cas 640-57-3, Benzene,1-methyl-4-(phenylsulfonyl)-

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Dispersible porous classical polymer photocatalysts for visible light-mediated production of pharmaceutically relevant compounds in multiple solvents
The dispersibility of photocatalytic polymeric materials is currently a limiting factor for wide scale use. Indeed, the dispersibility of photocatalytic material in solvents dictates its use as heterogenous catalysts, due in part to reagent solubility. Here, we describe a new platform for producing porous polymer photocatalytic nanoparticles that are easily dispersible in a broad range of solvents. Photocatalytic porous classical polymer nanoparticles have been designed, based on classical porous nanoparticles copolymerised with photocatalytic moieties. The combination of both classical and photocatalytic monomers results in an affordable highly photocatalytically effective material, that can be easily dispersed in a wide range of solvents. The versatility and useability of this new material has been demonstrated by photocatalysing a number of pharmaceutically relevant compounds in solvents with varying polarity.
Ferguson, Calum T. J.,Huber, Niklas,Kuckhoff, Thomas,Zhang, Kai A. I.,Landfester, Katharina
p. 1072 - 1076
(2020)
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Visible-Light-Mediated Late-Stage Sulfonylation of Boronic Acids via N-S Bond Activation of Sulfonamides
A visible-light-mediated late-stage arylation of N-S bonds in sulfonamides has been developed with using readily available imines as sulfonyl radical source. Diverse complex sulfones could be synthesized by prefunctionalizaiton and subsequent N-S bond ary
Du, Xian,Li, Yihui,Luo, Yong,Xu, Dejing,Xu, Xiaohong,Xue, Can,Yuan, Han,Zhen, Jingsong
p. 1986 - 1991
(2022/02/07)

Metal-free sulfonylation of arenes with: N -fluorobenzenesulfonimide via cleavage of S-N bonds: expeditious synthesis of diarylsulfones
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
supporting information
p. 768 - 772
(2022/02/03)

On the important transition of sugar-based surfactant as a microreactor for C-S coupling in water: From micelle to vesicle
A reversible, temperature-induced micelle-to-vesicle transition of a sugar-based pseudogemini surfactant (C11D12) was employed for copper-catalyzed C-S coupling in water. The phase behavior and morphology of the C11D12 aqueous solution were investigated by DLS and cryo-TEM. The aggregates undergo a series of transitions upon increasing the temperature: spherical micelles were initially transformed into large vesicles, but they eventually transformed into smaller vesicles. The vesicular catalytic protocol accommodates an excellent substrate scope with moderate to high yields. The mechanisms of temperature-induced aggregate transition and vesicular catalysis were elucidated by experimental results and DFT calculations. It was revealed that the charge layer of the vesicle grants stronger nucleophilicity to the PhSO2-Cu-D12Ga intermediate. Furthermore, the aqueous reaction medium can be recycled and reused several times after easily separating the precipitated product.
Ge, Xin,Lei, Qiuyun,Liao, Xiong,Liu, Xuemin,Song, Weili,Wu, Lei,Wu, Siyuan,Zhou, Shaodong
(2021/09/15)

Interfacing sugar-based surfactant micelles and Cu nanoparticles: A nanoreactor for C-S coupling reactions in water
A simple and sustainable synergistic catalytic protocol by interfacing nanomicelles and metal nanoparticles (MNPs) is reported for C-S coupling reactions in water. The sugar-based surfactant GluM was synthesized by introducing a PEG chain to stabilize MNPs and self-assembled to form nanomicelles. Cu2O nanoparticles were generated via in situ reduction of copper salt in an aqueous solution of the sugar-based surfactant. The nature of the interaction between nanomicelles and Cu2O nanoparticles was revealed by XPS, XRD, in situ IR, TEM, and 1H NMR. A broad substrate scope with moderate to excellent yields was documented and the recycling of the GluM/Cu aqueous mixture was surprising.
Ge, Xin,He, Xi,Liu, Xuemin,Qian, Chao,Song, Weili,Yang, Jinguo,Zhou, Shaodong
supporting information
p. 6322 - 6329
(2021/09/10)

