- Metal-free sulfonylation of arenes with: N -fluorobenzenesulfonimide via cleavage of S-N bonds: expeditious synthesis of diarylsulfones
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A novel metal-free sulfonylation of arenes with N-fluorobenzenesulfonimide (NFSI) toward the synthesis of diarylsulfones has been developed. The reaction represents a rare example of sulfonylation reaction using NFSI as an efficient sulfonyl donor and the first example of acid-mediated sulfonylation of unactivated arenes with NFSI via selective cleavage of S-N bonds. This protocol provides a concise approach for the construction of pharmaceutically and biologically important diarylsulfones. Applications in the functionalization of natural products (e.g., β-estradiol) and in the synthesis of a key intermediate to an inhibitor of farnesyl-protein transferase, as well as in the gram-scale synthesis of the EPAC2 antagonist, are demonstrated. This journal is
- Feng, Yueji,Tuo, Yanyan,Zhang, Xiaohui,Zheng, Qing-Zhong
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supporting information
p. 768 - 772
(2022/02/03)
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- Sulfonylation of Aryl Halides by Visible Light/Copper Catalysis
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An efficient visible-light-assisted, copper-catalyzed sulfonylation of aryl halides with sulfinates is reported. In our protocol, a single ligand CuI photocatalyst formed in situ was used in the photocatalytic transformation. Diverse organosulfones were obtained in moderate to good yields. This strategy demonstrates a promising approach toward the synthesis of diverse and useful organosulfones.
- Cui, Wenwen,Jiang, Min,Lv, Jian,Song, Xiuyan,Sun, Kai,Xu, Guiyun,Yan, Qiuli,Yang, Daoshan
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supporting information
p. 3663 - 3668
(2021/05/31)
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- Selective synthesis of sulfoxides and sulfonesviacontrollable oxidation of sulfides withN-fluorobenzenesulfonimide
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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
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supporting information
p. 8691 - 8695
(2021/10/22)
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- Synergistic cooperative effect of CF3SO2Na and bis(2-butoxyethyl)ether towards selective oxygenation of sulfides with molecular oxygen under visible-light irradiation
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A safe, practical and eco-friendly method for the switchable synthesis of sulfoxides and sulfones through visible-light-initiated oxygenation of sulfides at ambient temperature under transition-metal-, additives-free and minimal solvent conditions. The synergistic catalytic efforts between CF3SO2Na and 2-butoxyethyl ether represents the key promoting factor for the reaction. This journal is
- Liu, Kai-Jian,Wang, Zheng,Lu, Ling-Hui,Chen, Jin-Yang,Zeng, Fei,Lin, Ying-Wu,Cao, Zhong,Yu, Xianyong,He, Wei-Min
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supporting information
p. 496 - 500
(2021/01/28)
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- Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones
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A practical and eco-friendly method for the controllable aerobic oxygenation of sulfides by electrochemical catalysis was developed. The switchable preparation of sulfoxides and sulfones was effectively controlled by reaction time, in which both molecular oxygen and water can be used as the oxygen source under catalyst and external oxidant-free conditions. The electrochemical protocol features a broad substrate scope and excellent site selectivity and is successfully applied to the modification of some sulfide-containing pharmaceuticals and their derivatives. This journal is
- Li, Jin-Heng,Li, Yang,Sun, Qing,Xue, Qi,Zhang, Ting-Ting
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supporting information
p. 10314 - 10318
(2021/12/17)
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- Synthesis, spectra (FT-IR, NMR) investigations, DFT, FMO, MEP, NBO analysis and catalytic activity of MoO2(VI) complex with ONO tridentate hydrazone Schiff base ligand
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A new dioxomolybdenum(VI) complex has been successfully prepared by the reaction of an ONO donor Schiff base, derived by condensing 4-amino-2-hydroxybenzohydrazide and 3-ethoxysalicylaldehyde, with MoO2(acac)2. The structures of synthesized products were explored spectroscopically through FT-IR, 1H & 13C NMR and by elemental composition (CHN) through combustion analysis. The tridentate Schiff base ligand is bonded to the central metal through its deprotonated enolic and phenolic oxygen atoms and by the nitrogen of the azomethine group. The interpretation of the data obtained through diffraction analysis validates the distorted octahedral geometry for the prepared metal complex. Furthermore, the catalytic potential of the molybdenum complex was explored for the selective oxidation of the aryl and alkyl sulfides to the corresponding sulfones in the presence of 30% aqueous H2O2 in ethanol. The main edge of the present catalytic work is the accomplishment of reaction in a short period of time, high percentage yield and easy work-up procedure.
