnetic nanoparticles modified with 2-aminopyridine ligand. The structure of the as-fabricated Fe3O4@SiO2/2-aminopyridine-Pd(II) nanocomposite was characterized by a series of spectroscopic techniques including FT-IR, SEM, TEM, EDX, TGA, XRD, VSM and ICP-OES techniques. The Fe3O4@SiO2/2-aminopyridine-Pd(II) nanocomposite was utilized under mild and eco-friendly conditions in C–S and C–Se coupling reactions to afford a vast variety of diaryl sulfides and diaryl selenides with good to excellent yields. This heterogeneous palladium catalyst can be magnetically separated and reused for at least 7 consecutive trials without any reduction in activity. Graphical Abstract: [Figure not available: see fulltext.]
Lu, Lu,Luo, Jia,Wang, Weiqi,Xu, Xiaoqing,Zhang, Jingzheng
(2022/01/12)

N-bromosuccinimide/HCl mediated reduction of sulfoxides to sulfides
An efficient reduction of sulfoxides to sulfides mediated by N-bromosuccinimide (NBS)/HCl system has been developed. This protocol shows good functional group compatibility as well as broad substrates scope with operational simplicity.
Wang, Jianqiang,Shi, Fangmin,Dai, Dongyan,Xiong, Liping,Yang, Yongpo
supporting information
p. 439 - 443
(2021/02/03)

Scalable electrochemical reduction of sulfoxides to sulfides
A scalable reduction of sulfoxides to sulfides in a sustainable way remains an unmet challenge. This report discloses an electrochemical reduction of sulfoxides on a large scale (>10 g) under mild reaction conditions. Sulfoxides are activated using a substoichiometric amount of the Lewis acid AlCl3, which could be regeneratedviaa combination of inexpensive aluminum anode with chloride anion. This deoxygenation process features a broad substrate scope, including acid-labile substrates and drug molecules.
Kong, Zhenshuo,Pan, Chao,Li, Ming,Wen, Lirong,Guo, Weisi
supporting information
p. 2773 - 2777
(2021/04/21)

Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
A practical and mild method for the switchable synthesis of sulfoxides or sulfonesviaselective oxidation of sulfides using cheapN-fluorobenzenesulfonimide (NFSI) as the oxidant has been developed. These highly chemoselective transformations were simply achieved by varying the NFSI loading with H2O as the green solvent and oxygen source without any additives. The good functional group tolerance makes the strategy valuable.
Cao, Zhong-Yan,Li, Xiaolong,Lu, Hao,Wang, Panpan,Wang, Shengqiang,Xu, Xiaobo,Yan, Leyu,Yang, A-Xiu
supporting information
p. 8691 - 8695
(2021/10/22)

Catalytic dehydrogenation of amines to imines and the in-situ reduction of sulfoxides into sulfides
The catalytic acceptorless dehydrogenation of primary amines into imines and H2 represents one of the most important organic transformations, and the in-situ utilization of the generated H2 for chemical reduction reactions has never
Li, Bo,Liu, Bing,Liu, Xixi,Wang, Wei,Wang, Yanxin,Xiang, Nian,Zhang, Zehui
p. 81 - 88
(2021/07/30)

B2cat2-Mediated Reduction of Sulfoxides to Sulfides
An efficient and operationally simple method for the reduction of sulfoxides to sulfides has been developed using bis(catecholato)diboron (B2cat2) as a reducing agent. The present method accommodates various functional groups which are generally prone to reduction: halides, alkynes, carbonyls, nitriles, and heterocycles are totally intact, and only sulfoxide moieties undergo reduction chemoselectively. Moreover, the remaining diboron and the resulting boron-containing wastes are readily removable, the practicality of this protocol being thus demonstrated.
Takahashi, Fumiya,Nogi, Keisuke,Yorimitsu, Hideki
supporting information
p. 3009 - 3012
(2020/03/25)

Efficient hydrodeoxygenation of sulfoxides into sulfides under mild conditions using heterogeneous cobalt-molybdenum catalysts
Nitrogen-doped carbon-supported cobalt-molybdenum bimetallic catalysts (abbreviated as Co-Mo/NC) are active for the hydrodeoxygenation of sulfoxides to sulfides under mild conditions (25-80 °C and 10 bar H2), which represents the first example of the use of heterogeneous non-noble metal catalysts for this transformation. MoO3 with Lewis acid sites assists the hydrodeoxygenation of sulfoxides into sulfides by hydrogen over cobalt nanoparticles.
Yao, Kaiyue,Yuan, Ziliang,Jin, Shiwei,Chi, Quan,Liu, Bing,Huang, Renjie,Zhang, Zehui
supporting information
p. 39 - 43
(2020/01/13)

Nickel phosphide nanoalloy catalyst for the selective deoxygenation of sulfoxides to sulfides under ambient H2pressure
Exploring novel catalysis by less common, metal-non-metal nanoalloys is of great interest in organic synthesis. We herein report a titanium-dioxide-supported nickel phosphide nanoalloy (nano-Ni2P/TiO2) that exhibits high catalytic activity for the deoxygenation of sulfoxides. nano-Ni2P/TiO2 deoxygenated various sulfoxides to sulfides under 1 bar of H2, representing the first non-noble metal catalyst for sulfoxide deoxygenation under ambient H2 pressure. Spectroscopic analyses revealed that this high activity is due to cooperative catalysis by nano-Ni2P and TiO2. This journal is
Fujita, Shu,Mitsudome, Takato,Mizugaki, Tomoo,Yamaguchi, Sho,Yamasaki, Jun,Yamazoe, Seiji
supporting information
p. 8827 - 8833
(2020/11/23)