Method for synthesizing diaryl sulfone compound by photocatalytic oxidation of diaryl sulfide
The invention discloses a method for synthesizing a diaryl sulfone compound by photocatalytic oxidation of diaryl sulfide, which comprises the following steps: in an oxygen-containing atmosphere and under the condition of 370-375nm ultraviolet irradiation, carrying out one-pot reaction on the diaryl sulfide compound and sodium difluoromethanesulfinate in a dioxane solution system to generate the diaryl sulfone compound. The method has the advantages of mild conditions, simple operation, environmental protection, easily available raw materials, excellent compatibility of substrate functional groups, high reaction yield and the like.
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Paragraph 0037-0057; 0062-0065

(2021/02/20)

Synthesis of Sulfones and Sulfonyl Derivatives using Sodium (tert-butyldimethylsilyl)oxymethanesulfinate
The present invention relates to a method for manufacturing a sulfone and sulfonyl derivative compound using sodium (tert-butyldimethylsilyl)oxymethanesulfinate, which is a novel organic sulfin salt, wherein the novel organic sulfin salt has good stability, environmental friendliness and economy, and is easy to handle, and thus significantly reduces the amount of transition metal catalysts and the amount of organic sulfin salts used when introducing aryl or alkenyl. Also, alkylation, arylation, amination, and fluorination are all possible during secondary functionalization. Therefore, the present invention can be usefully used in preparation and mass production of various kinds of sulfones and derivatives thereof including asymmetric sulfone derivatives.
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Paragraph 0704-0710; 0712; 0714-0715; 0717-0720; 0727-0730

(2021/04/29)

Electrochemical oxygenation of sulfides with molecular oxygen or water: Switchable preparation of sulfoxides and sulfones
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
supporting information
p. 10314 - 10318
(2021/12/17)

Synergistic cooperative effect of CF3SO2Na and bis(2-butoxyethyl)ether towards selective oxygenation of sulfides with molecular oxygen under visible-light irradiation
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
supporting information
p. 496 - 500
(2021/01/28)

Sulfoxide and Sulfone Synthesis via Electrochemical Oxidation of Sulfides
The oxidation of diaryl sulfides and aryl alkyl sulfides to the corresponding sulfoxides and sulfones under electrochemical conditions is reported. Sulfoxides are selectively obtained in good yield under a constant current of 5 mA for 10 h in DMF, while sulfones are formed as the major product under a constant current of 10 or 20 mA for 10 h in MeOH. The oxygen of both the sulfoxide and sulfone function is derived from water.
Lee, Sunwoo,Park, Jin Kyu
p. 13790 - 13799
(2021/10/12)

A Copper(I)-Catalyzed Sulfonylative Hiyama Cross-Coupling
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
supporting information
p. 18047 - 18053
(2021/11/16)

Primary Sulfonamide Functionalization via Sulfonyl Pyrroles: Seeing the N?Ts Bond in a Different Light
Despite common occurrence in molecules of value, methods for transforming sulfonamides are distinctly lacking. Here we introduce easy-to-access sulfonyl pyrroles as synthetic linchpins for sulfonamide functionalization. The versatility of the sulfonyl pyrrole unit is shown by generating a variety of products through chemical, electrochemical and photochemical pathways. Preliminary results on the direct functionalization of primary sulfonamides are also provided, which may lead to new modes of activation.
Ozaki, Tomoya,Yorimitsu, Hideki,Perry, Gregory J. P.
p. 15387 - 15391
(2021/10/04)

Sulfonylation of Bismuth Reagents with Sulfinates or SO2through BiIII/BiV Intermediates
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
supporting information
p. 2400 - 2404
(2021/07/28)

Method for synthesizing sulfone compounds under photocatalysis condition
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 0046-0051

(2021/03/31)

Pd/NHC-catalyzed arylsulfonylation of boronic acids: A general and direct protocol to access diarylsulfones
For the first time, robust NHC-Pd complexes have been demonstrated as highly efficient catalysts in the direct arylsulfonylation of boronic acids. Remarkably, a broad number of diaryliodonium salts as powerful electrophilic arylation reagents are well compatible to form functional ortho-substituted diarylsulfones in satisfactory yields. Owing to the stronger σ-donor and weaker π-acceptor properties, the acenaphthoimidazolylidene ligands exhibit higher catalytic activities towards this challenging one-step arylsulfonylation reaction.
Zhu, Haibo,Yang, Liu,Meng, Jia,Xie, Zongbo,Le, Zhang-Gao,Tu, Tao
supporting information

(2020/12/29)