- Behjatmanesh-Ardakani, Reza,Fallah-Mehrjardi, Mehdi,Kargar, Hadi,Munawar, Khurram Shahzad
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- Visible-light-driven electron donor-acceptor complex induced sulfonylation of diazonium salts with sulfinates
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This work reports an efficient sulfonylation reaction enabled by a visible-light-induced radical coupling reaction between phenyl/heterocyclic diazonium salts and sulfinates. Mechanistic experiments disclosed the formation of a versatile electron donor-acceptor (EDA) complex. This transformation is characterized by an easy operational procedure under mild conditions which avoids transition metals, ligands, catalysts, and oxidants.
- Cheng, Lan,Guo, Jianbo,Li, Yufei,Liang, Xin,Wang, Qingmin,Xia, Qing,Zhang, Pei,Zhang, Weihua
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supporting information
p. 8865 - 8870
(2021/11/30)
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- A Copper(I)-Catalyzed Sulfonylative Hiyama Cross-Coupling
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An air-tolerant Cu-catalyzed sulfonylative Hiyama cross-coupling reaction enabling the formation of diaryl sulfones is described. Starting from aryl silanes, DABSO and aryliodides, the reaction tolerates a large variety of polar functional groups (amines, ketones, esters, aldehydes). Control experiments coupled with DFT calculations shed light on the mechanism, characterized by the formation of a Cu(I)-sulfinate intermediate via fast insertion of a SO2 molecule.
- Adenot, Aurélien,Anthore-Dalion, Lucile,Nicolas, Emmanuel,Berthet, Jean-Claude,Thuéry, Pierre,Cantat, Thibault
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supporting information
p. 18047 - 18053
(2021/11/16)
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- Sulfonylation of Bismuth Reagents with Sulfinates or SO2through BiIII/BiV Intermediates
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Studies to explore the catalytic activities of main-group elements are attractive. We report here our study of sulfonylation of bismuth reagents with sulfinates or SO2 surrogates. Under oxidative conditions, triarylbismuthines and sulfinates were transformed into diaryl sulfones. A transition-metal-like two-electron redox process at the Bi center was achieved in this reaction. Sulfur dioxide generated in situ can also replace sulfinates to deliver the corresponding symmetric diaryl sulfones. A rational mechanism for this reaction was also proposed that involves a Bi(III)-Bi(V) manifold.
- Zhao, Fengqian,Wu, Xiao-Feng
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supporting information
p. 2400 - 2404
(2021/07/28)
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- Catalyst-free arylation of sulfonamidesviavisible light-mediated deamination
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A novel arylation of sulfonamides with boronic acids to afford numerous diaryl sulfonesviaa visible light-mediated N-S bond cleavage other than the typical transition-metal-catalyzed C(O)-N bond activation is described. This methodology, which represents the first catalyst-free protocol for the sulfonylation of boronic acids, is characterized by its simple reaction conditions, good functional group tolerance and high efficiency. Several successful examples for the late-stage functionalization of diverse sulfonamides indicate the high potential utility of this method in pharmaceutical science and organic synthesis.
- Ding, Hao,Ding, Qiuping,Du, Xian,Li, Yi-Hui,Liu, Bing-Zhe,Lu, Shi-Man,Luo, Yong,Qi, Wan-Ying,Xu, Xiao-Hong,Xue, Can,Yuan, Han,Zhen, Jing-Song
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p. 9556 - 9560
(2021/07/25)
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- Method for synthesizing sulfone compounds under photocatalysis condition
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The invention belongs to the technical field of compound preparation, and particularly relates to a method for synthesizing sulfone compounds under a photocatalysis condition. Aromatic hydrazine and sulfinate are used as raw materials, and under the action of alkali and a solvent, a sulfone compound is generated through reaction under the condition of air or oxygen under the illumination of visible light. According to the method disclosed by the invention, aryl hydrazine is used as an arylation reagent, polyacid salt is used as a catalyst or an organic photosensitizer is used as a catalyst, and the sulfones compound can be efficiently synthesized by coupling with sulfinate under the condition of room temperature through visible light irradiation. The method has good substrate universalityand relatively mild reaction conditions, is not only a substitute for synthesizing sulfone compounds by coupling from simple substrates reported at present, but also broadens the new application of the polyacid salt in the field of photocatalysis.
- -
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Paragraph 0114-0118
(2021/03/31)
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- Heterogeneous copper-catalyzed synthesis of diaryl sulfones
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A carbon-supported copper nanoparticle (Cu-NP) with high catalytic activity for the synthesis of diaryl sulfones is reported. For the first time, this Cu-NP is proved to be able to effectively promote the reaction of arylboronic acids and arylsulfonyl hydrazides to generate diaryl sulfones at room temperature. The reaction shows excellent substrate universality, and substrates with different substituents can undergo the reaction smoothly, leading to the desired products in good yields. The Cu-NP is found to be made of low valence Cu based on XRD. Hence, the reaction catalyzed by the Cu-NP is believed to involve a Cu-mediated organometallic cycle.