Room temperature nickel-catalyzed cross-coupling of aryl-boronic acids with thiophenols: Synthesis of diarylsulfides
A NiCl2/2,2′-bipyridine-catalyzed cross-coupling of thiophenols with arylboronic acids has been developed for the synthesis of symmetric and unsymmetric diarylsulfides at room temperature and in air. This methodology is reliable and offers a mild and easy to operate process for the synthesis of arylthioethers, which are essential compounds with applications in the pharmaceutical and agricultural industries. This method avoids the use of expensive transition metals, such as Pd, Ir or Rh, sophisticated ligands and elevated temperatures. It also has a wide substrate scope (55 examples) and provides products in good to excellent yields (72-93%).
Bhowmik, Amit,Fernandes, Rodney A.,Yadav, Mahesh
p. 2447 - 2458
(2020/04/15)

Magnetically recoverable ferromagnetic 3D hierarchical core-shell Fe3O4@NiO/Co3O4 microspheres as an efficient and ligand-free catalyst for C–S bond formation in poly (ethylene glycol)
A simple and efficient protocol for the synthesis of diaryl thioethers from the reaction of thiourea with a wide variety of aryl halides, including aryl iodides, aryl bromides and aryl chlorides in the presence of 3D hierarchical core-shell Fe3O4@NiO/Co3O4 microspheres has been described. This reaction enables the one-pot synthesis of diaryl thioethers in good to high yields using a non-toxic and magnetically separable catalyst in PEG-400 as an eco-friendly, safe, inexpensive and thermally stable solvent. Magnetic separation and reusability of catalyst for eight times without any significant loss of activity, the use of a commercially available, eco-friendly, cheap and chemically stable sulfur transfer agent and solvent, operational simplicity, environmentally benign, easier work-up procedure and cost efficiency make this method a promising candidate for potential applications in some organic reactions. The catalytic activity of Fe3O4@NiO/Co3O4 as a novel and inexpensive catalyst was investigated in the C-S cross coupling reaction.
Vatandoust Namanloo, Ahad,Akhlaghinia, Batool,Mohammadinezhad, Arezou
p. 446 - 461
(2020/05/13)

Trisaminomethane–cobalt complex supported on Fe3O4 magnetic nanoparticles as an efficient recoverable nanocatalyst for oxidation of sulfides and C–S coupling reactions
In this work, trisaminomethane–cobalt complex immobilized onto the surface of Fe3O4 magnetic nanoparticles was successfully prepared via a simple and inexpensive procedure. The prepared nanocatalyst was considered a robust and clean nanoreactor catalyst for the oxidation and synthesis of sulfides under green conditions. This ecofriendly heterogeneous catalyst was characterized by Fourier transform infrared spectroscopy, X-ray diffractometry, energy-dispersive X-ray spectroscopy, inductively coupled plasma-atomic emission spectroscopy, thermogravimetric analysis, vibrating sample magnetometry, X-ray mapping, scanning electron microscopy, and transmission electron microscopy techniques. Use of green medium, easy separation and workup, excellent reusability of the nanocatalyst, and short reaction time are some outstanding advantages of this method.
Ashraf, Muhammad Aqeel,Liu, Zhenling,Peng, Wan-Xi
(2019/11/16)

Solid-State C-S Coupling in Nickel Organochalcogenide Frameworks as a Route to Hierarchical Structure Transfer to Binary Nanomaterials
In this work, the transfer of the flexible and easily tunable hierarchical structure of nickel organochalcogenides to different binary Ni-based nanomaterials via selective coupling of organic units was developed. We suggested the use of substituted aryl groups in organosulfur ligands (SAr) as traceless structure-inducing units to prepare nanostructured materials. At the first step, it was shown that the slight variation of the type of SAr units and synthetic procedures allowed us to obtain nickel thiolates [Ni(SAr)2]n with diverse morphologies after a self-assembly process in solution. This feature opened the way for the synthesis of different nanomaterials from a single type of precursor using the phenomenon of direct transfer of morphology. This study revealed that various nickel thiolates undergo selective C-S coupling under high-temperature conditions with the formation of highly demanding nanostructured NiS particles and corresponding diaryl sulfides. The in situ oxidation of the formed nickel sulfide in the case of reaction in an air atmosphere provided another type of valuable nanomaterial, nickel oxide. The high selectivity of the transformation allowed the preservation of the initial organochalcogenide morphologies in the resulting products.
Ananikov, Valentine P.,Degtyareva, Evgeniya S.,Galushko, Alexey S.,Kashin, Alexey S.
(2020/08/12)

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.
Cao, Fei,Chen, Jinhong,Deng, Jiedan,Deng, Xuemei,Hou, Yongsheng,Shao, Xiangfeng,Shi, Tao,Wang, Yongqiang,Wang, Zhen,Wu, Lingxi,Yang, Jinru,Yang, Yuhang
p. 2707 - 2712
(2020/03/11)

