- Visible-Light-Mediated Synthesis of Sulfonyl Fluorides from Arylazo Sulfones
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Sulfonyl fluorides are useful motifs for a wide range of applications in organic synthesis including sulfur (VI) fluoride exchange-based “click chemistry.” Herein, a visible-light-mediated synthesis of sulfonyl fluorides from arylazo sulfones is described. In the present study, K2S2O5 and N-fluorobenzenesulfonimide (NFSI) were used as the sulfonyl source and fluorinating agent, respectively, for visible-light-mediated fluorosulfonylation of arylazo sulfones to prepare various sulfonyl fluorides in 60–85% yield. This protocol is a synthetic approach to provide useful sulfonyl fluoride structures at room temperature. (Figure presented.).
- Bui, Tien Tan,Tran, Van Hieu,Kim, Hee-Kwon
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supporting information
p. 341 - 347
(2021/10/14)
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- Copper-catalyzed three-component reaction of arylhydrazine hydrochloride, DABSO, and NFSI for the synthesis of arenesulfonyl fluorides
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This paper reports a convenient copper-catalyzed three-component conversion of arylhydrazine hydrochlorides to arenesulfonyl fluorides in good yields under mild conditions, using 1,4-diazabicyclo [2.2.2]octane bis(sulfur dioxide) (DABSO) as a sulfonyl source andN-fluorobenzenesulfonimide (NFSI) as a fluorine source based on a radical sulfur dioxide insertion and fluorination strategy. Notably, arylhydrazine hydrochloride is used as a safe precursor of aryl radicals.
- Chen, Qing-Yun,Guo, Yong,Hu, Xiaojun,Liu, Chao,Liu, Yongan,Ma, Xiaoyu,Pan, Qijun,Pang, Wan,Wu, Jingjing
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supporting information
p. 8999 - 9003
(2021/11/04)
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- Method for preparing aryl sulfonyl fluoride by using aryl hydrazine hydrochloride as raw material
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The invention relates to a method for preparing aryl sulfonyl fluoride by using aryl hydrazine hydrochloride as a raw material. According to the method, aryl sulfonyl fluoride is synthesized by taking the aryl hydrazine hydrochloride as a raw material and adding a sulfur dioxide source and a fluorination reagent under the conditions of copper salt catalysis and alkali promotion through a strategy of insertion and fluorination of free radical sulfur dioxide. Compared with the prior art, the aryl sulfonyl fluoride is synthesized under the oxidation condition, and the influence of air on the reaction is not obvious in an experiment; and the reaction synthesis method is simple, good in selectivity, excellent in yield, mild in reaction condition, short in reaction time and universal to various aryl hydrazine hydrochloride substrates, and the method provides a new thought for synthesis of aryl sulfonyl fluoride.
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Paragraph 0088-0092
(2021/11/06)
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- Unbalanced-Ion-Pair-Catalyzed Nucleophilic Fluorination Using Potassium Fluoride
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An unbalanced ion pair promoter (e.g., tetrabutylammonium sulfate), consisting of a bulky and charge-delocalized cation and a small and charge-localized anion, greatly accelerates nucleophilic fluorinations using easy handling KF. We also successfully converted an inexpensive and commercially available ion-exchange resin to the polymer-supported ion pair promoter (A26–SO42–), which could be reused after filtration. Moreover, A26–SO42– can be used in continuous flow conditions. In our conditions, water is well-tolerated.
- Hammond, Gerald B.,Li, Wangbing,Lu, Zhichao,Xu, Bo
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supporting information
p. 9640 - 9644
(2021/12/14)
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- Metal-Free Visible-Light Synthesis of Arylsulfonyl Fluorides: Scope and Mechanism
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The first metal-free procedure for the synthesis of arylsulfonyl fluorides is reported. Under organo-photoredox conditions, aryl diazonium salts react with a readily available SO2 source (DABSO) to afford the desired product through simple nucleophilic fluorination. The reaction tolerates the presence of both electron-rich and -poor aryls and demonstrated a broad functional group tolerance. To shed the light on the reaction mechanism, several experimental techniques were combined, including fluorescence, NMR, and EPR spectroscopy as well as DFT calculations.