- Gong, Xinchi,Qu, Lingling,Shen, Zhengqi,Wang, Ganghu,Zhu, Chunyin
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supporting information
p. 10662 - 10668
(2021/12/27)
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- Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions
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The development of eco-friendly and switchable catalytic systems for the conversion of a sole raw-material into distinct high-value products is a particularly attractive concept and a daunting synthetic challenge. In the present work, the first example of efficient and selective oxidation of sulfides to sulfones and sulfoxides using molecular oxygen under clean conditions was established.
- Liu, Kai-Jian,Deng, Ji-Hui,Yang, Jie,Gong, Shao-Feng,Lin, Ying-Wu,He, Jun-Yi,Cao, Zhong,He, Wei-Min
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supporting information
p. 433 - 438
(2020/02/13)
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- Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones
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The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted. The sulfoxides and sulfones could be obtained by simply switching the reaction media, i.e., bis(2-butoxyethyl)ether (BBE) or poly(ethylene glycol)dimethyl ether (PEGDME). The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents. This strategy represents an economic and eco-friendly method that could find potential applications.
- Tang, Lili,Du, Kejie,Yu, Bing,He, Liangnian
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p. 2991 - 2992
(2020/03/24)
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- A biradical oxo-molybdenum complex containing semiquinone and: o -aminophenol benzoxazole-based ligands
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We report a new mononuclear molybdenum(iv) complex, MoOLBISLSQ, in which LSQ (2,4-di-tert-butyl o-semibenzoquinone ligand) has been prepared from the reaction of the o-iminosemibenzoquinone form of a tridentate non-innocent benzoxazole ligand, LBIS, and MoO2(acac)2. The complex was characterized by X-ray crystallography, elemental analysis, IR and UV-vis spectroscopy and magnetic susceptibility measurements. The crystal structure of MoOLBISLSQ revealed a distorted octahedral geometry around the metal centre, surrounded by one O and two N atoms of LBIS and two O atoms of LSQ. The effective magnetic moment (μeff) of MoOLBISLSQ decreased from 2.36 to 0.2 μB in the temperature range of 290 to 2 K, indicating a singlet ground state caused by antiferromagnetic coupling between the metal and ligand centred unpaired electrons. Also, the latter led to the EPR silence of the complex. Cyclic voltammetry (CV) studies indicate both ligand and metal-centered redox processes. MoOLBISLSQ was applied as a catalyst for the oxidative cleavage of cyclohexene to adipic acid and selective oxidation of sulfides to sulfones with aqueous hydrogen peroxide. This journal is
- Galindo, Agustín,Jagli?i?, Zvonko,Masoumpour, Marzieh Sadat,Nasibipour, Mina,Safaei, Elham,Wojtczak, Andrzej
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p. 40853 - 40866
(2020/11/23)
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- Nano copper catalyzed synthesis of symmetrical/unsymmetrical sulfones from aryl/alkyl halides and p-toluenesulfonylmethylisocyanide: TosMIC as a tosyl source
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A magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of diaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. Sulfones containing molecules have medicinal relevance as they are known to possess various activities such as antifungal, anti-HIV, antitumor, and anticancer. Herein, a magnetically induced nano copper-catalyzed efficient and mild route for the synthesis of biaryl and alkyl/aryl sulfones from aryl/alkyl halides and tosylmethyl isocyanide (TosMIC) has been developed. A variety of aryl and alkyl sulfones have been obtained in very good to excellent yields. In this newly developed protocol TosMIC acts as sulfonyl source. The catalyst can magnetically be recovered and recycled five times without significant loss in activity.
- Phanindrudu, Mandalaparthi,Jaya, Pogula,Likhar, Pravin R.,Tiwari, Dharmendra Kumar
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- Facile synthesis of diarylsulfones from arenes and 3CdSO4·xH2O via mechanochemistry
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A variety of substituted diarylsulfones could be synthesized by simple arenes and 3CdSO4·xH2O in the presence of P2O5 under high-speed ball milling. It was suggest the aromatic sulfonation was performed by arene and in situ generated H2SO4, following-up by electrophilic substitution with another arene to give diarylsulfone.
- Qin, Shuai,Zhang, Pu,Qin, Yu-Jun,Guo, Zhi-Xin
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supporting information
(2020/01/06)
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- Synthetic method of diarylsulfone compound
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The invention relates to a synthetic method of a diarylsulfone compound. The method is characterized in that a copper complex and aryl sulfonyl hydrazide are dissolved in an organic solvent, air serves as an oxidizing agent, a reaction is conducted at the room temperature, separation and purification are conducted to obtain the corresponding diarylsulfone compound, the molar ratio of the copper complex to the aryl sulfonyl hydrazide is (0.01-0.03):1.0, and the reaction time is 2-5 h. Compared with the prior art, the synthesis process provided by the invention has excellent selectivity and highyield, the catalyst copper complex in the reaction can catalyze the self-coupling of aryl sulfonyl hydrazide to synthesize the diarylsulfone compound at room temperature, and the reaction has the characteristics of mild and simple conditions, wide substrate range, convenient product separation, high reaction efficiency and the like.