A Manganese N-Heterocyclic Carbene Catalyst for Reduction of Sulfoxides with Silanes
The first reduction of sulfoxides catalysed by a well-defined manganese complex is described. A variety of sulfoxides are reduced to the corresponding sulfides in high yields using phenylsilane, diphenylsilane, and the economically feasible 1,1,3,3-tetramethyldisiloxane (TMDS) as reducing agents in the presence of a Mn-NHC complex. The reaction is performed under air and without the need of any additive. The involvement of radicals in the catalytic reaction is probed by spin-trap experiments.
Sousa, Sara C. A.,Carrasco, Carlos J.,Pinto, Mara F.,Royo, Beatriz
p. 3839 - 3843
(2019/06/24)

Efficient Chemoselective Reduction of N-Oxides and Sulfoxides Using a Carbon-Supported Molybdenum-Dioxo Catalyst and Alcohol
The chemoselective reduction of a wide range of N-oxides and sulfoxides with alcohols is achieved using a carbon-supported dioxo-molybdenum (Mo@C) catalyst. Of the 10 alcohols screened, benzyl alcohol exhibits the highest reduction efficiency. A variety of N-oxide and both aromatic and aliphatic sulfoxide substrates bearing halogens as well as additional reducible functionalities are efficiently and chemoselectively reduced with benzyl alcohol. Chemoselective N-oxide reduction is effected even in the presence of potentially competing sulfoxide moieties. In addition, the Mo@C catalyst is air- and moisture-stable, and is easily separated from the reaction mixture and then re-subjected to reaction conditions over multiple cycles without significant reactivity or selectivity degradation. The high stability and recyclability of the catalyst, paired with its low toxicity and use of earth-abundant elements makes it an environmentally friendly catalytic system.
Li, Jiaqi,Liu, Shengsi,Lohr, Tracy L.,Marks, Tobin J.
p. 4139 - 4146
(2019/05/27)

Mild and Regioselective Bromination of Phenols with TMSBr
In this work, an unexpected promoting effect of by-product thioether was observed, leading to a mild and regioselective bromination of phenols with TMSBr. This method can tolerate a series of functional groups such as the reactive methoxyl, amide, fluoro, chloro, bromo, aldehyde, ketone and ester groups, and has the potential to recycle the by-product thioether and isolate the desired product under column chromatography-free conditions. Mechanism studies revealed that O–H···S hydrogen bond may be formed between phenol and by-product thioether. Possibly owing to the steric hindrance effect from by-product thioether, the electrophilic bromination at para-position of phenols is much favorable.
Ma, Xiantao,Yu, Jing,Jiang, Mengyuan,Wang, Mengyu,Tang, Lin,Wei, Mengmeng,Zhou, Qiuju
supporting information
p. 4593 - 4596
(2019/07/05)

Aryldithiocarbamates as thiol alternatives in Cu-catalyzed C(aryl)-S coupling reactions using aryldiazonium tetrafluoroborate salts
An efficient method for the synthesis of unsymmetrical diaryl sulfides has been developed by the C-S cross coupling of aryldithiocarbamates and aryldiazonium salts in the presence of CuI-2,2′-bipyridine and Zn. Aryldithiocarbamate compounds have been used here as thiol substitutes. The protocol shows wide substrate scope and good yields of the products.
Dutta, Soumya,Saha, Amit
p. 9360 - 9366
(2019/11/13)

Copper-Catalyzed Three-Component Coupling Reaction of Aryl Iodides, a Disilathiane, and Alkyl Benzoates Leading to a One-Pot Synthesis of Alkyl Aryl Sulfides
A copper-catalyzed three-component coupling reaction of aryl iodides, hexamethyldisilathiane and alkyl benzoates leading to alkyl aryl sulfides has been demonstrated. A disilathiane acted as both a sulfur source and a promoter of the sulfidation, and the alkyl moiety of the alkyl benzoate was effectively introduced on one side of the sulfide. Moreover, we found that the protocol can be expanded to the preparation of ethyl phenyl selenide with diphenyl diselenide.
Sakai, Norio,Maeda, Hiromu,Ogiwara, Yohei
p. 2323 - 2330
(2019/05/24)

Synthesis and nano-Pd catalyzed chemoselective oxidation of symmetrical and unsymmetrical sulfides
A highly chemoselective, efficient and nano-Pd catalyzed protocol for the rapid construction of sulfoxides and sulfones via the oxidation of symmetrical and unsymmetrical sulfides using H2O2 as an oxidant has been developed, respectively. The ready availability of starting materials, easy recovery and reutilization of the catalyst, wide substrate scope, and high yields make this protocol an attractive alternative. The process also involves the metal-free and microwave-promoted synthesis of symmetrical diarylsulfides, and FeCl3-mediated preparation of symmetrical diaryldisulfides through the reaction of arenediazonium tetrafluoroborates with Na2S·9H2O as a sulfur source. In addition, unsymmetrical sulfides were generated via the K2CO3-mediated reaction of arenediazonium tetrafluoroborates with symmetrical disulfides.
Li, Xing,Du, Jia,Zhang, Yongli,Chang, Honghong,Gao, Wenchao,Wei, Wenlong
p. 3048 - 3055
(2019/03/21)

