- Pyridylidene Amide Ru Complex for Selective Oxidation in Organic Synthesis
-
The ruthenium(II) bis(PYA) complex 1 (PYA = p-pyridylidene amide) is a powerful catalyst for the oxidation of sulfides to sulfones, of alkenes to carbonyl compounds, and of terminal alkynes to carboxylic acids by using NaIO4 as the terminal oxidant. The catalytic system shows a broad functional group tolerance and rate differences between alkyne and sulfide oxidation that are sufficiently large to effectively achieve selective sulfide oxidation with exquisite selectivity.
- Bertini, Simone,Henryon, Dorothée,Edmunds, Andrew J. F.,Albrecht, Martin
-
supporting information
p. 1378 - 1382
(2022/02/23)
-
- Microwaves assisted synthesis of antitumor agents of novel azoles, azines, and azoloazines pendant to phenyl sulfone moiety and molecular docking for VEGFR-2 kinase
-
The present research article contains two valuable starting phenylsulfone-enaminones which were synthesized in short reaction time with excellent yield under microwaves irradiation. These two enaminones were reacted with both nucleophiles and electrophiles to afford novel heterocycles bearing phenylsulfone moiety. The structure of all prepared phenylsulfone derivatives as well as their mechanistic pathways were studied based on their spectral data. Moreover, seventeen phenylsulfone derivatives were screened in vitro for their anticancer activity against HepG-2 and HCT-116 cell lines. Compounds 4 and 7a were equipotent to doxorubicin against HepG-2 cell line. Moreover, diphenyl sulfone derivative 7a was 3-fold more potent than doxorubicin against human colon cancer cell line with IC50 = 3.13 and 9.4 μg/mL, respectively. Remarkably, compound 7b was 2-fold more active than doxorubicin against the two tested cell lines. A docking study of title compounds into VEGFR-2 kinase was also conducted.
- Abdulwahab, Hanan Gaber,Alsaedi, Amani M. R.,Farghaly, Thoraya A.,Shaaban, Mohamed R.
-
-
- 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)
-
- Sulfonylation of Aryl Halides by Visible Light/Copper Catalysis
-
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
-
p. 3663 - 3668
(2021/05/31)
-
- 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.
- -
-
Paragraph 0075-0079
(2021/03/31)
-
- 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
-
-
- 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)
-
- 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)
-
- HETEROCYCLIC CARBOXYLIC ACID AMIDE LIGAND AND APPLICATIONS THEREOF IN COPPER CATALYZED COUPLING REACTION OF ARYL HALOGENO SUBSTITUTE
-
Provided are a heterocyclic carboxylic acid amide ligand and applications thereof in a copper catalyzed coupling reaction. Specifically, provided are uses of a compound represented by formula (I), definitions of radical groups being described in the specifications. The compound represented by formula (I) can be used as the ligand in the copper catalyzed coupling reaction of the aryl halogeno substitute, and is used or catalyzing the coupling reaction for forming the aryl halogeno substitute having C—N, C—O, C—S and other bonds.
- -
-
Paragraph 0293-0294
(2019/05/15)
-
- 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.
- -
-
Paragraph 0060-0063
(2019/02/13)
-
- 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)
-
- A Class of Amide Ligands Enable Cu-Catalyzed Coupling of (Hetero)aryl Halides with Sulfinic Acid Salts under Mild Conditions
-
The amide derived from 4-hydroxy-l-proline and 2,6-dimethylaniline is a powerful ligand for Cu-catalyzed coupling of (hetero)aryl halides with sulfinic acid salts, allowing the formation of a wide range of (hetero)aryl sulfones from the corresponding (hetero)aryl halides at considerably low catalytic loadings. The coupling of (hetero)aryl iodides and sodium methanesulfinate proceeds at room temperature with only 0.5 mol % CuI and ligand, representing the first example for Cu-catalyzed arylation at both low catalytic loading and room temperature.
- Zhao, Jinlong,Niu, Songtao,Jiang, Xi,Jiang, Yongwen,Zhang, Xiaojing,Sun, Tiemin,Ma, Dawei
-
p. 6589 - 6599
(2018/05/31)
-
- 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)
-
- 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)
-
- 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
-
-
- 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)
-
- 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)
-
- A PROCESS FOR THE SYNTHESIS OF ARYL SULFONES
-
The present patent discloses a novel, efficient and transition-metal-free room temperature single step process for synthesis of aryl sulfones and substituted aryl sulfones starting from aryl substrates.