- -
-
Paragraph 0029; 0033-0036
(2020/10/04)
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- A Convenient Synthesis of Sulfones via Light Promoted Coupling of Sodium Sulfinates and Aryl Halides
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A convenient and e?cient synthesis of sulfones from sulfinates and aryl halides was developed. The reaction occurred under UV irradiation without transition metal catalyst or photocatalyst. A radical pathway via single-electron transfer (SET) of electron donor-acceptor (EDA) complex was proposed based on UV-vis spectroscopy, radical inhibiting and trapping experiments. (Figure presented.).
- Chen, Lei,Liang, Jie,Chen, Zhen-yu,Chen, Jie,Yan, Ming,Zhang, Xue-jing
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p. 956 - 960
(2019/01/25)
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- Palladium-catalyzed one-step synthesis of symmetrical diaryl sulfones from aryl halides and a sulfur dioxide surrogate
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A convenient method for the one-step synthesis of symmetrical diaryl sulfones from aryl halides has been developed. A keystone of the method is the use of K2S2O5, which can be easily and safely handled, as a sulfur dioxide surrogate. The palladium catalyst bearing P(t-Bu)3 as a ligand enables formation of the desired sulfones without significant formation of byproducts.
- Tanaka, Hiromichi,Konishi, Hideyuki,Manabe, Kei
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supporting information
p. 760 - 763
(2019/08/02)
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- Method for preparing diphenyl sulfone compound through catalysis of palladium acetate
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The invention discloses a method for preparing a diphenyl sulfone compound shown in formula (III) through catalysis of palladium acetate. The method comprises the following steps: fully reacting a bromobenzene compound as shown in formula (I), sodium sulfate and a benzoic acid compound as shown in formula (II) in a reaction medium with dimethylformamide (DMF) as a solvent under the action of palladium acetate as a catalyst and alkali metal carbonate as a base to prepare a reactant, and carrying out aftertreatment on the reactant to prepare the diphenyl sulfone compound. The catalyst is 20-mol%equivalent of the palladium acetate, and the alkali metal carbonate is cesium carbonate; in a reaction formula as shown in specification, R1 is selected from one of the following components: hydrogenand methyl; R2 is selected from one of the following components: hydrogen, methyl, methoxyl and trifluoromethoxy; the raw materials are simple, convenient and easy to obtain, and the preparation conditions are mild; the cost is low, and the requirement on equipment is low; aftertreatment is facilitated; and a catalytic system has wide adaptability and is suitable for large-scale industrial production.
- -
-
Paragraph 0018; 0019
(2019/07/04)
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- Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides: Sulfonyl Donors
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Sulfonyl azides have been widely used as sulfonamido, diazo, and azido donors, as well as all-nitrogen 1,3-dipoles donors in synthetic chemistry. Here, the sulfonyl azides were used as efficient sulfonyl donors, which is very unusual. Trifluoromethanesulfonic acid-induced formation of the sulfonyl cation reactive species from sulfonyl azides was developed and used for the first time to couple various inactivated arenes to prepare sulfones at ambient temperature.
- Zhang, Zhiguo,Wang, Songnan,Zhang, Yong,Zhang, Guisheng
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p. 3919 - 3926
(2019/03/29)
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- Organic photoredox catalysis enabled cross-coupling of arenediazonium and sulfinate salts: Synthesis of (un)symmetrical diaryl/alkyl aryl sulfones
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We disclose herein the first transition-metal-and external oxidant/reductant-free visible-light-mediated synthesis of (un)symmetrical diaryl/alkyl aryl sulfones from arenediazonium tetrafluoroborates and sodium sulfinates using eosin Y as an organic photoredox catalyst. The utilization of visible light as an inexpensive and ecosustainable energy source, operational simplicity, ambient temperature and clean reaction in aqueous acetonitrile are the salient features of the developed protocol. The desired sulfones were also synthesized via a one-pot, two-step process directly from anilines and sulfinate salts in good to excellent yields.
- Chawla, Ruchi,Yadav, Lal Dhar S.
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supporting information
p. 4761 - 4766
(2019/05/24)
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- A practical synthesis of aryl sulfones via cross-coupling of sulfonyl hydrazides with aryltriazenes using copper/ionic liquid combination
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A new and efficient approach adopting copper-catalyzed cross-coupling of sulfonyl hydrazides with aryltriazenes has been developed to synthesize aryl sulfones using Br?nsted acidic ionic liquid as promoter under ambient conditions. The process employs stable and easy to handle reacting partners, and is endowed with broad substrate scope.