METHOD FOR PRODUCING SULFIDE
PROBLEM TO BE SOLVED: To provide a method that performs a deoxygenation reaction of a sulfoxide using hydrogen as a reductant, and produces a corresponding sulfide. SOLUTION: A method for producing a sulfide is characterized by performing a deoxygenation reaction of a sulfoxide in the presence of a platinum-carrying molybdenum trioxide catalyst in which a platinum particle is immobilized to a molybdenum trioxide, and hydrogen, to obtain a corresponding sulfide. SELECTED DRAWING: None COPYRIGHT: (C)2018,JPO&INPIT
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Paragraph 0075-0077; 0079; 0083

(2018/06/07)

Supported Rhodium Nanoparticles Catalyzed Reduction of Nitroarenes, Arylcarbonyls and Aryl/Benzyl Sulfoxides using Ethanol/Methanol as In Situ Hydrogen Source
A facile reduction reaction of nitroarenes, aryl carbonyls and aryl/benzyl sulfoxides was performed under polystyrene supported rhodium (Rh@PS) catalyzed conditions using ethanol/methanol as in situ hydrogen source. The catalyst Rh@PS played a pivotal role in the oxidation of ethanol/methanol in the presence of traces of aerial oxygen and base to produce hydrogen gas, enough for further reduction reaction. Transmission electron microscopy (TEM) analysis indicated that the average particle size of the Rh nanoparticles (NPs) lies between 2–3 nm; this is responsible for its high catalytic activity. The advantages of Rh@PS are its catalytic activity, easy preparation, recovery, recyclability for several runs, and low metal leaching during reaction. (Figure presented.).
Sharma, Saurabh,Bhattacherjee, Dhananjay,Das, Pralay
supporting information
p. 2131 - 2137
(2018/04/17)

Mild Deoxygenation of Sulfoxides over Plasmonic Molybdenum Oxide Hybrid with Dramatic Activity Enhancement under Visible Light
Harvesting solar light to boost commercially important organic synthesis still remains a challenge. Coupling of conventional noble metal catalysts with plasmonic oxide materials which exhibit intense plasmon absorption in the visible light region is a promising option for efficient solar energy utilization in catalysis. Herein, we for the first time demonstrate that plasmonic hydrogen molybdenum bronze coupled with Pt nanoparticles (Pt/HxMoO3-y) shows a high catalytic performance in the deoxygenation of sulfoxides with 1 atm of H2 at room temperature, with dramatic activity enhancement under visible light irradiation relative to dark conditions. The plasmonic molybdenum oxide hybrids with strong plasmon resonance peaks pinning at around 556 nm are obtained via a facile H-spillover process. Pt/HxMoO3-y hybrid provides excellent selectivity for the deoxygenation of various sulfoxides as well as pyridine N-oxides, in which drastically improved catalytic efficiencies are obtained under the irradiation of visible light. Comprehensive analyses reveal that oxygen vacancies massively introduced via a H-spillover process are the main active sites, and the reversible redox property of Mo atoms and strong plasmonic absorption play key roles in this reaction. The catalytic system works under extremely mild conditions and can boost the reaction by the assistance of visible light, offering an ultimately greener protocol to produce sulfides from sulfoxides. Our findings may open up a new strategy for designing plasmon-based catalytic systems that can harness visible light efficiently.
Kuwahara, Yasutaka,Yoshimura, Yukihiro,Haematsu, Kohei,Yamashita, Hiromi
p. 9203 - 9210
(2018/06/25)

An efficient and recyclable catalytic system for carbon–sulfur coupling reaction and synthesis of 5-substituted 1H-tetrazoles
In this research paper, efficient and economical protocols for the synthesis of symmetrical sulfides and 5-substituted 1H-tetrazoles have been reported using Fe3O4@SBTU@Ni(II) as a heterogeneous and recoverable nanocatalyst. The noticeable features of this catalytic system are: operational simplicity, environmentally benign, easier work-up procedure, green and efficient synthetic entry to excellent yield of products in a high reusability and applicability to various starting materials and, therefore, cost efficiency.
Ghorbani-Choghamarani, Arash,Moradi, Zahra,Azadi, Gouhar
p. 237 - 251
(2018/01/04)

Copper-Catalyzed Production of Diaryl Sulfides Using Aryl Iodides and a Disilathiane
A disilathiane was found to be a novel S1 source for the copper-catalyzed synthesis of diaryl sulfides using aryl iodides. The reaction of iodoarenes and hexamethyldisilathiane, (Me 3 Si) 2 S, in the presence of a catalytic amount of CuI/1,10-phenanthroline provided various types of diaryl sulfides in good yields.
Ogiwara, Yohei,Maeda, Hiromu,Sakai, Norio
supporting information
p. 655 - 657
(2017/11/29)

A novel heterogeneous nanocatalyst: 2-Methoxy-1-phenylethanone functionalized MCM-41 supported Cu(II) complex for C-S coupling of aryl halides with thiourea
An environmentally friendly copper-based catalyst supported on 2-Methoxy-1-phenylethanone functionalized MCM-41 was prepared and characterized by FT-IR, FE-SEM, TEM, XRD, EDX, BET and ICP techniques. The catalyst was applied for the C?S cross-coupling reaction of aryl halides with thiourea. Corresponding products were produced in good yields in aerobic conditions. The catalyst could be recovered and recycled for several times.
Hajipour, Abdol R.,Fakhari, Farzaneh,Nabi Bidhendi, Gholamreza
(2018/02/06)