Heterogeneous copper-catalyzed synthesis of diaryl sulfones
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
supporting information
p. 10662 - 10668
(2021/12/27)

Hantzsch Ester as a Visible-Light Photoredox Catalyst for Transition-Metal-Free Coupling of Arylhalides and Arylsulfinates
Diethyl 2,6-dimethyl-1,4-dihydropyridine-3,5-dicarboxylate (HEH) has been utilized as a visible-light photoredox catalyst for the cross coupling of arylhalides and arylsulfinates without transition metal, sacrificial agent, and mediator. This method is compatible with various functional groups and provides diaryl sulfones in good to high yields. Mechanistic studies indicate that this reaction undergoes the stepwise light irradiation of HE?, single electron transfer (SET) in donor–acceptor complex (DAC) from *HE? to arylhalide, trapping of aryl radical with sulfinate, and SET oxidation of sulfone radical anion by HE. to sulfone by the DAC method.
Zhu, Da-Liang,Wu, Qi,Li, Hai-Yan,Li, Hong-Xi,Lang, Jian-Ping
supporting information
p. 3484 - 3488
(2020/03/05)

Micelle catalysis and extraction separation coupling method based on nonionic surfactant (by machine translation)
The invention discloses a micelle catalysis and extraction separation coupling method based on a nonionic surfactant, and belongs to the technical field of chemical synthesis. M 202070 is used as a reaction medium, the Ullmann C-S coupling reaction is catalyzed, and the product is separated by directly heating to a cloud point after the reaction is completed. The method provided by the invention is mild in condition, convenient to operate, less in organic matter content in the reaction waste liquid, small in environmental pollution, green and environment-friendly; meanwhile, the yield of the aromatic sulfone can reach 75% or above, the extraction yield reaches 100%, and the method is suitable for industrial mass production. (by machine translation)
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Paragraph 0042-0046; 0075; 0079; 0083

(2020/08/18)

Selective oxidation of (hetero)sulfides with molecular oxygen under clean conditions
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
supporting information
p. 433 - 438
(2020/02/13)

Oxidation of aromatic sulfides with molecular oxygen: Controllable synthesis of sulfoxides or sulfones
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
p. 2991 - 2992
(2020/03/24)

Silyloxymethanesulfinate as a sulfoxylate equivalent for the modular synthesis of sulfones and sulfonyl derivatives
An efficient protocol for the modular synthesis of sulfones and sulfonyl derivatives has been developed utilizing sodium tert-butyldimethylsilyloxymethanesulfinate (TBSOMS-Na) as a sulfoxylate (SO22-) equivalent. TBSOMS-Na, easily prepared from the commercial reagents Rongalite and TBSCl, serves as a potent nucleophile in S-alkylation and Cu-catalyzed S-arylation reactions with alkyl and aryl electrophiles. The sulfone products thus obtained can undergo the second bond formation at the sulfur center with various electrophiles without a separate unmasking step to afford sulfones and sulfonyl derivatives such as sulfonamides and sulfonyl fluorides.
Kim, Dae-Kwon,Um, Hyun-Suk,Park, Hoyoon,Kim, Seonwoo,Choi, Jin,Lee, Chulbom
p. 13071 - 13078
(2021/01/09)

TosMIC and its derivatives as versatile sulfonylating agents for the synthesis of p-toluenesulfonylarenes from aryl halides and arylboronic acids
An efficient copper(II) catalyzed sulfonyation of aryl halides has been achieved using TosMIC (p-toluenesulfonylmethyl isocyanide) as a sulfonylating agent. This newly developed sulfonylation approach provides an easy access for the synthesis of diaryl sulfones from aryl bromides, iodides and boronic acids with TosMIC under neutral conditions. This method is useful for the sulfonylation of aryl boronic acids under similar conditions. This is the first report on the sulfonylation of aryl bromides, iodides and boronic acids using TosMIC.
Ravi Kumar,Ramesh,Banik, Swarnayu,Subba Reddy
(2020/11/02)

Nano copper catalyzed synthesis of symmetrical/unsymmetrical sulfones from aryl/alkyl halides and p-toluenesulfonylmethylisocyanide: TosMIC as a tosyl source
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
(2020/05/18)

