- Direct conversion of thiols and disulfides into sulfonamides
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The H2O2-ZrCl4 reagent system is used as a new and efficient reagent for the conversion of thiols and disulfides into sulfonamides. The protocol offers several advantages such as excellent yields of products and extremely fast reactions at room temperature. The reagent system is very easy to handle and is environmentally safe and economical.
- Bahrami, Kiumars,Khodaei, Mohammad M.,Soheilizad, Mehdi
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Read Online
- Metal-Free Mediated Meerwein-Type Reaction: A Radical Cascade Arylation/Aryl Migration/Desulfonylation of Conjugated Alkenes
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A metal-free cascade arylation/aryl migration/desulfonylation of N-phenyl-N-(phenylsulfonyl)methacrylamide is described. The in situ generated diazonium salts from anilines and t-BuONO are used as aryl precursors. This process provides an efficient strategy for the synthesis of α-all-carbon quaternary stereocenters amides. A radical mechanism was proposed for this transformation.
- Ni, Zhangqin,Huang, Xin,Pan, Yuanjiang
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Read Online
- A new generation of terminal copper nitrenes and their application in aromatic C-H amination reactions
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Copper nitrene complexes are highly reactive species and are known as intermediates in the copper catalyzed C-H amination. In this study, three novel copper tosyl nitrene complexes were synthesized at low temperatures, stabilized with heteroscorpionate ligands of the bis(pyrazolyl)methane family. The copper nitrenes were obtained by the reaction of a copper(i) acetonitrile complex with SPhINTs in dichloromethane. We show that the ligand design has a major influence on the catalytic activity and the thermal stability of the copper nitrene complex. Not only the choice of the third N donor, but also the substituent in the 5-position of the pyrazolyl moiety, have an impact on the stability. Furthermore, the novel copper nitrene complexes were used for catalytic aziridination of styrenes and C-H amination reactions of aromatic and aliphatic substrates under mild reaction conditions. Even challenging substrates like benzene and cyclohexane were aminated with good yields. The copper nitrene complexes were characterized using UV/Vis spectroscopy, low temperature Evans NMR spectroscopy, density functional theory, domain-based local pair natural orbital coupled cluster calculations (DLPNO-CCSD(T)) and cryo-UHR mass spectrometry.
- Amarouch, Benedikt,G?bgen, Kai C.,Hoffmann, Alexander,Oster, Matthias,Sch?n, Florian,Steden, Dominik,Thomas, Fabian
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supporting information
p. 6444 - 6462
(2021/05/26)
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- Synthesis of magnetic chitosan supported metformin-Cu(II) complex as a recyclable catalyst for N-arylation of primary sulfonamides
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The application of chitosan, which has received much attention as a natural polymer and effective support, has many advantages such as biodegradability and biocompatibility. In this study, the immobilization of a copper complex on the magnetic chitosan bearing metformin ligand has been developed through immobilizing structurally defined metformin with long tail of (3-chloropropyl)trimethoxysilane (TMOS). The synthesized Fe3O4-chitosan@metformin-Cu(II) complex (Fe3O4-CS@Met-Cu(II)) was used as an effective, reusable and magnetic catalyst in the N-arylation of different derivatives of primary sulfonamides with arylboronic acids in ethanol. The primary sulfonamides were prepared from the reaction of sulfonyl chlorides with sodium cyanate in water under ultrasonic irradiation. Utilizing a wide variety of substrates in EtOH as a green solvent, high yields of the primary and secondary sulfonamides, easy work-up along with the excellent recovery and reusability of the catalyst, make this process a simple, economic and environmentally benign method. The synthesized Fe3O4-CS@Met-Cu(II) was characterized using various techniques such as XRD (X-ray diffraction), EDS (energy-dispersive X-ray spectroscopy), elemental mapping, TEM (transmission electron microscopy), FESEM (field emission scanning electron microscopy), VSM (vibrating sample magnetometer), ICP-MS (inductively coupled plasma mass spectroscopy), TGA (thermogravimetric analysis) and FT-IR (Fourier-transform infrared spectroscopy) analyses. The catalyst can be recycled and reused 5 times with no considerable loss of catalytic activity.
- Ahmadpoor, Fatemeh,Nasrollahzadeh, Mahmoud,Nezafat, Zahra,Pakzad, Khatereh
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- Nickel-Catalyzed Reductive Cross-Coupling of N-Acyl and N-Sulfonyl Benzotriazoles with Diverse Nitro Compounds: Rapid Access to Amides and Sulfonamides
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Herein we report a Ni-catalyzed reductive transamidation of conveniently available N-acyl benzotriazoles with alkyl, alkenyl, and aryl nitro compounds, which afforded various amides with good yields and a broad substrate scope. The same catalytic reaction conditions were also applicable for N-sulfonyl benzotriazoles, which could undergo smooth reductive coupling with nitroarenes and nitroalkanes to afford the corresponding sulfonamides.