Preparation and Characterization of Ni-Modified Graphene Oxide Complex as an Efficient Catalyst for the Synthesis of Sulfides via Reaction of Arylhalides with S8 or Thiourea
In this work, complex of Ni-modified graphene oxide was prepared and characterized using FT-IR spectroscopy, SEM, XRD, TGA and ICP-OES techniques. This compound used as an efficient and recoverable catalyst for the C–S coupling reaction using sulfur-transfer reagents (S8 or thiourea). The catalyst was easily separated using a simple filtration and reusable without significant loss of their catalytic efficiency.
Ghafouri-Nejad, Raziyeh,Hajjami, Maryam,Nejat, Razieh
(2018/01/27)

One-pot synthesis method for substituted diphenyl sulfide
The invention relates to a one-pot synthesis method for substituted diphenyl sulfide. The process comprises the following steps: adding thiophenol or diphenyl disulfide and derivatives thereof into asolvent, dropwise adding sulfonyl chloride for a reaction so as to obtain a substituted benzene sulfuryl chloride solution, removing a part of the solvent at a normal pressure, adding Lewis acid, thendropwise adding substituted benzene for a Friedel-Crafts reaction, and carrying out distillation or recrystallization so as to obtain the substituted diphenyl sulfide. The method provided by the invention has the advantages of high safety, simple and convenient raw material recovery, greatly-reducedpurifying difficulty, easily-available raw materials, simple unit operation, low requirements on reaction equipment, mild reaction conditions, high yield and content and applicability to industrial production; and the content of the finally obtained substituted diphenyl sulfide product generally reaches 98% or more.
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Paragraph 0091; 0092; 0093

(2019/01/08)

Method of preparing diarylthioether
The invention discloses a method of preparing diarylthioether. In the method, with diarylsulfoxide as a reaction raw material, the diarylthioether is produced through a reaction in a solvent under the effects of an electrophilic reagent and alkali. In the method, the diarylthioether is produced by reducing the diarylsulfoxide, as a substrate, under mild conditions. The method has mild reaction conditions, high selectivity and yield and simple operations. The products are easy to separate.
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Paragraph 0043-0045

(2017/08/31)

Rapid and efficient deoxygenation of sulfoxides to sulfides with tantalum(V) chloride/sodium iodide system
TaCl5/NaI system converts a wide range of sulfoxides to the corresponding sulfides in high yields with short reaction times, under mild conditions. It is worth mentioning that this protocol is chemoselective and tolerates various functional groups (such as –Br, –Cl, –OCH3, –CHO, and –NO2) and double bond.
Yoo, Byung Woo,Park, Jeeyeon,Shin, Hyo Jong,Yoon, Cheol Min
p. 597 - 603
(2017/10/06)

Mild synthesis of triarylsulfonium salts with arynes
Reactions between arynes and alkyl sulfides have been extensively studied over the past few decades. These reactions commonly end with a dealkylation process and thus deliver thioethers as final products. In contrast, the transformation described furnishes valuable triarylsulfonium salts, in lieu of thioethers, from arynes and diarylsulfides. The reaction features mild conditions and a broad substrate scope. A suite of functional groups such as ketones, esters, nitriles, aryl ethers and aryl halides is tolerated, which can be issues faced by traditional synthetic methods. The practicality of the reaction and its extension to the synthesis of triphenyl selenonium salt are also exhibited herein.
Zhang, Lei,Li, Xiaojin,Sun, Yan,Zhao, Weizhao,Luo, Fan,Huang, Xin,Lin, Lihui,Yang, Ying,Peng, Bo
supporting information
p. 7181 - 7189
(2017/09/07)

B(C 6 F 5) 3 -Catalyzed Reduction of Sulfoxides and Sulfones to Sulfides with Hydrosilanes
B(C 6 F 5) 3 is shown to catalyze the deoxygenation of sulfoxides and sulfones to the corresponding sulfides with Et 3 SiH as the stoichiometric hydride source. While the method is limited in terms of functional group tolerance, it is applicable to the reduction of alkyl/aryl-, aryl/aryl-, and alkyl/alkyl-substituted sulfoxides, including the benzyl/benzyl-substituted derivative. The same protocol converts alkyl/aryl- but not aryl/aryl-substituted sulfones into sulfides.
Porwal, Digvijay,Oestreich, Martin
p. 4698 - 4702
(2017/10/05)