- Pandey, Anand Kumar,Kumar, Saurabh,Singh, Rahul,Singh, Krishna Nand
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supporting information
p. 6704 - 6709
(2018/10/15)
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- Copper-mediated sulfonylation of aryl iodides and bromides with arylsulfonyl hydrazides in PEG-400
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Sulfonylation using stable and readily available arylsulfonyl hydrazides and aryl iodides or bromides mediated by cupric acetate has been achieved. Using polyethylene glycol (PEG-400) as an eco-friendly medium, the coupling reaction could afford a series of unsymmetrical diaryl sulfones in moderate to good yields without the presence of additional ligands and base.
- Wu, Xiangmei,Wang, Yan
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supporting information
p. 10953 - 10957
(2018/07/06)
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- Nickel-Catalyzed Synthesis of Diaryl Sulfones from Aryl Halides and Sodium Sulfinates
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A novel nickel-catalyzed cross-coupling of sulfinic acid salts with aryl halides is described. The reaction provides access to various diaryl sulfones in moderate to excellent yields. A broad range of functional groups and heteroaromatic compounds is tolerated under the reaction conditions.
- Liu, Nai-Wei,Liang, Shuai,Margraf, Natalie,Shaaban, Saad,Luciano, Vanessa,Drost, Marcella,Manolikakes, Georg
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supporting information
p. 1208 - 1210
(2018/03/21)
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- A Simple Metal Free Oxidation of Sulfide Compounds
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Abstract: This work reports simple, efficient, selective protocol for the oxidation of sulfide compounds. Various sulfides were selectively and completely converted into their corresponding sulfoxides and sulfones using H2O2as an oxidant in presence of catalytic amount of caprylic acid. The reaction proceeds at room temperature to give sulfoxide and by increasing the reaction temperature to 50 °C, this system provides selective formation of sulfone with high conversion and excellent yields. Green, convenient, easy work-up, chemoselectivity, broad substrate scope and regeneration of catalyst are the important highlights of this protocol. Graphical Abstract: [Figure not available: see fulltext.] Using H2O2as an oxidant in presence of catalytic amount of caprylic acid various sulfides were selectively and completely converted into their corresponding sulfoxides and sulfones.
- Wagh, Ravindra B.,Nagarkar, Jayashree M.
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p. 181 - 187
(2017/02/18)
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- Copper catalyzed synthesis of unsymmetrical diaryl sulfones from an arenediazonium salt and sodium p-toluenesulfinate
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Aryl sulfones have been for the first time synthesized by the reaction of sodium p-toluenesulfinate and arenediazonium salts using a CuI catalyzed homogeneous system. The developed protocol is a simple and efficient new route for the synthesis of diaryl sulfones with excellent product yields. The mild reaction conditions tolerate a range of functional groups. The best results were obtained with CuI, N,N′-dimethylethylenediamine, TBAI and K2CO3 in dimethyl sulfoxide at 100°C under an inert atmosphere.
- Gund, Sitaram Haribhau,Shelkar, Radheshyam Suresh,Nagarkar, Jayashree Milind
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p. 62926 - 62930
(2015/08/06)
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- Synthesis of diaryl sulfones at room temperature: Cu-catalyzed cross-coupling of arylsulfonyl chlorides with arylboronic acids
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An efficient and convenient method for the synthesis of diaryl sulfones was developed through the Cu-catalyzed cross-couplings of arylsulfonyl chlorides and arylboronic acids at room temperature in open air. This method is characterized by the use of inexpensive and readily available catalyst and substrates, mild reaction conditions, wide functionality tolerance, short reaction times for most substrates, and moderate to good yields. Stitch it up with copper: An efficient and convenient method for the synthesis of diaryl sulfones was developed through the Cu-catalyzed cross- couplings of arylsulfonyl chlorides and arylboronic acids at room temperature in open air.
- Hu, Feng,Lei, Xiangyang
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p. 1539 - 1542
(2015/05/27)
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- A new class of bifunctional chiral phase transfer catalysts for highly enantioselective asymmetric epoxidation of α,β-unsaturated ketones at ambient temperature
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A new type of bis-quaternary ammonium bromide as chiral multifunctional phase transfer catalysts derived from readily available inexpensive cinchona alkaloids has been developed and evaluated for the enantioselective asymmetric epoxidation of various chalcones in the presence of lower concentrations of various oxidants, bases, solvents and ambient temperature conditions. Under optimized reaction conditions, highest chemical yields of up to 98% along with the excellent enantioselectivities of about 99% were obtained by using the cinchona based chiral multifunctional phase transfer catalysts.
- Ashokkumar, Veeramanoharan,Balasaravanan, Rajendiran,Sadhasivam, Velu,Jenofar, Seenisultanmaideen Mehtob,Siva, Ayyanar
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p. 127 - 136
(2015/09/15)
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- A highly active and easily recoverable chitosan@copper catalyst for the C-S coupling and its application in the synthesis of zolimidine
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Aryl sulfones were synthesized using a highly active and easily recoverable heterogeneous Cu catalyst which was prepared by simply stirring an aqueous suspension of chitosan in water with copper salts. The chitosan@copper catalyst catalyzed the coupling reactions of aryl halides with sodium sulfinates to readily give the corresponding sulfones in good to excellent yields. The highly active catalyst can be reused many times without losing its catalytic activity. In addition, by using this protocol, the marketed drug zolimidine (antiulcer) could be synthesized easily. This journal is the Partner Organisations 2014.