- -
-
Page/Page column 10; 12; 18
(2015/06/25)
-
- Copper-catalysed coupling of aryl tosylates with sodium arylsulfinates
-
Diaryl sulfones derivatives were easily synthesised from aryl tosylates and sodium arylsulfinates in high yields using [Cu(CH3CN)4]PF6 as catalyst. The transformation is efficient, simple and the starting materials are readily available.
- Wang, Chunjie,Zhang, Hui,Li, Zhiwei,Wang, Ziyun
-
p. 639 - 642
(2015/02/02)
-
- Magnetically separable copper ferrite nanoparticles-catalyzed synthesis of diaryl, alkyl/aryl sulfones from arylsulfinic acid salts and organohalides/boronic acids
-
A recyclable, inexpensive, non-toxic and environmentally benign catalytic system comprised of magnetically separable copper ferrite (CuFe 2O4) nanoparticles has been developed for the synthesis of diaryl, alkyl/aryl sulfones. Arylsulfinic acid salts are coupled with various alkyl/aryl halides/boronic acids to afford the corresponding diaryl, alkyl/aryl sulfones in good to excellent yields under the identical catalytic system. A wide range of functional group tolerance, with facile recovery of the catalyst by application of an external magnetic field, and consistently high catalytic efficiency for five consecutive cycles render the protocol operationally attractive.
- Srinivas,Rawat, Vikas S.,Konda, Kavitha,Sreedhar, Bojja
-
p. 805 - 817
(2014/04/03)
-
- Transition-metal-free C-S bond formation: A facile access to aryl sulfones from sodium sulfinates via arynes
-
Sulfones have been attractive targets for synthetic organic chemists owing to their immense applications in medicinal, material, and synthetic chemistry. In this context, an efficient transition-metal-free process has been demonstrated, wherein a broad range of alkyl/aryl/heteroaryl sodium sulfinates react with varyingly substituted aryne precursors (o-silyl aryl triflates) under mild reaction conditions to afford structurally diverse sulfones in good to excellent yields.
- Pandya, Virat G.,Mhaske, Santosh B.
-
supporting information
p. 3836 - 3839
(2014/08/05)
-
- Diaryl sulfones synthesis with aryltrifluoroborates and aryl sulfinic salts under mild conditions
-
CuI-catalysed cross-coupling reactions of various aryltrifluoroborates with aryl sulfinic salts have been achieved in good yields. A new efficient method is described for the conversion of potassium aryltrifluoroborates into diaryl sulfones. The reported reactions are tolerant to common functional groups regardless of whether they are electron-rich or electron-deficient, making this transformation an attractive alternative to traditional approaches.
- Zhang, Wei,Li, Ke,Zhao, Baoli
-
p. 269 - 271
(2014/06/09)
-
- A highly active and easily recoverable chitosan@copper catalyst for the C-S coupling and its application in the synthesis of zolimidine
-
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
-
supporting information
p. 3007 - 3012
(2014/06/10)
-
- D-Glucosamine as a green ligand for copper catalyzed synthesis of aryl sulfones from aryl halides and sodium sulfinates
-
d-Glucosamine is reported for the first time as a green ligand for copper catalyzed coupling of aryl halides and sodium sulfinates, which provides a simple and extremely efficient new route to unsymmetrical diaryl sulfones. The catalytic reaction proceeded in DMSO-H2O at 100°C and gave a variety of aryl sulfones in high yields. The high water solubility of the ligand enables easy catalyst removal. The scope of the method was validated by a single step synthesis of marketed drug zolimidine, a drug used for peptic ulcers, in 65% yield.
- Yang, Ming,Shen, Hongyun,Li, Yuanyuan,Shen, Chao,Zhang, Pengfei
-
p. 26295 - 26300
(2014/07/08)
-
- BIARYL INHIBITORS OF THE SODIUM CHANNEL
-
The invention relates to compounds useful in treating conditions associated with voltage- gated ion channel function, particularly conditions associated with sodium channel activity. More specifically, the invention concerns biaryl derivatives (e.g., compounds according to any of Formulas (I)-(XII) or Compounds (l)-(372) of Table 1) that are that are useful in treatment of conditions such as epilepsy, cancer, pain, migraine, Parkinson's Disease, mood disorders, schizophrenia, psychosis, tinnitus, amyotropic lateral sclerosis, glaucoma, ischaemia, spasticity disorders, obsessive compulsive disorder, restless leg syndrome and Tourette syndrome.