Platinum-supporting hollandite-type vanadium-chromium mixed oxides as efficient heterogeneous catalysts for deoxygenation of sulfoxides under atmospheric H2 pressure
Deoxygenation of sulfoxides to their corresponding sulfides is an important reaction, and the development of efficient heterogeneous catalysts that can utilize molecular hydrogen (H2) as a reducing agent is highly desired. In this study, we successfully developed a new concept in heterogeneous catalysts, platinum-supporting hollandite-type vanadium-chromium mixed oxide catalysts (Pt/V(1-x)Crx-Hol, x: Cr/(V + Cr) molar ratio of the precursor solution), for sulfoxide deoxygenation with H2. Hollandite-type vanadium-chromium mixed oxides (V(1-x)Crx-Hol) that did not support platinum could stoichiometrically deoxygenate methyl phenyl sulfoxide to methyl phenyl sulfide, and the V3+ species in V(1-x)Crx-Hol were oxidized to V4+ after deoxygenation. However, the V4+ species could not be re-reduced with H2. By supporting platinum nanoparticles on V(1-x)Crx-Hol, the re-reduction of the oxidized vanadium species with H2 became possible. Thus, in the presence of Pt/V(1-x)Crx-Hol, catalytic sulfoxide deoxygenation with H2 as the reducing agent can be realized; the deoxygenation occurs on V(1-x)Crx-Hol, and the role of platinum is to re-reduce the oxidized vanadium species with H2. In the presence of Pt/V0.7Cr0.3-Hol, various types of structurally diverse sulfoxides could be selectively converted into their corresponding sulfides under atmospheric H2 pressure (1 atm). In addition, the present system was applicable to the deoxygenation of pyridine N-oxides to their corresponding pyridines. The observed catalysis was truly heterogeneous, and the Pt/V0.7Cr0.3-Hol catalyst could be reused for sulfoxide deoxygenation, although the performance was reduced.
Uematsu, Tsubasa,Ogasawara, Yoshiyuki,Suzuki, Kosuke,Yamaguchi, Kazuya,Mizuno, Noritaka
p. 1912 - 1920
(2017/07/15)

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.
Liu, Li,Qiang, Jian,Bai, Shuhua,Li, Yang,Li, Jian
p. 2365 - 2371
(2017/09/30)

Nickel(II) N-Heterocyclic Carbene Complexes: Versatile Catalysts for C–C, C–S and C–N Coupling Reactions
A variety of NiII complexes with a wide range of electronic and steric properties, bearing picolylimidazolidene ligands (a–g) and Cp (Cp = η5-C5H5; 2a–f) or Cp* (Cp* = η5-C5Me5; 3a, c, g) groups, have been synthesised and characterised by using NMR spectroscopy and single-crystal X-ray crystallography. The complexes have been used as precatalysts for a wide range of catalytic transformations, which most likely involve a Ni0/NiII catalytic cycle. In particular, the new well-defined 2a, 2c, 3a and 3c complexes have demonstrated great efficiency and versatility towards Suzuki–Miyaura coupling reactions, hydroamination of activated olefins and C–S cross-coupling reactions of aryl halides and thiols under mild conditions.
Junquera, Lourdes Benítez,Fernández, Francys E.,Puerta, M. Carmen,Valerga, Pedro
supporting information
p. 2547 - 2556
(2017/05/29)

The first report on the preparation of peptide nanofibers decorated with zirconium oxide nanoparticles applied as versatile catalyst for the amination of aryl halides and synthesis of biaryl and symmetrical sulfides
We have reported the preparation of peptide nanofibers decorated with zirconium oxide nanoparticles for the first time as a novel, non-toxic, inexpensive and recyclable catalyst for the amination of aryl halides and synthesis of biaryl and symmetrical sulfides (via reaction of aryl halides with S8 or 2-thiobarbituric acid as sulfur transfer reagents). The structure of the catalyst was studied by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), atomic absorption spectroscopy (AAS), UV-visible absorption and fluorescence spectroscopy.
Ghorbani-Choghamarani, Arash,Taherinia, Zahra
p. 9414 - 9423
(2017/08/29)

Iron(III) chloride (FeCl3)-catalyzed electrophilic aromatic substitution of chlorobenzene with thionyl chloride (SOCl2) and the accompanying auto-redox in sulfur to give diaryl sulfides (Ar2S): Comparison to catalysis by aluminum chloride (AlCl3)
The Lewis acids MCl3(M = Fe and Al)-catalyzed electrophilic aromatic (ArH) substitution reactions with thionyl chloride (SOCl2) have been shown to give diaryl sulfoxide (Ar2SO) and the reduced diaryl sulfide (Ar2S). Under various selected conditions, the FeCl3-catalyzed reactions of chlorobenzene gave substantially much higher percent yields of Ar2S (Ar = p-ClC6H4) than the reactions catalyzed by AlCl3, showing that FeCl3facilitates the reduction in the sulfur center of SOCl2. A dπ?>pπ*back bond between Fe(III) and the O?S group is thought to be responsible for enhancement of the reduction.
Sun, Xiaoping,Haas, David,Lockhart, Chyress
p. 376 - 380
(2017/02/18)

SINGLE-STEP SYNTHESIS METHOD OF ARYL THIOL AND APPLICATION THEREOF
The present invention relates to a single-step synthesis method of aryl thiol, and more specifically, to a method of synthesizing aryl thiol in a single-step by making aryl halide react with alkane dithiol in the presence of a transition metal catalyst. According to the present invention, a single-step synthesis method using the transition metal catalyst, the synthesis method which is capable of synthesizing aryl thiol from aryl halide at a high yield, can be provided. Various aryl halides may be applied to the synthesis method. Further, the synthesis method has advantages that an easily usable reagent may be used, operations are simple, and reactions can be performed under mild conditions. In addition, the synthesized aryl thiol may be used in the synthesis of advanced molecules such as diaryl sulfides and benzothiophenes.COPYRIGHT KIPO 2017
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Paragraph 0036; 0037; 0083; 0087; 0088; 0091