- Shen, Chao,Xu, Jun,Yu, Wenbo,Zhang, Pengfei
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supporting information
p. 3007 - 3012
(2014/06/10)
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- The synthesis of diarylsulfones with simple arenes and K2S2O8 through double C-S bond formation
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An unprecedented double C-S bond formation method has been developed to prepare both symmetric and unsymmetric diarylsulfones with simple arenes in a single step. This represents the first example that K2S2O8 can be employed as a highly effective sulfonating agent to synthesize diarylsulfones. The reaction demonstrates excellent reactivity, good functional group tolerance and high yields.
- Yang, Yiqing,Chen, Zhang,Rao, Yu
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p. 15037 - 15040
(2014/12/11)
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- A mild and base-free synthesis of unsymmetrical diaryl sulfones from arylboronic acids and arylsulfonyl hydrazides
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A mild and efficient synthesis of diaryl sulfones from arylboronic acids and arylsulfonyl hydrazides is described. Promoted by cupric acetate and in the absence of additional ligand and base, the cross-coupling reaction could afford a series of unsymmetrical diaryl sulfones in moderate to good yields at room temperature under neutral and ambient conditions. Georg Thieme Verlag Stuttgart New York.
- Wu, Xiang-Mei,Wang, Yan
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supporting information
p. 1163 - 1167
(2014/05/20)
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- Synthesis of symmetrical diaryl sulfone by homocoupling of sodium arylsulfinate
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An efficient practical homocoupling reaction of sodium arylsulfinate promoted by Cu(II) is reported whereby symmetrical diaryl sulfone derivatives are obtained with high selectivity and reactivity by intermolecular cross-coupling. This homocoupling reacti
- Peng, Yao
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p. 265 - 268
(2014/06/09)
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- Copper-mediated cascade synthesis of diaryl sulfones via the sandmeyer reaction
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A convenient and efficient method for the copper-mediated cascade synthesis of diaryl sulfones via the Sandmeyer reaction has been developed. The protocol uses readily available aryl amines and arylsulfinic acids as the starting materials, isoamyl nitrite as the diazotizating reagent of the aryl amines, and the method shows mild reaction conditions and high tolerance towards various functional groups in the substrates. Georg Thieme Verlag Stuttgart New York.
- Yang, Xiaobo,Shi, Liangliang,Fu, Hua
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p. 847 - 852
(2014/04/17)
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- An unprecedented use for glycerol: Chemoselective reducing agent for sulfoxides
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A new application for glycerol that expands its possibilities beyond a green solvent and a precursor of value-added products has been demonstrated. Simple, easily available, and environmentally friendly dioxomolybdenum(vi) complexes are highly efficient catalysts for the chemoselective sulfoxide deoxygenation with this biomass-derived chemical feedstock. Both refined glycerol and crude glycerin can be used, thus expanding the potential application of this reaction. Subsequent transformation of glycerol during this reductive process has also been investigated.
- Garcia, Nuria,Garcia-Garcia, Patricia,Fernandez-Rodriguez, Manuel A.,Garcia, Daniel,Pedrosa, Maria R.,Arnaiz, Francisco J.,Sanz, Roberto
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p. 999 - 1005
(2013/07/25)
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- Investigations on the Lewis-acids-catalysed electrophilic aromatic substitution reactions of thionyl chloride and selenyl chloride, the substituent effects, and the reaction mechanisms
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The previously established aluminium-chloride-(AlCl3)-catalysed electrophilic aromatic substitution (EAS) of benzene (PhH) with thionyl chloride (SOCl2) has been extended to toluene (PhCH3), chlorobenzene (PhCl), and phenol (PhOH). -CH3 was found to be mainly a para-director with a minor ortho-directing effect on the EAS reactions giving diaryl sulfoxides (Ar2SO). -Cl was found to be exclusively a para-director for formation of Ar2SO. All the -CH3, -Cl, and -OH groups were shown to be exclusive para-directors for formation of diaryl sulfides (Ar2S) from the EAS reactions. Although the reactions of PhH and PhCH3 with SOCl2 in the presence of AlCl 3 gave the major Ar2SO and minor Ar2S at ambient temperature, the phenol (PhOH) reaction was shown to give only the reduced sulfide (p-HOC6H4)2S with no sulfoxide (p-HOC6H4)2SO formed. The mixed diaryl sulfoxides ArSOAr′ (Ar, Ar′=C6H5, p-CH 3C6H4; C6H5, o-CH 3C6H4; and C6H5, p-ClC6H4) were produced in the AlCl3-catalysed reactions of SOCl2 with molar 1:1 PhH-PhX mixtures (X=CH3 and Cl). Efforts to enhance the yield of S-aryl arenesulfonothioates ArSO 2SAr (Ar=Ph, p-CH3C6H4, and p-ClC6H4) from the AlCl3-catalysed EAS reactions of SOCl2 were made, showing that decreasing the molar ratios of ArH/SOCl2 or lowering the temperature resulted in an increase in the product yield. A detailed mechanism has been proposed to account for the formation of ArSO2SAr. The Lewis-acid-MCl3-(M=Al and Fe)-catalysed EAS reactions of PhH with selenyl chloride (SeOCl2) were demonstrated to give the reduced diphenyl selenide (Ph2Se) and diphenyl diselenide (PhSeSePh) via novel auto-redox processes in selenium of the key EAS intermediates.