- -
-
-
- A mild and efficient synthesis of aryl sulfones from aryl chlorides and sulfinic acid salts using microwave heating
-
The CuCl-catalyzed coupling of aryl chlorides and sulfinic acid salts provides a simple and extremely efficient route to unsymmetrical aryl sulfones in high to excellent yields under microwave irradiation within 3-30 minutes. Georg Thieme Verlag Stuttgart · New York.
- Yuan, Yan-Qin,Guo, Sheng-Rong
-
supporting information; experimental part
p. 2750 - 2756
(2011/12/04)
-
- The synthesis and SAR of novel diarylsulfone 11β-HSD1 inhibitors
-
In this communication, human 11β-hydroxysteroid dehydrogenase type 1 (11β-HSD1) inhibitory activities of a novel series of diarylsulfones are described. Optimization of this series resulted in several highly potent 11β-HSD1 inhibitors with excellent pharmacokinetic (PK) properties. Compound (S)-25 showed excellent efficacy in a non-human primate ex vivo pharmacodynamic model.
- Yan, Xuelei,Wang, Zhulun,Sudom, Athena,Cardozo, Mario,Degraffenreid, Michael,Di, Yongmei,Fan, Pingchen,He, Xiao,Jaen, Juan C.,Labelle, Marc,Liu, Jinsong,Ma, Ji,McMinn, Dustin,Miao, Shichang,Sun, Daqing,Tang, Liang,Tu, Hua,Ursu, Stefania,Walker, Nigel,Ye, Qiuping,Powers, Jay P.
-
scheme or table
p. 7071 - 7075
(2011/01/03)
-
- Synthesis of aryl sulfones via L-proline-promoted CuI-catalyzed coupling reaction of aryl halides with sulfinic acid salts
-
(Chemical Equation Presented) The CuI/L-proline sodium salt catalyzed coupling reaction of aryl halides with sulfinic acid salts readily occurs at 80-95°C in DMSO to give the corresponding aryl sulfones in good to excellent yields. This process is well-tolerated by a wide range of functional groups including hydroxyl, amino, acetanilide, ketone, ester, and nitrile. Using this method, 4-phenylsulfonyl- and 4-methanesulfonyl-substituted L-phenylalanine derivatives are prepared.
- Zhu, Wei,Ma, Dawei
-
p. 2696 - 2700
(2007/10/03)
-
- Synthesis and Biological Activity of a Series of Diaryl-Substituted α-Cyano-β-hydroxypropenamides, a New Class of Anthelmintic Agents
-
A series of α-cyano-β-hydroxypropenamides was prepared and tested for anthelmintic activity. α-Cyano-β-hydroxy-N--3-propenamide (1) showed good activity against the nematode Nematospirodes dubius in a mixed parasite infection in mice; several of the analogues were also effective against the cestode Hymenolepis nana.In sheep trials, 1 caused 100percent reduction of the hematophagous nematode Haemonchus contortus after a single dose of 20 mg/kg but did not show satisfactory control of Trichostrongylus colubriformis or Ostertagia circumcincta.Against the liver fluke Fasciola hepatica, 1 suppressed egg production but only temporarily, suggesting that the adult flukes were not eliminated.Mechanism of action studies on 1 using Ascaris mitochondria showed it to be an uncoupler of oxidative phosphorylation.
- Sjogren, Eric B.,Rider, Michael A.,Nelson, Peter H.,Bingham, Stanford,Poulton, Anthony L.,et al.
-
p. 3295 - 3301
(2007/10/02)
-
- 1-[β(R-thio)phenethyl]imidazoles and derivatives thereof
-
Novel 1-[β-(R-thio)phenethyl]-imidazoles and the corresponding 1-[β-(R-sulfinyl)phenethyl]imidazoles and 1-[β-(R-sulfonyl)phenethyl]imidazoles wherein R is alkyl, alkenyl, aralkenyl, substituted aralkenyl, alkynyl, cycloalkyl, cycloalkyl alkyl, aralkyl, substituted aralkyl, aryl or substituted aryl; and the antimicrobial acid addition salts thereof, are useful as antifungal, anti-bacterial and anti-protozoal agents.
- -
-
-