(2017/09/02)

Photoredox catalysis for oxygenation/deoxygenation between sulfides and sulfoxides by visible-light-responsive polyoxometalates
In this paper, we report the unique visible-light-responsive photoredox catalysis of a divacant lacunary silicotungstate TBA4H4[γ-SiW10O36] (SiW10) for functional group transformations of sulfur-containing compounds; namely, (i) aerobic oxygenation of sulfides to sulfoxides and (ii) deoxygenation of sulfoxides to sulfides. In the presence of suitable additives, such as Ce3+ (electron transfer mediator for oxygenation) and an alcohol (electron and proton donor for deoxygenation), SiW10 shows visible-light-induced charge transfers by using the newly formed highest occupied molecular orbitals derived from the coordinating Ce3+ or alcohol at the vacant site of SiW10. Consequently, oxygenation of sulfides and deoxygenation of sulfoxides can selectively proceed by irradiation with visible light (λ > 400 nm) to afford the corresponding desired products in high yields. The SiW10 photocatalysts can readily be recovered and reused for these transformations. Based on evidence from several experiments, the roles of the additives as well as the reaction mechanisms for these transformations are also discussed.
Suzuki, Kosuke,Jeong, Jinu,Yamaguchi, Kazuya,Mizuno, Noritaka
p. 1014 - 1021
(2016/02/19)

A mild, efficient, and selective procedure for the deoxygenation of sulfoxides with the TaCl5/indium system
The TaCl5/In systemwas found to be a new reagent for reducing a wide range of structurally diverse sulfoxides to the corresponding sulfides with high yields under mild conditions. This protocol is chemoselective and tolerates several functional groups, such as Br, Cl, OCH3, CHO, and CH= CH2.
Yoo, Byung Woo,Lee, Min Kyung,Yoon, Cheol Min
p. 807 - 810
(2016/07/06)

A practical and chemoselective Mo-catalysed sulfoxide reduction protocol using a 3-mercaptopropyl-functionalized silica gel (MPS)
A convenient sulfoxide deoxygenation procedure using a mercaptopropyl-functionalized silica gel as the reducing agent is described. This new protocol based on a heterogeneous reagent displays broad scope and tolerance to reducible functional groups and, from an experimental point of view, enhances previous methods by simplifying the isolation of the sulfide to a simple filtration.
García, Nuria,Fernández-Rodríguez, Manuel A.,García-García, Patricia,Pedrosa, María R.,Arnáiz, Francisco J.,Sanz, Roberto
p. 27083 - 27086
(2016/03/25)

Hydrodeoxygenation of sulfoxides to sulfides by a Pt and MoOx co-loaded TiO2 catalyst
Supported metal nanoparticle catalysts were studied for the hydrodeoxygenation of sulfoxides to sulfides under solvent-free and mild conditions (50-155 °C, 1 or 7 atm H2). The catalytic activity for the model reaction of diphenyl sulfoxide depended on the type of metals, support materials and co-loaded oxides of transition metals (V, Nb, Mo, W, Re). Pt and MoOx co-loaded TiO2 (Pt-MoOx/TiO2) showed the highest activity. Pt-MoOx/TiO2 was reusable after the reaction and was effective for the reduction of various sulfoxides and showed a higher turnover number (TON) than previously reported catalysts. Using Pt-MoOx/TiO2, benzylphenylsulfone was reduced by H2 to give phenylbenzyl sulfide via benzylphenyl sulfoxides, which represented the first example of catalytic conversion of a sulfone to a sulfide by H2. Characterization studies of Pt-MoOx/TiO2 show that the surface of TiO2 is covered by small (or thin layer) Mo oxide species with exposed Mo cations as Lewis acid sites, and 4-5 nm sized Pt metal nanoparticles are supported on the Mo oxide-covered TiO2.
Touchy, Abeda Sultana,Hakim Siddiki,Onodera, Wataru,Kon, Kenichi,Shimizu, Ken-Ichi
p. 2554 - 2560
(2016/05/19)

A simple one-pot and transition metal-free synthesis of diaryl- and dialkyl sulfides via grignard reaction/deoxygenation
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Jung, Hee Seon,Suh, Nuri,Jeon, Heung Bae
supporting information
p. 779 - 782
(2016/05/19)

The reactivity of (Me3Si)3SiH with sulfoxides under free radical conditions
The radical-initiated reaction of (Me3Si)3SiH with a variety of sulfoxides has been investigated. The reactivity varies significantly with the nature of the starting materials. The reactions of diaryl sulfoxides provide the corresponding sulfides in high yields while the related reactions with dialkyl sulfoxides occur more slowly and in moderate yields. The rate constant for the addition of (Me3Si)3Si[rad] radical with dibutyl sulfoxide is in the range 103–104M?1s?1at 80 °C. The reactivity of (Me3Si)3SiH with 1,3-dithiolane derivatives has also been investigated in a comparative study. The 2,2-dimethyl-1,3-dithiolane and the corresponding 1,1-dioxide give very smooth reaction with (Me3Si)3Si[rad] radical attack at sulfur followed by the ring opening at S–CMe2bond and subsequent H-abstraction from the silane in very high yield, whereas the 2,2-dimethyl-1,3-dithiolane-1-oxide behaves quite differently and unexpectedly.
Chatgilialoglu, Chryssostomos,Ferreri, Carla
p. 7764 - 7769
(2016/11/18)

