- Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid-Photoredox Hybrid Catalyst for the Generation of α-Carbonyl Radicals
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A readily accessible organic-inorganic hybrid catalyst is reported for the reductive fragmentation of α-halocarbonyl compounds. The robust hybrid catalyst is a self-stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic study enabled the discovery of the appropriate Lewis acid for the effective LUMO stabilization of α-halocarbonyl compounds and thereby lowering of reduction potential within the range of a standard organic dye. This strategy resolves the issues like dehalogenative hydrogenation or homo-coupling of alkyl radicals by guiding the photoredox cycle through an oxidative quenching pathway. The cooperativity between the photoactive organic dye and the Lewis acid counterparts empowers functionalization with a wide range of coupling partners through efficient and controlled generation of alkyl radicals and serves as an appropriate alternative to the expensive late transition metal-based photocatalysts. To demonstrate the application potential of this cooperative catalytic system, four different synthetic transformations of α-carbonyl bromides were explored with broad substrate scopes.
- Das, Sanju,De Sarkar, Suman,Mandal, Tanumoy
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supporting information
(2021/12/10)
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- Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
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We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
- Zhao, Bin,Hammond, Gerald B.,Xu, Bo
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supporting information
(2021/09/13)
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- Method for preparing beta-carbonyl sulfone
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The invention discloses a method for preparing beta-carbonyl sulfone. The preparation method comprises the following steps: by taking an alpha-carbonyl diazo compound and sodium arylsulfinate as reaction substrates, cheap silver nitrate as an optimal catalyst, 1, 10-phenanthroline as a ligand and potassium persulfate as an oxidant, carrying out coupling reaction in a mixed solvent of acetonitrileand water to obtain the beta-carbonyl sulfone compound. Compared with the prior art, the method has the advantages of wide reaction substrate range, short reaction time, high reaction yield, mild reaction conditions and the like. Non-toxic and harmless reagents are used as reaction raw materials, so that the method is harmless to the environment and meets the requirements of modern green chemicaldevelopment. Post-reaction treatment is simple, and separation and purification are facilitated. In addition, the reaction can realize gram-scale synthesis, and lays a foundation for practical application.
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Paragraph 0032; 0033
(2020/03/12)
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- Cross coupling of sulfonyl radicals with silver-based carbenes: A simple approach to β-carbonyl arylsulfones
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A coupling reaction between sulfonyl radicals and silver-based carbenes has been well established. This simple radical-carbene coupling (RCC) process provided an efficient approach to a variety of β-carbonyl arylsulfones from sodium arylsulfinates and diazo compounds, and was characterized by wide substrate scope, easy scale-up, simple manipulation, accessible starting materials, and mild reaction conditions.
- Li, Jingjing,Lian, Pengcheng,Wan, Xiaobing,Wang, Hanghang,Zheng, Yonggao
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p. 2163 - 2169
(2020/03/27)
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- Modular Synthesis of Carbon-Substituted Furoxans via Radical Addition Pathway. Useful Tool for Transformation of Aliphatic Carboxylic Acids Based on "build-and-Scrap" Strategy
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Utilizing radical chemistry, a new general C-C bond formation on the furoxan ring was developed. By taking advantage of the lability of furoxans, a wide variety of transformation of the synthesized furoxans have been demonstrated. Thus, this developed methodology enabled not only the modular synthesis of furoxans but also short-step transformations of carboxylic acids to a broad range of functional groups.
- Matsubara, Ryosuke,Kim, Hojin,Sakaguchi, Takaya,Xie, Weibin,Zhao, Xufeng,Nagoshi, Yuto,Wang, Chaoyu,Tateiwa, Masahiro,Ando, Akihiro,Hayashi, Masahiko,Yamanaka, Masahiro,Tsuneda, Takao
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supporting information
p. 1182 - 1187
(2020/02/15)
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- Synthesis and biological evaluation of 2-(4-substituted benzene-1-sulfonyl)-N'-(substituted-1-sulfonyl)acetohydrazide as antibacterial agents
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In this study, a series of new sulfone derivatives containing a sulfonohydrazide moiety were synthesized and their structures were determined using 1H NMR, 13C NMR, and HRMS. Then, the in vitro antibacterial activities against Xanthomonas oryzae pv. oryzae (Xoo) and Xanthomonas axonopodis pv. citri (Xac) were evaluated by performing turbidimeter test. Bioactivity results showed that compound 2-(4-fluorobenzene-1-sulfonyl)-N′-(4-fluorobenzene-1-sulfonyl)acetohydrazide (5g) revealed the best antibacterial activities against Xoo and Xac, with the 50percent effective concentration (EC50) values of 25 and 36?μg/mL, respectively, which were superior to those of thiodiazole copper (110 and 230?μg/mL, respectively) and bismerthiazol (84 and 146?μg/mL, respectively).