- Louvel, Dan,Chelagha, Aida,Rouillon, Jean,Payard, Pierre-Adrien,Khrouz, Lhoussain,Monnereau, Cyrille,Tlili, Anis
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supporting information
p. 8704 - 8708
(2021/05/17)
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- Redox-Neutral Organometallic Elementary Steps at Bismuth: Catalytic Synthesis of Aryl Sulfonyl Fluorides
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A Bi-catalyzed synthesis of sulfonyl fluorides from the corresponding (hetero)aryl boronic acids is presented. We demonstrate that the organobismuth(III) catalysts bearing a bis-aryl sulfone ligand backbone revolve through different canonical organometallic steps within the catalytic cycle without modifying the oxidation state. All steps have been validated, including the catalytic insertion of SO2 into Bi-C bonds, leading to a structurally unique O-bound bismuth sulfinate complex. The catalytic protocol affords excellent yields for a wide range of aryl and heteroaryl boronic acids, displaying a wide functional group tolerance.
- Cornella, Josep,Magre, Marc
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supporting information
p. 21497 - 21502
(2022/01/03)
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- Synthesis of Sulfonyl Fluorides from Sulfonamides
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A simple and practical synthesis of sulfonyl fluorides from sulfonamides is reported. The method capitalizes on the formation of the sulfonyl chloride by virtue of the reaction of Pyry-BF4 and MgCl2, and subsequent in situ conversion to the more robust and stable sulfonyl fluoride by the presence of KF. The mild conditions and high chemoselectivity of the protocol enable the late-stage formation of sulfonyl fluorides from densely functionalized molecules.
- Pérez-Palau, Marina,Cornella, Josep
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supporting information
p. 2497 - 2500
(2020/03/11)
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- Arenesulfonyl Fluoride Synthesis via Copper-Catalyzed Fluorosulfonylation of Arenediazonium Salts
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We report herein a general and practical copper-catalyzed fluorosulfonylation reaction of a wide range of abundant arenediazonium salts to smoothly prepare various arenesulfonyl fluorides using the 1,4-diazabicyclo[2.2.2]octane-bis(sulfur dioxide) adduct as a convenient sulfonyl source in combination with KHF2 as an ideal fluorine source and without the need for additional oxidants. Interestingly, the electronic character of the arene ring in the starting arenediazonium salts has a significant impact on the reaction mechanistic pathway.
- Liu, Yongan,Yu, Donghai,Guo, Yong,Xiao, Ji-Chang,Chen, Qing-Yun,Liu, Chao
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supporting information
p. 2281 - 2286
(2020/03/13)
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- Fluorosulfonylation of arenediazonium tetrafluoroborates with Na2S2O5 and N-fluorobenzenesulfonimide
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A transition-metal-free Sandmeyer-type fluorosulfonylation reaction has been achieved by the three-component reaction of arenediazonium tetrafluoroborates, Na2S2O5, and N-fluorobenzenesulfonimide (NFSI). The reaction proceeds through a radical tandem process, affording various arenesulfonyl fluorides in moderate to high yields. This protocol not only provides a complement to the previous fluorosulfonylation reactions, but also extends the applications of Sandmeyer reaction.
- Huang, Yangen,Liu, Shuai,Qing, Feng-Ling,Xu, Xiu-Hua
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- Copper-free Sandmeyer-type Reaction for the Synthesis of Sulfonyl Fluorides
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A copper-free Sandmeyer-type fluorosulfonylation reaction is reported. Utilizing Na2S2O5 and Selectfluor as the sulfur dioxide and fluorine sources, respectively, aryldiazonium salts were transformed into sulfonyl fluorides. The one-pot direct synthesis of sulfonyl fluorides from aromatic amines was also realized via in situ diazotization. The practicality of this method was demonstrated by the broad functional group tolerance, gram-scale synthesis, and late-stage fluorosulfonylation of natural products and pharmaceuticals.
- Zhong, Tao,Pang, Meng-Ke,Chen, Zhi-Da,Zhang, Bin,Weng, Jiang,Lu, Gui
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supporting information
p. 3072 - 3078
(2020/04/10)
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- Arenesulfonyl Fluoride Synthesis via Copper-free Sandmeyer-type Fluorosulfonylation of Arenediazonium Salts
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The limited availability of highly valuable arenesulfonyl fluorides seriously hinders their further application in many research fields including medicinal chemistry and chemical biological, organic synthesis, polymer preparation, etc. We report herein a mild and efficient copper-free Sandmeyer-type fluorosulfonylation reaction of various arenediazonium salts to prepare valuable arenesulfonyl fluorides using K2S2O5 as both a reductant and a practical sulfonyl source in combination with N-fluorobenzenesulfonimide as an effective fluorine source. This methodology provides an attractive route to diverse important arenesulfonyl fluorides given the overall practicality and scope.