A designed bi-functional sugar-based surfactant: Micellar catalysis for C-X coupling reaction in water
A bi-functional sugar-based surfactant ALA14 was designed as the ligand and micelle constructor and demonstrated to promote the copper-catalyzed C-X coupling reaction in water. The nature of this micelle, formed by sugar-based surfactants, was investigated with CMC, DLS, and TEM, by which encapsulation and aggregation of the substrates in micelles were verified. Additionally, it was addressed by 1H-NMR analysis that the enrichment position of the substrates is in the lipophilic alkyl chain. Finally, moderate to excellent yields of the aimed products were obtained in this work. This remarkably simple strategy expanded the scope of C-X coupling reaction in water; most notably, both water and ALA14 can be recycled and reused.
Ge, Xin,Zhang, Shihui,Chen, Xinzhi,Liu, Xuemin,Qian, Chao
supporting information
p. 2771 - 2776
(2019/06/13)

Method for preparing aryl sulfone compound as well as method for extracting catalyst and aryl sulfone compound
The invention provides a preparation method of an aryl sulfone compound, which is characterized in that in an organic solvent and under an aerobic atmosphere, a catalytic system composed of a metal-ligand-TEMPO is used for catalytic oxidation of a thioether compound to obtain the aryl sulfone compound. The preparation method is simple, green, and efficient, the reaction condition is mild, and theapplication range is wide; the invention also provides a method for extracting a catalyst and the product aryl sulfone compound used in the preparation process. The ethyl acetate is added to a reaction mixture, steps of filtering and condensation under reduced pressure are carried out to obtain a filtrate and the catalyst, and silica gel column chromatography and concentration extraction are carried out to obtain the aryl sulfone compound. The extraction method is simple, and the extracted catalyst has high activity and good cycle stability, and the extraction rate of the product aryl sulfonecompound is high.
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Paragraph 0052-0055

(2019/02/13)

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)

Synthesis method of diaryl sulfone compound (by machine translation)
The invention discloses a synthesis method of a diaryl sulfone compound, wherein the, reaction equation of the series of N - diarylsulfone compounds is prepared by (NFSI) sulfonylating the aromatic hydrocarbon under the non-metal condition with the source of the, benzenesulfonyl group as the benzenesulfonyl group, and: the reaction equation is as follows. STR3, #, STR2, #, STR2, #, #, #, # STR2. # STR2# STR2# STR2, , STR2 STR2 STR2 N - # (NFSI) STR2# STR2 STR2 STR2, #, # STR1 STR8# STR2 STR1 STR8. AlCl R3 , FeCl3 The other precious, and metals of, other metals such as the precious metals of, the other noble metals not cause the environment, to pollute, the environment and are suitable for the concise and high-efficiency synthesis of. the diarylsulfone compounds, and have good application prospects in the fields of organic synthesis, drug research and development and the like. (by machine translation)
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Paragraph 0007; 0017-0018; 0032-0034

(2019/12/31)

Method for preparing diphenyl sulfone compound through catalysis of palladium acetate
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.
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Paragraph 0017; 0018

(2019/07/04)

Regiospecific Cleavage of S-N Bonds in Sulfonyl Azides: Sulfonyl Donors
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
p. 3919 - 3926
(2019/03/29)

Organic photoredox catalysis enabled cross-coupling of arenediazonium and sulfinate salts: Synthesis of (un)symmetrical diaryl/alkyl aryl sulfones
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.
supporting information
p. 4761 - 4766
(2019/05/24)

An efficient heterogeneous copper fluorapatite (CuFAP)-catalysed oxidative synthesis of diaryl sulfone under mild ligand- and base-free conditions
A simple, eco-friendly and efficient method for the synthesis of unsymmetrical diaryl sulfones using heterogeneous copper fluorapatite (CuFAP)-catalysed coupling of aryl sulfonic acid and phenyl boronic acid has been developed with good to excellent yields without use of any ligand, base or co-catalyst. Broad substrate scope and gram scale operations are the important features of this method.
Kamble, Rohit B.,Chavan, Santosh S.,Suryavanshi, Gurunath
supporting information
p. 1632 - 1636
(2019/01/21)

SO2 conversion to sulfones: Development and mechanistic insights of a sulfonylative Hiyama cross-coupling
A Pd-catalyzed Hiyama cross-coupling reaction using SO2 is described. The use of silicon-based nucleophiles leads to the formation of allyl sulfones under mild conditions with a broad functional group tolerance. Control experiments coupled with DFT calculations shed light on the key steps of the reaction mechanism, revealing the crucial role of a transient sulfinate anion.
Adenot, Aurélien,Char, Jo?lle,Von Wolff, Niklas,Lefèvre, Guillaume,Anthore-Dalion, Lucile,Cantat, Thibault
supporting information
p. 12924 - 12927
(2019/11/05)