- Bai, Jin,Li, Shangzhang,Li, Wanfang,Qu, Erdong,Zheng, Yan
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- Design, Synthesis, and in vitro Evaluation of Tubulin-Targeting Dibenzothiazines with Antiproliferative Activity as a Novel Heterocycle Building Block
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We prepared a series of free NH and N-substituted dibenzonthiazines with potential anti-tumor activity from N-aryl-benzenesulfonamides. A biological test of synthesized compounds (59 samples) was performed in vitro measuring their antiproliferative activity against a panel of six human solid tumor cell lines and its tubulin inhibitory activity. We identified 6-(phenylsulfonyl)-6H-dibenzo[c,e][1,2]thiazine 5,5-dioxide and 6-tosyl-6H-dibenzo[c,e][1,2]thiazine 5,5-dioxide as the best compounds with promising values of activity (overall range of 2–5.4 μM). Herein, we report the dibenzothiazine core as a novel building block with antiproliferative activity, targeting tubulin dynamics.
- Guerra, Walter D.,Lucena-Agell, Daniel,Hortigüela, Rafael,Rossi, Roberto A.,Fernando Díaz,Padrón, José M.,Barolo, Silvia M.
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p. 3003 - 3016
(2021/08/06)
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- Deconstructing Noncovalent Kelch-like ECH-Associated Protein 1 (Keap1) Inhibitors into Fragments to Reconstruct New Potent Compounds
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Targeting the protein-protein interaction (PPI) between nuclear factor erythroid 2-related factor 2 (Nrf2) and Kelch-like ECH-associated protein 1 (Keap1) is a potential therapeutic strategy to control diseases involving oxidative stress. Here, six classes of known small-molecule Keap1-Nrf2 PPI inhibitors were dissected into 77 fragments in a fragment-based deconstruction reconstruction (FBDR) study and tested in four orthogonal assays. This gave 17 fragment hits of which six were shown by X-ray crystallography to bind in the Keap1 Kelch binding pocket. Two hits were merged into compound 8 with a 220-380-fold stronger affinity (Ki = 16 μM) relative to the parent fragments. Systematic optimization resulted in several novel analogues with Ki values of 0.04-0.5 μM, binding modes determined by X-ray crystallography, and enhanced microsomal stability. This demonstrates how FBDR can be used to find new fragment hits, elucidate important ligand-protein interactions, and identify new potent inhibitors of the Keap1-Nrf2 PPI.
- Pallesen, Jakob S.,Narayanan, Dilip,Tran, Kim T.,Solbak, Sara M. ?.,Marseglia, Giuseppe,S?rensen, Louis M. E.,H?j, Lars J.,Munafò, Federico,Carmona, Rosa M. C.,Garcia, Anthony D.,Desu, Haritha L.,Brambilla, Roberta,Johansen, Tommy N.,Popowicz, Grzegorz M.,Sattler, Michael,Gajhede, Michael,Bach, Anders
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p. 4623 - 4661
(2021/05/07)
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- Ultrasound-assisted one-pot three-component synthesis of new isoxazolines bearing sulfonamides and their evaluation against hematological malignancies
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In the present study, following a one-pot two-step protocol, we have synthesized novel sulfonamides-isoxazolines hybrids (3a-r) via a highly regioselective 1,3-dipolar cycloaddition. The present methodology capitalized on trichloroisocyanuric acid (TCCA) as a safe and ecological oxidant and chlorinating agent for the in-situ conversion of aldehydes to nitrile oxides in the presence of hydroxylamine hydrochloride, under ultrasound activation. These nitrile oxides could be engaged in 1,3-dipolar cycloaddition reactions with various alkene to afford the targeted sulfonamides-isoxazolines hybrids (3a-r). The latter were assessed for their antineoplastic activity against model leukemia cell lines (Chronic Myeloid Leukemia, K562 and Promyelocytic Leukemia, HL-60).
- Talha, Aicha,Favreau, Cécile,Bourgoin, Maxence,Robert, Guillaume,Auberger, Patrick,EL Ammari, Lahcen,Saadi, Mohamed,Benhida, Rachid,Martin, Anthony R.,Bougrin, Khalid
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- Copper-Catalyzed Aminoarylation of Alkenes via Aminyl Radical Addition and Aryl Migration
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We describe a new strategy for aminoarylation of alkenes by copper-catalyzed smiles rearrangement using O-benzoylhydroxylamines as the amine reagent. This method affords various β-amino amide derivatives possessing a quaternary carbon center with wide functional group tolerance and high regioselectivity. The mechanistic studies indicate that the transformation can involve aminyl radical intermediates under acid-free condition.
- Liu, Mei-Ling,Liu, Xue-Yuan,Sun, Wen-Hui,Wang, Jin-Lin,Zou, Jian-Yu
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supporting information
(2022/01/04)
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- Sequential C-S and S-N Coupling Approach to Sulfonamides
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A one-pot three-component reaction involving nitroarenes, (hetero)arylboronic acids, and potassium pyrosulfite leading to sulfonamides was described. A broad range of sulfonamides bearing different reactive functional groups were obtained in good to excellent yields through sequential C-S and S-N coupling that does not require metal catalysts.