- Lin, Qiongzhen,Ma, Zhanhu,Zheng, Changge,Hu, Xiao-Jun,Guo, Yong,Chen, Qing-Yun,Liu, Chao
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supporting information
p. 1107 - 1110
(2020/07/06)
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- Directed ortho-Metalation of Arenesulfonyl Fluorides and Aryl Fluorosulfates
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Studies on directed ortho -metalation (DoM) of arenesulfonyl fluorides (ArSO 2 F) with in situ electrophile trapping are presented. Under optimized conditions (LDA, THF, -78 °C), a series of model substrates was mono- and difunctionalized with trimethylsilyl chloride in good yields. The synthetic results reveal powerful directing character of the SO 2 F group, being ahead of bromine and methoxy substituents. Under the same metalation conditions, aryl fluorosulfates (ArOSO 2 F) display fragmentation to arynes and migration of the SO 2 F group to the ortho position (anionic thia-Fries rearrangement).
- Talko, Alicja,Antoniak, Damian,Barbasiewicz, Micha?
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p. 2278 - 2286
(2019/05/24)
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- One-pot fluorosulfurylation of Grignard reagents using sulfuryl fluoride
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Herein, we report a new method for the one-pot syntheses of sulfonyl fluorides. Addition of an alkyl, aryl, or heteroaryl Grignard to a solution of sulfuryl fluoride at ambient temperature affords the desired sulfonyl fluorides in 18-78% yield. Furthermore, this method is applicable for in situ sequential reactions, whereby the Grignard reagent can be converted to the corresponding diarylsulfone, sulfonate ester, or sulfonamide in a one-pot process.
- Lee, Cayo,Ball, Nicholas D.,Sammis, Glenn M.
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supporting information
p. 14753 - 14756
(2019/12/23)
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- Sulfonyl Fluoride Synthesis through Electrochemical Oxidative Coupling of Thiols and Potassium Fluoride
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Sulfonyl fluorides are valuable synthetic motifs for a variety of applications, among which sulfur(VI) fluoride exchange-based "click chemistry" is currently the most prominent. Consequently, the development of novel and efficient synthetic methods to access these functional groups is of great interest. Herein, we report a mild and environmentally benign electrochemical approach to prepare sulfonyl fluorides using thiols or disulfides, as widely available starting materials, in combination with KF, as an inexpensive, abundant and safe fluoride source. No additional oxidants nor additional catalysts are required and, due to mild reaction conditions, the reaction displays a broad substrate scope, including a variety of alkyl, benzyl, aryl and heteroaryl thiols or disulfides.
- Laudadio, Gabriele,Bartolomeu, Aloisio De A.,Verwijlen, Lucas M. H. M.,Cao, Yiran,De Oliveira, Kleber T.,No?l, Timothy
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supporting information
p. 11832 - 11836
(2019/08/26)
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- Merging [2+2] Cycloaddition with Radical 1,4-Addition: Metal-Free Access to Functionalized Cyclobuta[a]naphthalen-4-ols
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A metal-free [2+2] cycloaddition and 1,4-addition sequence induced by S-centered radicals has been achieved by treating benzene-linked allene-ynes with aryldiazonium tetrafluoroborates and DABCO-bis(sulfur dioxide) in a one-pot procedure. The reaction provides a greener and more practical access to functionalized cyclobuta[a]naphthalen-4-ols with valuable applications. More than 50 examples are demonstrated with excellent diastereoselectivity and chemical yields. The reaction pathway is proposed to proceed by the following steps:[2+2] cycloaddition, insertion of SO2, 1,4-addition, diazotization, and tautomerization.
- Liu, Feng,Wang, Jia-Yin,Zhou, Peng,Li, Guigen,Hao, Wen-Juan,Tu, Shu-Jiang,Jiang, Bo
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supporting information
p. 15570 - 15574
(2017/12/02)
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- A study of the reactivity of S(VI)-F containing warheads with nucleophilic amino-acid side chains under physiological conditions
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Sulfonyl fluorides (SFs) have recently emerged as a promising warhead for the targeted covalent modification of proteins. Despite numerous examples of the successful deployment of SFs as covalent probe compounds, a detailed exploration of the factors influencing the stability and reactivity of SFs has not yet appeared. In this work we present an extensive study on the influence of steric and electronic factors on the reactivity and stability of the SF and related SVI-F groups. While SFs react rapidly with N-acetylcysteine, the resulting adducts were found to be unstable, rendering SFs inappropriate for the durable covalent inhibition of cysteine residues. In contrast, SFs afforded stable adducts with both N-acetyltyrosine and N-acetyllysine; furthermore, we show that the reactivity of arylsulfonyl fluorides towards these nucleophilic amino acids can be predictably modulated by adjusting the electronic properties of the warhead. These trends were largely conserved when the covalent reaction occurred within a protein binding pocket. We have also obtained a crystal structure depicting covalent modification of the catalytic lysine of a tyrosine kinase (FGFR1) by the ATP analog 5′-O-3-((fluorosulfonyl)benzoyl)adenosine (m-FSBA). Highly reactive warheads were demonstrated to be unstable with respect to hydrolysis in buffered aqueous solutions, indicating that warhead reactivity must be carefully tuned to provide optimal rates of protein modification. Our results demonstrate that the reactivity of SFs complements that of more commonly studied acrylamides, and we hope that this work spurs the rational design of novel SF-containing covalent probe compounds and inhibitors, particularly in cases where a suitably positioned cysteine residue is not present.