- Li, Pei,Zhou, Junliang,Liu, Yan,Wang, Xiang
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p. 4559 - 4565
(2020/07/10)
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- Switching of Sulfonylation Selectivity by Nature of Solvent and Temperature: The Reaction of β-Dicarbonyl Compounds with Sodium Sulfinates under the Action of Iron-Based Oxidants
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Selectivity of sulfonylation of β-keto esters with sodium sulfinates under the action of iron(III) salts as oxidants can be regulated by the type of solvent used and the reaction temperature. α-Sulfonyl β-keto esters are obtained when the process is conducted in THF/H2O solution at 40 °C. The change of the solvent to iPrOH/H2O and refluxing of a reaction mixture provides α-sulfonyl esters – the products of successive sulfonylation-deacylation. When β-diketones are applied as starting materials, only α-sulfonyl ketones are formed. The reaction pathway includes sulfonylation of dicabonyl compounds under the action of Fe(III) to form α-sulfonylated dicarbonyl compounds, which are then attacked by a solvent as the nucleophile, resulting in the products of successive sulfonylation-deacylation. Participation of the solvent in the reaction pathway determines the products structure.
- Mulina, Olga M.,Pirgach, Dmitry A.,Nikishin, Gennady I.,Terent'ev, Alexander O.
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p. 4179 - 4188
(2019/05/08)
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- O -Iodoxybenzoic Acid (IBX)-Iodine Mediated One-Pot Deacylative Sulfonylation of 1,3-Dicarbonyl Compounds: A Synthesis of β-Carbonyl Sulfones
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A combination of o-iodoxybenzoic acid (IBX) and a catalytic amount of iodine is found to promote a facile one-pot deacylative sulfonylation reaction of 1,3-dicarbonyl compounds with sodium sulfinates to yield β-carbonyl sulfones. The present method provides the target products bearing a wide variety of functional groups in one step and in good yields.
- Katrun, Praewpan,Songsichan, Teerawat,Soorukram, Darunee,Pohmakotr, Manat,Reutrakul, Vichai,Kuhakarn, Chutima
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supporting information
p. 1109 - 1121
(2017/02/24)
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- Efficient synthesis of aliphatic sulfones by Mg mediated coupling reactions of sulfonyl chlorides and aliphatic halides
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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
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p. 2841 - 2845
(2017/04/03)
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- Bu4NI-Catalyzed Cross-Coupling between Sulfonyl Hydrazides and Diazo Compounds to Construct β-Carbonyl Sulfones Using Molecular Oxygen
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A new cross-coupling reaction between sulfonyl hydrazides and diazo compounds has been established, leading to a variety of β-carbonyl sulfones in good yields. This methodology was distinguished by simple manipulation, easily available starting materials, and wide substrate scope. A plausible mechanism involving a radical process was proposed based upon the experimental observations and literature.
- Wang, Yaxiong,Ma, Liang,Ma, Meihua,Zheng, Hao,Shao, Ying,Wan, Xiaobing
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supporting information
p. 5082 - 5085
(2016/10/14)
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- A method for synthesis of diazo methane compounds
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The invention provides a synthetic method of a diazomethane compound. Diazotized sulfonyl-3,5,5-trimethyl-2-cyclohexenyl acetate is decarboxylated under the action of neutral alumina to obtain the high-purity and high-yield diazomethane compound. The synthetic method is carried out without using nitrosyl chloride which has the characteristics of high toxicity and easy blasting as a reaction raw material is environmentally-friendly and safe. The reaction yield is good, all the reactions are carried out with the temperature in a range from 0 to room temperature, and requirements on energy are low. The posttreatment process of the final product is simple, so expensive silica gel column chromatography separation is avoided. The reactant alumina has the effects of impurity separation and product purification, so the high-purity sulfonyl diazomethane derivative can be obtained through simple reduced pressure pumping filtration and concentration.