Copper-mediated sulfonylation of aryl iodides and bromides with arylsulfonyl hydrazides in PEG-400
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
supporting information
p. 10953 - 10957
(2018/07/06)

Mechanistic aspects of copper (II)-catalyzed synthesis of sulfones from sulfinate salts and aryl halides under C-S coupling
Copper(II)-catalyzed synthesis of sulfones from sulfinate salts and aryl halides was investigated by means of a combination of experiment and DFT calculation. Experimental results demonstrated the wide applicability of the title approach. The reaction mechanisms are revealed by in-situ IR and theoretical study. It reveals remarkable ligand effect the bidentate amine plays in the reaction, that is, it initially activats the C-I bond of iodobenzene so as to enhance the whole catalytic process.
Ge, Xin,Sun, Fengli,Liu, Xuemin,Chen, Xinzhi,Qian, Chao,Zhou, Shaodong
p. 72 - 78
(2018/04/26)

Efficient Ullmann C-X coupling reaction catalyzed by a recoverable functionalized-chitosan supported copper complex
Three different types of functionalized-CS were prepared and anchored with copper salts for use as the catalyst for the Ullmann C-X coupling reaction. The Schiff-basic chitosan supported copper complex (PCCS@CuI) exhibits the highest catalytic activity. The structure of the catalyst was characterized by FTIR spectroscopy, TG, XRD, SEM, EDS and XPS. This catalyst exhibited high applicability for the C-N and C-S coupling reactions, in which good to excellent yields were obtained. Its easy separation, good reusability and stability were notable.
Liu, Xuemin,Chang, Shuo,Chen, Xinzhi,Ge, Xin,Qian, Chao
supporting information
p. 16013 - 16020
(2018/10/04)

Engaging sulfinate salts via Ni/photoredox dual catalysis enables facile Csp2-SO2R coupling
This report details the development and implementation of a strategy to construct aryl- and heteroaryl sulfones via Ni/photoredox dual catalysis. Using aryl sulfinate salts, the C-S bond can be forged at room temperature under base-free conditions. An array of aryl- and heteroaryl halides are compatible with this approach. The broad tolerance and mild nature of the described reaction could potentially be employed to prepare sulfones with biological relevance (e.g., in bioconjugation, drug substance synthesis, etc.) as demonstrated in the synthesis of drug-like compounds or their precursors. When paired with existing Ni/photoredox chemistry for Csp3-Csp2 cross-coupling, an array of diverse sulfone scaffolds can be readily assembled from bifunctional electrophiles. A mechanistic manifold consistent with experimental and computational data is presented.
Cabrera-Afonso, María Jesús,Lu, Zhi-Peng,Kelly, Christopher B.,Lang, Simon B.,Dykstra, Ryan,Gutierrez, Osvaldo,Molander, Gary A.
p. 3186 - 3191
(2018/03/30)

Visible-Light Photoredox/Nickel Dual Catalysis for the Cross-Coupling of Sulfinic Acid Salts with Aryl Iodides
An efficient cross-coupling of sodium or lithium sulfinates with aryl iodides, using a combination of nickel and photoredox catalysis, is described. The dual catalyst system enables a versatile synthesis of aryl sulfones at room temperature in good yields and displays a broad functional group compatibility. The potential utility of this method in the late-stage diversification of complex molecules and in the conversion of organolithium reagents and sulfur dioxide into sulfones is demonstrated.
Liu, Nai-Wei,Hofman, Kamil,Herbert, André,Manolikakes, Georg
supporting information
p. 760 - 763
(2018/02/09)

Cross-Coupling of Sodium Sulfinates with Aryl, Heteroaryl, and Vinyl Halides by Nickel/Photoredox Dual Catalysis
An efficient photoredox/nickel catalyzed sulfonylation reaction of aryl, heteroaryl, and vinyl halides has been achieved for the first time. This newly developed sulfonylation protocol provides a versatile method for the synthesis of diverse aromatic sulfones at room temperature and shows excellent functional group tolerance. The electrophilic coupling partners are not limited to aryl, heteroaryl, and vinyl bromides and iodides, but also includes less reactive aryl chlorides as suitable substrates for this transformation.
Yue, Huifeng,Zhu, Chen,Rueping, Magnus
supporting information
p. 1371 - 1375
(2018/01/27)