- Mukherjee,Debreczeni,Breed,Tentarelli,Aquila,Dowling,Whitty,Grimster
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supporting information
p. 9685 - 9695
(2017/11/30)
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- Pd-Catalyzed Conversion of Aryl Iodides to Sulfonyl Fluorides Using SO2 Surrogate DABSO and Selectfluor
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A one-pot Pd-catalyzed conversion of aryl iodide to aryl sulfonyl fluorides using DABSO and Selectfluor has been developed generating aryl sulfonyl fluorides in good to excellent yields. The reaction results in the generation of electronically and sterically diverse sulfonyl fluorides. Additionally, sulfonyl fluorides can be converted to aryl sulfonamides and sulfonic esters using Cs2CO3 under mild conditions.
- Tribby, Ariana L.,Rodríguez, Ismeraí,Shariffudin, Shamira,Ball, Nicholas D.
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p. 2294 - 2299
(2017/02/26)
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- One-pot palladium-catalyzed synthesis of sulfonyl fluorides from aryl bromides
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A mild, efficient synthesis of sulfonyl fluorides from aryl and heteroaryl bromides utilizing palladium catalysis is described. The process involves the initial palladium-catalyzed sulfonylation of aryl bromides using DABSO as an SO2 source, followed by in situ treatment of the resultant sulfinate with the electrophilic fluorine source NFSI. This sequence represents the first general method for the sulfonylation of aryl bromides, and offers a practical, one-pot alternative to previously described syntheses of sulfonyl fluorides, allowing rapid access to these biologically important molecules. Excellent functional group tolerance is demonstrated, with the transformation successfully achieved on a number of active pharmaceutical ingredients, and their precursors. The preparation of peptide-derived sulfonyl fluorides is also demonstrated.
- Davies, Alyn T.,Curto, John M.,Bagley, Scott W.,Willis, Michael C.
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p. 1233 - 1237
(2017/02/10)
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- Copper(i)-catalyzed sulfonylative Suzuki-Miyaura cross-coupling
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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.
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p. 3249 - 3253
(2017/04/04)
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- Oxidation of disulfides with electrophilic halogenating reagents: Concise methods for preparation of thiosulfonates and sulfonyl halides
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The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. Conversely, the reaction of disulfides with 6.5 equiv of Selectfluor or thiosulfonates with 4.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluorides in high yields. Accufluor and FP-T300 are also effective in preparing sulfonyl fluorides from disulfides under the similar reaction conditions. Sulfonyl chlorides or sulfonyl bromides were effectively obtained from the reaction of disulfides with 6 equiv of either N-chlorosuccinimide or N-bromosuccinimide in acetonitrile/water (10:1) at room temperature. Some other electrophilic chlorinating or brominating reagents are also able to be used instead of N-chlorosuccinimide or N-bromosuccinimide for the syntheses of sulfonyl halides from disulfides. These reactions of disulfides with electrophilic halogenating reagents are convenient methods to prepare thiosulfonates and sulfonyl halides.
- Kirihara, Masayuki,Naito, Sayuri,Nishimura, Yuki,Ishizuka, Yuki,Iwai, Toshiaki,Takeuchi, Haruka,Ogata, Tomomi,Hanai, Honoka,Kinoshita, Yukari,Kishida, Mari,Yamazaki, Kento,Noguchi, Takuya,Yamashoji, Shiro
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p. 2464 - 2471
(2014/04/03)
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- Ascertaining the suitability of aryl sulfonyl fluorides for [18F]radiochemistry applications: A systematic investigation using microfluidics
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Optimization of [18F]radiolabeling conditions and subsequent stability analysis in mobile phase, PBS buffer, and rat serum of 12 aryl sulfonyl chloride precursors with various substituents (electron-withdrawing groups, electron-donating groups, increased steric bulk, heterocyclic) were performed using an Advion NanoTek Microfluidic Synthesis System. A comparison of radiochemical yields and reaction times for a microfluidics device versus a conventional reaction vessel is reported. [18F]Radiolabeling of sulfonyl chlorides in the presence of competing nucleophiles, H-bond donors, and water was also assessed and demonstrated the versatility and potential utility of [18F]sulfonyl fluorides as synthons for indirect radiolabeling. Published 2013 by the American Chemical Society.