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Paragraph 0049; 0050
(2016/10/08)
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- Palladium-Catalyzed Synthesis of (Hetero)Aryl Alkyl Sulfones from (Hetero)Aryl Boronic Acids, Unactivated Alkyl Halides, and Potassium Metabisulfite
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A palladium-catalyzed one-step synthesis of (hetero)aryl alkyl sulfones from (hetero)arylboronic acids, potassium metabisulfite, and unactivated or activated alkylhalides is described. This transformation is of broad scope, occurs under mild conditions, and employs readily available reactants. A stoichiometric experiment has led to the isolation of a catalytically active dimeric palladium sulfinate complex, which was characterized by X-ray diffraction analysis.
- Shavnya, Andre,Hesp, Kevin D.,Mascitti, Vincent,Smith, Aaron C.
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supporting information
p. 13571 - 13575
(2015/11/16)
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- An efficient electrochemical synthesis of β-keto sulfones from sulfinates and 1,3-dicarbonyl compounds
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An efficient electrochemical synthesis of β-keto sulfones from sulfinates and 1,3-dicarbonyl compounds has been developed. The present electrochemical route could afford the target products in high to excellent yields under mild conditions.
- Pan, Xiao-Jun,Gao, Jian,Yuan, Gao-Qing
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p. 5525 - 5530
(2015/08/03)
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- Preparation and reductive transformations of vinylogous sulfonamides (β-sulfonyl enamines), and application to the synthesis of indolizidines
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Condensation between the methiodide salts of 1-alkylpyrrolidine-2-thiones and ethyl [(4-methylphenyl)sulfonyl]acetate or 1-[(4-methylphenyl)sulfonyl]propan-2-one afforded several 2-{[(4-methylphenyl)sulfonyl]methylene}pyrrolidines in good yield. These β-sulfonyl enamines are sufficiently nucleophilic for cyclisation with internal electrophiles to give sulfone-substituted indolizines, potentially useful scaffolds for alkaloid synthesis. The carbon-carbon double bond in vinylogous sulfonamides was reduced stereoselectively either by catalytic hydrogenation or by treatment with sodium borohydride to yield β-sulfonyl amines. The sulfone group in β-acyl-β-sulfonyl enamines could be removed by hydrogenolysis with sodium amalgam in THF-methanol to give enaminones.
- Michael, Joseph P.,De Koning, Charles R.,Malefetse, Tshepo J.,Yillah, Ibrahim
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p. 3510 - 3517
(2007/10/03)
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- Organic reactions in ionic liquids: An efficient method for the synthesis of aryl sulfones by alkylation of sodium arenesulfinates with alkyl halides
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An ionic liquid based on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) is used as a reusable reaction medium for the alkylation of sodium arenesulfinates with alkyl halides. This procedure is convenient, efficient and generally gives rise to the S-alkylated product with high selectivity when applied to active halides.
- Hu, Yi,Chen, Zhen-Chu,Le, Zhang-Gao,Zheng, Qin-Guo
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p. 267 - 269
(2007/10/03)
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- Inhibitors of macrophage migration inhibitory factor and methods for identifying the same
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Inhibitors of MIF are provided which have utility in the treatment of a variety of disorders, including the treatment of pathological conditions associated with MIF activity. The inhibitors of MIF have the following structures: including stereoisomers, prodrugs and pharmaceutically acceptable salts thereof, wherein n, R1, R2, R3, R4, X, Y and Z are as defined herein. Compositions containing an inhibitor of MIF in combination with a pharmaceutically acceptable carrier are also provided, as well as methods for use of the same.
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- Aluminum chloride-iron promoted coupling of sulfonyl chlorides with alkyl halides in aqueous media
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A simple and inexpensive procedure for the coupling of sulfonyl chlorides and alkyl halides with aluminum chloride-iron system at ambient temperature in high yield is achieved in aqueous media.