A practical synthesis of aryl sulfones via cross-coupling of sulfonyl hydrazides with aryltriazenes using copper/ionic liquid combination
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
supporting information
p. 6704 - 6709
(2018/10/15)

Visible-Light-Driven Silver-Catalyzed One-Pot Approach: A Selective Synthesis of Diaryl Sulfoxides and Diaryl Sulfones
An efficient one-pot approach for the synthesis of diaryl sulfoxides and diaryl sulfones using aryl thiols and aryl diazonium salts was developed. The use of a visible-light-driven silver catalysis and the subsequent singlet-oxygen-induced oxidation enabled selective synthesis of sulfoxides and sulfones in the absence of a photocatalyst. The reactions were carried out under mild reaction conditions; the desired products were obtained under air atmosphere at room temperature.
Kim, Dong Hyuk,Lee, Juyoung,Lee, Anna
supporting information
p. 764 - 767
(2018/02/09)

Effective Utilization of in Situ Generated Hydroperoxide by a Co-SiO2@Ti-Si Core-Shell Catalyst in the Oxidation Reactions
A core-shell catalyst (Co-SiO2@Ti-Si) with cobalt-based SiO2 nanocomposite (Co-SiO2) as the core and Ti-doped mesoporous silica as the shell was designed to catalyze a one-pot reaction of sulfide oxidation with in situ generated hydroperoxide. The catalyst was characterized by SEM, TEM, UV-vis spectroscopy, and XPS, among other methods. Compared to Co-SiO2 and the physical mixture of the two components (Co-SiO2 + Ti-Si), the core-shell catalyst significantly enhanced the reaction rate of the sulfide oxidation. The utilization efficiency of the hydroperoxide was an important factor responsible for the differences in the reaction rates. A further mechanism study showed that the improvement of the efficiency was due to the existence of a coordination pathway. The core-shell structure of a bifunctional catalyst represents a strategy for improving the utilization efficiency of hydroperoxide.
Liu, Meng,Shi, Song,Zhao, Li,Wang, Min,Zhu, Guozhi,Zheng, Xi,Gao, Jin,Xu, Jie
p. 683 - 691
(2018/01/17)

Nickel-Catalyzed Synthesis of Diaryl Sulfones from Aryl Halides and Sodium Sulfinates
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
supporting information
p. 1208 - 1210
(2018/03/21)

Copper(i)-catalyzed sulfonylative Suzuki-Miyaura cross-coupling
Using a simple copper(i) catalyst has allowed a high yielding sulfonylative-Suzuki-Miyaura cross-coupling reaction to be developed. The process provides a single step route to diaryl sulfones from the direct combination of aryl boronic acids, sulfur dioxide and aryl iodides, and represents the first sulfonylative variant of a classic cross-coupling reaction. Sulfur dioxide is delivered from the surrogate reagent, DABSO. Variation of the reaction conditions allowed interruption of the sulfonylative-Suzuki coupling, resulting in the formation of a presumed Cu-sulfinate intermediate. These sulfinates could be trapped as their sodium salts and treated with electrophiles to allow access to arylalkyl sulfones, β-hydroxyl sulfones, sulfonamides and sulfonyl fluorides.
Chen, Yiding,Willis, Michael C.
p. 3249 - 3253
(2017/04/04)

CuI promoted sulfenylation of organozinc reagents with arylsulfonyl chlorides
A CuI promoted sulfenylation of organozinc reagents with arylsulfonyl chlorides/PPh3 has been explored. This reaction proceeded smoothly through an alkyl/aryl radical (generated from organometallics) under mild conditions and produced the desired sulfide products in excellent yields.
Fu, Ying,Su, Yuhu,Xu, Qin-Shan,Du, Zhengyin,Hu, Yulai,Wang, Ke-Hu,Huang, Danfeng
p. 6018 - 6022
(2017/02/05)