- Sun, Xiaoping,Haas, David,McWilliams, Samantha,Smith, Benjamin,Leaptrot, Katrina
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p. 736 - 744
(2014/01/23)
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- A Metal-Free and Microwave-Assisted Efficient Synthesis of Diaryl Sulfones
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An efficient and general protocol for the synthesis of diaryl sulfones via the metal-free coupling of readily available diaryliodonium salts and arenesulfinates in PEG-400 under microwave irradiation has been developed. Utilizing this metal-free and eco-friendly protocol, we have prepared various diaryl sulfones in high yields and shorter reaction times under mild conditions. Furthermore, the coupling of diaryliodonium with arenesulfinate salts with and without copper iodide provides a convenient access to various diaryl sulfones with high selectivity. Georg Thieme Verlag Stuttgart · New York.
- Kumar, Dalip,Arun,Pilania, Meenakshi,Shekar, K.P. Chandra
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p. 831 - 836
(2013/06/05)
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- Highly efficient rhenium-catalyzed deoxygenation of sulfoxides without adding any reducing agent
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This work reports a novel method for the deoxygenation of aromatic and aliphatic sulfoxides catalyzed by oxo-rhenium complexes without adding any reducing agent. The oxo-rhenium complex ReOCl3(PPh3) 2 proved to be very efficient for the deoxygenation of several sulfoxides with tolerance of different functional groups.
- Sousa, Sara C.A.,Bernardo, Joana R.,Rom?o, Carlos C.,Fernandes, Ana C.
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experimental part
p. 8194 - 8197
(2012/09/22)
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- Sulfonylation of aromatic compounds with methyl p-toluenesulfonate as a sulfonylating precursor
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We have developed Friedel-Crafts (FC) sulfonylation of aromatic compounds with methyl p-toluenesulfonate as a sulfonylating precursor. In this procedure, methyl p-toluenesulfonate was treated and activated with pyridine to produce N-methylpyridinium p-toluenesulfonate as a sulfonylation reagent. Reactivity of this salt for the sulfonylation of mesitylene was investigated in the presence of three different promoters, such as triflic anhydride, dimethylsulfide ditriflate, and triphenylphosphine ditriflate (TPPD). All of the promoters show chemoselectivity and among them, TPPD presents a chemoselectivity in FC sulfonylation. Iranian Chemical Society 2012.
- Khodaei,Nazari
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p. 507 - 512
(2013/02/22)
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- Palladium-catalyzed desulfitative arylation of azoles with arylsulfonyl hydrazides
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Palladium-catalyzed desulfitative and denitrogenative arylation of azoles with arylsulfonyl hydrazides has been achieved. A broad scope of azoles and arylsulfonyl hydrazides has been used to produce arylated azoles in high yields.
- Yu, Xinzhang,Li, Xingwei,Wan, Boshun
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p. 7479 - 7482
(2012/10/29)
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- General copper-catalyzed transformations of functional groups from arylboronic acids in water
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A simple and general copper-catalyzed method has been developed for transformations of various functional groups (i I, i N3, i SO2R, i OH, i NH2, and i NO 2) on aromatic rings from arylboronic acids in water under air. The protocol uses cheap and readily available inorganic salts (KI, NaN3, NaSO2R, NaOH, NaNO2) and aqueous ammonia as the functional-group sources, simple Cu2O/NH3 as the catalyst system, environmentally friendly water as the solvent, and oxygen in air as the oxidant. Importantly, the copper catalyst system in water was recyclable. This study should provide a useful strategy for interconversions of the functional groups on aromatic rings.
- Yang, Haijun,Li, Yong,Jiang, Min,Wang, Junmei,Fu, Hua
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experimental part
p. 5652 - 5660
(2011/06/23)
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- Palladium-catalyzed aromatic sulfonylation: A new catalytic domino process exploiting in situ generated sulfinate anions
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Allylic sulfones are excellent precursors of aryl sulfones via a new Pd-catalyzed domino sequence involving in situ generation of sulfinate anions and subsequent cross-coupling with aryl -iodides or bromides. Georg Thieme Verlag Stuttgart · New York.