- Saikia, Promod,Laskar, Dhrubojyoti D.,Prajapati, Dipak,Sandhu, Jagir S.
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p. 512 - 513
(2007/10/03)
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- Synthesis of sulfones from arenesulfonyl chlorides and alkyl halides using the Sm/HgCl2 bimetallic system
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A simple and convenient procedure for the synthesis of sulfones from arenesulfonyl chlorides and alkyl halides using the Sm/HgCl2 bimetallic system in tetrahydrofuran is presented.
- Zhang, Jiming,Zhang, Yongmin
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p. 516 - 517
(2007/10/03)
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- A convenient synthesis of sulfones using zinc mediated coupling reaction of sulfonyl chlorides with alkyl halides in aqueous media
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An efficient procedure for the preparation of sulfones has been developed through a simple reaction of aromatic sulfonyl chlorides with suitable alkyl halides mediated by commercial zinc powder in aqueous media at 0 °C ~ room temperature.
- Sun, Xinghua,Wang, Lei,Zhang, Yongmin
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p. 1785 - 1791
(2007/10/03)
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- Indium-mediated Coupling Reaction of Sulfonyl Chlorides with Alkyl Bromides in Water. A Facile Synthesis of Sulfones
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Indium-mediated coupling of alkyl bromides with aromatic sulfonyl chlorides gives the corresponding sulfones in aqueous media with moderate to good yields.
- Wang, Lei,Zhang, Yongmin
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p. 588 - 589
(2007/10/03)
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- Convenient and Regioselective Syntheses of 3,4-Disubstituted Δ3-Pyrrolin-2-ones Derivatives Starting from 2-Tosyl-3,4-Disubstituted Pyrroles
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3,4-Disubstituted Δ3-pyrrolin-2-ones were prepared in high yields via 5-tosyl-Δ3-pyrrolin-2-ones (4) starting from 2-tosylpyrroles regioselectively.The compounds 4 were found to be useful intermediates for the preparation of variety of Δ3-pyrrolin-2-one derivatives.The reactions of 4 with various nucleophiles and active methylene compounds bearing an appropriate leaving group are described.
- Kinoshita, Hideki,Hayashi, Yoshio,Murata, Yasue,Inomata, Katsuhiko
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p. 1437 - 1440
(2007/10/02)
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- A Novel Synthesis of Sulfones via the O,O-Diethylphosphorotellurite Ion-Assisted Coupling of Arenesulfonyl Chlorides with Active Halides
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Arenesulfonyl chlorides undergo a facile onepot coupling reaction with active halides assisted by sodium O,O-diethylphosphorotellurite to give the corresponding sulfones in excellent yield.
- Huang, Xian,Pi, Jin-Hong
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p. 2291 - 2295
(2007/10/02)
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- A simple and rapid preparation of sulfones from alkyl halides using ultrasound
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Appropriate alkyl halides and sodium p-toluenesulfinates react rapidly in DMF-water at room temperature under the influence of ultrasound to afford sulfones. Using this procedure a wide variety of sulfones have been prepared.
- Biswas,Jash,Bhattacharyya
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p. 491 - 492
(2007/10/02)
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- The Cathodic Desulfonylation of 1-Ethoxycarbonyl- and 1-Cyano-1-(p-tolylsulfonyl)-2-phenylethenes at the Mercury Electrode in Nonaqueous Solvents
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The cathodic reduction of 1-ethoxycarbonyl-1-(p-tolylsulfonyl)-2-phenylethene in MeCN and DMF is characterized by the selective elimination of the p-tolylsulfonyl group, resulting in the formation of ethyl (E)-cinnamate in good yields, in the presence of such efficient proton donors as benzoic acid and acetic acid.On the other hand, the cathodic desulfonylation of 1-cyano-1-(p-tolylsulfonyl)-2-phenylethene proceeds with low efficiencies, even in the presence of acetic acid and benzoic acid.
- Kunugi, Akira,Abe, Kyo
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p. 3329 - 3331
(2007/10/02)
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