Efficient synthesis of aliphatic sulfones by Mg mediated coupling reactions of sulfonyl chlorides and aliphatic halides
Sulfonyl chlorides were reduced to anhydrous sulfinate salts with magnesium under sonication. These sulfinates were alkylated to sulfones with alkyl chlorides in the presence of catalytic sodium iodide under sonication. A variety of aliphatic sulfones was efficiently prepared by this one-pot two-step procedure.
Fu, Ying,Xu, Qin-Shan,Li, Quan-Zhou,Du, Zhengyin,Wang, Ke-Hu,Huang, Danfeng,Hu, Yulai
supporting information
p. 2841 - 2845
(2017/04/03)

An efficient Cu-catalyzed microwave-assisted synthesis of diaryl sulfones
An efficient and microwave-assisted simple protocol for the synthesis of symmetrical/asymmetrical diaryl sulfones through the Cu(II)-catalyzed reaction of sodium salt of sulfinic acid with aryl boronic acid has been described. Various diaryl sulfones have been synthesized in very short reaction times with moderate to very good yields. Additionally, the method is also useful for the synthesis of aryl vinyl sulfones.
Nandi, Ganesh C.
supporting information
p. 319 - 323
(2017/02/10)

The highly selective metal-free oxidation of sulfides, tellurides and phosphines using sodium bromate in the presence of recyclable ionic liquid [bmim]HSO4, at 80°C
The metal-free oxidation of sulfides to sulfones using sodium bromate (NaBrO3) in [bmim]HSO4:H2O (3:1, v/v) at 80°C is reported. Phenylalkyl, phenylbenzyl, diaryl and heteroaryl sulfides were transformed to the corresponding sulfones. Aryl tellurides and phosphines were oxidised to the corresponding telluroxides and phosphine oxides. All the reactions proceeded smoothly and gave high yields in 20-55 min. The ionic liquid [bmim]HSO4 was easily recovered and recycled.
Rajeswari,Lumb, Anshika,Khurana, Jitender M.
p. 442 - 444
(2016/07/21)

Palladium(II)-Catalyzed Synthesis of Sulfinates from Boronic Acids and DABSO: A Redox-Neutral, Phosphine-Free Transformation
A redox-neutral palladium(II)-catalyzed conversion of aryl, heteroaryl, and alkenyl boronic acids into sulfinate intermediates, and onwards to sulfones and sulfonamides, has been realized. A simple Pd(OAc)2 catalyst, in combination with the sulfur dioxide surrogate 1,4-diazabicyclo[2.2.2]octane bis(sulfur dioxide) (DABSO), is sufficient to achieve rapid and high-yielding conversion of the boronic acids into the corresponding sulfinates. Addition of C- or N-based electrophiles then allows conversion into sulfones and sulfonamides, respectively, in a one-pot, two-step process.
Deeming, Alex S.,Russell, Claire J.,Willis, Michael C.
supporting information
p. 747 - 750
(2016/02/27)

Multicomponent Coupling Cyclization Access to Cinnolines via in Situ Generated Diazene with Arynes, and α-Bromo Ketones
A transition-metal-free multicomponent coupling cyclization reaction was explored involving arynes, tosylhydrazine, and α-bromo ketones. The reaction proceeds via a formal [2 + 2 + 2] cycloaddition, giving access to cinnoline derivatives in moderate yields under mild conditions. Three chemical bonds were formed-two C-N bonds and one C-C bond-in a single step.
Shu, Wen-Ming,Ma, Jun-Rui,Zheng, Kai-Lu,Wu, An-Xin
p. 196 - 199
(2016/02/03)

Oxidation of Aryl Sulfides to Sulfones with Alumina-Supported Ruthenium Catalyst in Dimethyl Carbonate-Water Media
A new procedure for the oxidation of sulfides to sulfones utilizing heterogeneous ruthenium reagent has been developed. A small amount of ruthenium trichloride (RuCl3) supported on alumina and excess sodium metaperiodate (NaIO4) was used to produce the ruthenium oxidizing catalyst in the reaction mixture. Sodium metaperiodate oxidized the pre-catalyst RuCl3 to RuO4 and also maintained a constant supply of RuO4 by oxidizing lower valent ruthenium ions during the course of the reaction. An environmentally friendly solvent mixture of dimethyl carbonate (DMC) and water was employed. A wide variety of aromatic sulfides were oxidized to sulfones in good to excellent yields by utilizing this procedure.
Ali, Mohammed Hashmat,Olesen, Bjorn,Ranu, Brindaban,Clippard, Luke,Heath, Jacqueline,Meyer, Garrett,Williams, Tawanika
p. 429 - 436
(2016/01/28)