- Le Duc, Ga?tan,Bernoud, Elise,Prestat, Guillaume,Cacchi, Sandro,Fabrizi, Giancarlo,Iazzetti, Antonia,Madec, David,Poli, Giovanni
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supporting information; experimental part
p. 2943 - 2946
(2012/01/05)
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- Sulfonylation of aromatic compounds with sulfonic acids using silica gel-supported AlCl3 as a heterogeneous Lewis acid catalyst
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Silica gel-supported aluminum chloride (SiO2-AlCl3) has been shown to be a mild, efficient, and chemoselective heterogeneous Lewis acid catalyst for direct conversion of arenes to sulfones using sulfonic acids as sulfonylating agents. The catalyst can be prepared easily with cheap starting materials and is stable (as a bench-top catalyst) and reusable.
- Parvanak Boroujeni, Kaveh
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experimental part
p. 197 - 203
(2010/11/05)
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- Polystyrene supported Al(OTf)3: A stable, efficient, selective, and reusable catalyst for sulfonylation of arenes with sulfonic acids
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Cross-linked polystyrene supported aluminium triflate (Ps-Al(OTf) 3) was found to be an efficient and chemoselective heterogeneous Lewis acid catalyst for the direct conversion of arenes to sulfones using sulfonic acids as sulfonylating agents. The solid acid catalyst is stable (as a bench top catalyst) and can be easily recovered and reused without appreciable change in its efficiency.
- Boroujeni, Kaveh Parvanak
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experimental part
p. 1887 - 1890
(2010/11/18)
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- MoO2Cl2 as a novel catalyst for Friedel-Crafts acylation and sulfonylation
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The use of MoO2Cl2 as a novel catalyst for Friedel-Crafts acylation and sulfonylation is described. A series of aromatic ketones and sulfones were prepared in moderate to good yields using acyl chloride or sulfonyl chloride in the presence of MoO2Cl2 (20 mol %), under solvent-free conditions.
- de Noronha, Rita G.,Fernandes, Ana C.,Rom?o, Carlos C.
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experimental part
p. 1407 - 1410
(2009/06/18)
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- Synthesis and photovoltaic properties of novel solution-processable triphenylamine-based dendrimers with sulfonyldibenzene cores
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Three conjugated dendrimers containing electron-accepting sulfonyldibenzene (SDB) cores and electron-donating triphenylamine dendrons have been synthesized through a convergent synthetic strategy without any protection/deprotection chemistry. The dendrimers were highly soluble in common organic solvents, and could form good quality optical films by spin coating. Their thermal, optical and electrical properties are manipulated by attaching different peripheral dendrons. Using these dendrimers as donors and [6,6]-phenyl C61-butyric acid methyl ester (PCBM) as acceptor, the bulk heterojunction solar cells with a structure of ITO-PEDOT-dendrimers:PCBM-LiF-Al were fabricated. The cell based on dendrimer G0 shows a relatively high power-conversion efficiency (PCE) of 0.34% under AM 1.5 illumination of 100 mW cm-2.
- Li, Kunpeng,Qu, Jiali,Xu, Bin,Zhou, Yinhua,Liu, Leijing,Peng, Ping,Tian, Wenjing
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experimental part
p. 2120 - 2127
(2009/12/25)
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- Copper-Catalyzed Sulfonylation of Arylboronic Acids in Ionic Liquids
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Cupric acetate in ionic liquids (ILs) catalyzes coupling reaction of arylboronic acids with sulfinic acid salts to afford aryl sulfones in good yields under ambient conditions. This mild and efficient cross-coupling reaction gives access to a wide range of alkylaryl and diaryl sulfones in good yields. The use of ionic liquid allows for easy separation of the product and recycling of copper catalyst.
- Kantam, M. Lakshmi,Neelima,Sreedhar,Chakravarti, Rajashree
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experimental part
p. 1455 - 1458
(2009/04/07)
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- Highly selective catalytic Friedel-Crafts sulfonylation of aromatic compounds using a FeCl3-based ionic liquid
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Friedel-Crafts sulfonylation of aromatic compounds was carried out using FeCl3-based ionic liquid. These liquids serve as efficient media as well as Lewis acid catalyst.
- Bahrami, Kiumars,Khodei, Mohammad Mehdi,Shahbazi, Fomeida
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p. 3931 - 3934
(2008/09/21)
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- Sulfonylation of arenes with sulfonamides
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In the presence of triflic anhydride, sulfonylation of arenes with sulfonamides proceeded smoothly in Cl2CHCHCl2 at 80-140 °C, which gave rise to the desired products in good to excellent yields.
- Yao, Bangben,Zhang, Yuhong
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p. 5385 - 5388
(2008/12/21)
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