Highly efficient and reusable polystyrene-supported copper(II) catalytic system for S-arylation of potassium thiocyanate by aryl halides in water
An inexpensive, efficient and environmentally friendly copper(II) catalyst supported on polystyrene was successfully synthesized and used as a heterogeneous catalyst for S-arylation of potassium thiocyanate by aryl halides. Also this catalyst could be recovered and reused several times without any noticeable decrease in its catalytic activity. Copyright
Hajipour, Abdol R.,Jajarmi, Saeideh
p. 566 - 570
(2016/07/16)

Diarylation of chalcogen elements using arylboronic acids via copper- or palladium-catalyzed oxidative coupling
Transition metal-catalyzed diarylations of sulfur, selenium and tellurium were achieved using arylboronic acids in air. A copper-catalyzed reaction of sulfur or selenium efficiently yielded numerous symmetrical diaryl sulfides or selenides in the presence of NH4BF4. However, the diarylation of tellurium was not possible using this method, and required a palladium catalyst in the presence of KI and air for the reaction to proceed.
Taniguchi, Nobukazu
p. 5818 - 5823
(2016/08/30)

CuFe2O4 magnetic nanoparticle catalyzed odorless synthesis of sulfides using phenylboronic acid and aryl halides in the presence of S8
CuFe2O4 magnetic nanoparticles were prepared, characterized and used as a magnetically recoverable nanocatalyst for the one-pot synthesis of phenyl aryl/heteroaryl/benzyl sulfides through the cross-coupling reaction of phenylboronic acid with aryl/heteroaryl/benzyl halides in the presence of S8 as a sulfur source in PEG400 as a reusable solvent at 80 °C. Also, the synthesis of symmetrical sulfides from aryl/heteroaryl halides using S8, KF and Cs2CO3 in PEG400 at 120 °C is described. The magnetic nanocatalyst was recycled up to 6 times with little loss of activity.
Amiri, Kamran,Rostami, Amin,Rostami, Abed
p. 7522 - 7528
(2016/09/09)

Aryl diazonium salt and thioacetamide: A catalyst free, efficient blend of an inexpensive arylating agent with "s" surrogate for sulphide synthesis
Novel, facile C-S and S-S bond coupling reactions were achieved by using an aryl diazonium salt as an arylating agent and thioacetamide as a sulphur surrogate. The reaction proceeds smoothly at room temperature without using any transition metal catalyst, ligand or base. Aryl diazonium salts undergo rapid reactions with thioacetamide at room temperature to give the desired products in a much shorter period than the previously reported metal catalysed protocols.
Bhojane, Jeevan Manohar,Sarode, Sachin Ashok,Nagarkar, Jayashreemilind
p. 90046 - 90050
(2016/10/07)

Homolytic Cleavage of a B-B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification
Density functional theory (DFT) investigations revealed that 4-cyanopyridine was capable of homolytically cleaving the B-B σ bond of diborane via the cooperative coordination to the two boron atoms of the diborane to generate pyridine boryl radicals. Our experimental verification provides supportive evidence for this new B-B activation mode. With this novel activation strategy, we have experimentally realized the catalytic reduction of azo-compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones with B2(pin)2 at mild conditions. Breaking good: The diborane B-B bond can be homolytically cleaved via the cooperative catalysis of two 4-cyanopyridine molecules. Using this combination of a diborane (B2(pin)2) and 4-cyanopyridine also allows the catalytic reduction of the N=N double bond of azo-compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones under mild conditions.
Wang, Guoqiang,Zhang, Honglin,Zhao, Jiyang,Li, Wei,Cao, Jia,Zhu, Chengjian,Li, Shuhua
supporting information
p. 5985 - 5989
(2016/05/19)

A facile and efficient procedure for the deoxygenation of sulfoxides to sulfides with the HfCl4/Zn system
Treatment of sulfoxides with the HfCl4/Zn system in acetonitrile at room temperature has been shown to provide the corresponding sulfides in high yields. This new methodology is highly chemoselective, tolerating several functional groups such as-Br,-Cl,-OCH3,-CHO and double bond.
Yoo, Byung Woo,Yu, Bo Ran,Yoon, Cheol Min
p. 358 - 363
(2015/06/22)

Copper(II)-Catalyzed Single-Step Synthesis of Aryl Thiols from Aryl Halides and 1,2-Ethanedithiol
A highly efficient transition metal-catalyzed single-step synthesis of aryl thiols from aryl halides has been developed employing copper(II) catalyst and 1,2-ethanedithiol. The key features are use of readily available reagents, a simple operation, and relatively mild reaction conditions. This new protocol shows a broad substrate scope with excellent functional group compatibility. A variety of aryl thiols are directly prepared from aryl halides in high yields. Furthermore, the aryl thiols are used in situ for the synthesis of more advanced molecules such as diaryl sulfides and benzothiophenes.
Liu, Yajun,Kim, Jihye,Seo, Heesun,Park, Sunghyouk,Chae, Junghyun
supporting information
p. 2205 - 2212
(2015/07/27)