- Matesic, Lidia,Wyatt, Naomi A.,Fraser, Benjamin H.,Roberts, Maxine P.,Pham, Tien Q.,Greguric, Ivan
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p. 11262 - 11270
(2013/12/04)
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- Oxidation of disulfides with Selectfluor: Concise syntheses of thiosulfonates and sulfonyl fluorides
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The reaction of aromatic or benzylic disulfides with 2.5 equiv of Selectfluor in acetonitrile/water (10:1) at room temperature efficiently produced the corresponding thiosulfonates. On the other hand, the reaction of disulfides with 6.5 equiv of Selectfluor in refluxing acetonitrile/water (10:1) provided sulfonyl fluoride in high yields.
- Kirihara, Masayuki,Naito, Sayuri,Ishizuka, Yuki,Hanai, Honoka,Noguchi, Takuya
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experimental part
p. 3086 - 3089
(2011/06/26)
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- Muscarinic M2 antagonists: Anthranilamide derivatives with exceptional selectivity and in vivo activity
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Anthranilamide analogues such as 23 are potent and highly selective muscarinic M2 antagonists that also show good oral bioavailability and in vivo activity.
- Clader, John W.,Billard, William,Binch III, Herbert,Chen, Lian-Yong,Crosby Jr., Gordon,Duffy, Ruth A.,Ford, Jennifer,Kozlowski, Joseph A.,Lachowicz, Jean E.,Li, Shengjian,Liu, Charles,McCombie, Stuart W.,Vice, Susan,Zhou, Gowei,Greenlee, William J.
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p. 319 - 326
(2007/10/03)
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- Method for preparing alpha-sulfonyl hydroxamic acid derivatives
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Compounds of the formula: that can be important as matrix metalloproteinase (MMP) and TNF-alpha converting enzyme (TACE) inhibitors, phosphodiesterase inhibitors, renin inhibitors, antithrombotics, and 5-lipoxygenase inhibitors are prepared by novel methods of the present invention.
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- An efficient method to prepare α-sulfonyl hydroxamic acid derivatives
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α-Sulfonyl hydroxamic acid derivatives are biologically important molecules. An efficient protocol has been developed to make these molecules via a direct sulfonylation of enolates. Several piperidine containing α-sulfonyl hydroxamic acid compounds have been prepared by this procedure.
- Sandanayaka, Vincent P.,Zask, Arie,Venkatesan, Aranapakam M.,Baker, Jannie
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p. 4605 - 4607
(2007/10/03)
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- Oxidation of Aromatic Compounds. III. Oxidation of Substituted Phenols and Their O-Derivatives in the System HSO3F-PbO2
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Low-temperature oxidation of substituted phenols and their O-derivatives in the system HSO3F-PbO2 involves intermediate formation of radical cations and dications.The reaction allows preparative syntheses of aryl fluorosulfonates, various benzyl alcohol derivatives, biaryls, and diarylmethanes with electron-acceptor substituents.
- Aver'yanov, S. F.,Rudenko, A. P.
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p. 1089 - 1098
(2007/10/03)
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- Cross-interaction Constants as a Measure of the Transition-state Structure. Part 1. The Degree of Bond Formation in Nucleophilic Substitution Reactions
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The kinetic of seven reaction series in methanol involving halides as leaving groups and aromatic amines as nucleophiles are reported.Analyses of various Hammett ρ values, especially the cross-interaction constants ρXY between substituents X in the nucleophile and Y in the substrate, are used to characterize the transition-state structure for the nucleophilic substitution reactions.The degree of bond formation in the transition state as measured by /ρXY/ indicated that the reactions can be classified into two groups according to the magnitude of the cross-interaction constants; the fluoride series gave larger /ρXY/ values indicating a greater degree of bond formation, under the same reactants condition, compared with other series with relatively good leaving groups, e.g.Cl-, Br-, and -OSO2C6H5.When, however, a non-conjugative intervening group such as CO or CH2 is present between the reaction centre and the benzene ring of a reactant, the cross-interaction constant is reduced by a factor of ca. 2, demonstrating the fall-off of the susceptibility of the reaction centres to substituent changes.
- Lee, Ikchoon,Shim, Chang Sub,Chung, Soo Young,Kim, Hyung Yoon,Lee, Hai Whang
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p. 1919 - 1924
(2007/10/02)
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