- Chen, Kai,Chen, Wei,Han, Bing,Chen, Wanzhi,Liu, Miaochang,Wu, Huayue
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supporting information
p. 1841 - 1845
(2020/03/04)
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- Copper-catalyzed synthesis of sulfonamides from nitroarenes: Via the insertion of sulfur dioxide
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Nitroarenes are used as the coupling partners in the preparation of sulfonamides via the insertion of sulfur dioxide. A three-component reaction of arylboronic acids, nitroarenes, and potassium metabisulfite under copper catalysis proceeds smoothly, giving rise to a range of sulfonamides in good to excellent yields with broad substrate scope. Various functional groups including hydroxyl, cyano, amino, and carbonyl are all tolerated. A plausible mechanism is proposed, showing that arylsulfinate is the intermediate and the copper-assisted interaction of the nitroarene and arylsulfinate is the key step. This approach is also extended to the late-stage modification of a currently marketed drug (flutamide).
- Wang, Xuefeng,Yang, Min,Kuang, Yunyan,Liu, Jin-Biao,Fan, Xiaona,Wu, Jie
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supporting information
p. 3437 - 3440
(2020/03/30)
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- SuFEx Activation with Ca(NTf2)2: A Unified Strategy to Access Sulfamides, Sulfamates, and Sulfonamides from S(VI) Fluorides
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A method to activate sulfamoyl fluorides, fluorosulfates, and sulfonyl fluorides with calcium triflimide and DABCO for SuFEx with amines is described. The reaction was applied to a diverse set of sulfamides, sulfamates, and sulfonamides at room temperature under mild conditions. Additionally, we highlight this transformation to parallel medicinal chemistry to generate a broad array of nitrogen-based S(VI) compounds.
- Am Ende, Christopher W.,Ball, Nicholas D.,Bellenger, Justin,Butler, Todd W.,Carneiro, Sabrina N.,Dutra, Jason K.,Gu, Junha,Khasnavis, Samuel R.,Kwan, Sabrina C.,Mahapatra, Subham,Vetelino, Beth C.,Woroch, Cristian P.
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supporting information
(2020/06/05)
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- Metal-free one-pot synthesis of N-arylsulfonamides from nitroarenes and sodium sulfinates in an aqueous medium
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A metal-free one-pot two-step synthesis of sulfonamides from readily available nitroarenes and sodium arylsulfinates in a mixture of methanol and water has been developed. In this procedure, the aryl amines were produced in situ by the reduction of nitroarenes mediated by diboronic acid, and then coupled with sodium arylsulfinates in the presence of iodine. A series of N-arylsulfonamides with various functional groups were obtained in moderate to good yields under the optimal reaction conditions. In addition, this one-pot process is applicable for gram-scale synthesis.
- Jiang, Xiaolan,Zhang, Kaili,Zhao, Rongrong,Bai, Die,Wang, Jinlong,Li, Binbin,Liu, Qixing,Zhou, Haifeng
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supporting information
(2020/09/10)
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- Transition-Metal-Free and Visible-Light-Mediated Desulfonylation and Dehalogenation Reactions: Hantzsch Ester Anion as Electron and Hydrogen Atom Donor
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Novel approaches for N- and O-desulfonylation under room temperature (rt) and transition-metal-free conditions have been developed. The first methodology involves the transformation of a variety of N-sulfonyl heterocycles and phenyl benzenesulfonates to the corresponding desulfonylated products in good to excellent yields using only KOtBu in dimethyl sulfoxide (DMSO) at rt. Alternately, a visible light method has been used for deprotection of N-methyl-N-arylsulfonamides with Hantzsch ester (HE) anion serving as the visible-light-absorbing reagent and electron and hydrogen atom donor to promote the desulfonylation reaction. The HE anion can be easily prepared in situ by reaction of the corresponding HE with KOtBu in DMSO at rt. Both protocols were further explored in terms of synthetic scope as well as mechanistic aspects to rationalize key features of desulfonylation processes. Furthermore, the HE anion induces reductive dehalogenation reaction of aryl halides under visible light irradiation.
- Heredia, Micaela D.,Guerra, Walter D.,Barolo, Silvia M.,Fornasier, Santiago J.,Rossi, Roberto A.,Budén, Mariá E.
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supporting information
p. 13481 - 13494
(2020/12/15)
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- Synthesis of N-substituted sulfonamides containing perhalopyridine moiety as bio-active candidates
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A series of new halogenated aryl sulfonamides, as bio-active candidates, was synthesized from the reaction of the corresponding aryl sulfonamides with pentafluoro- and pentachloropyridines. Surprisingly, unlike aryl sulfonamides, the reaction of sulfamides with pentafluoro- and pentachloropyridines gave unexpected bis-perfluoro(chloro)pyridin-4-ylamines.
- Hosseini, Raziyeh,Mohammadiannejad, Kazem,Ranjbar-Karimi, Reza
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- Environment-friendly synthesis method of scorch retarder N-phenyl-N-trichloromethylthio benzene sulfonamide
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The invention discloses an environment-friendly synthesis method of a scorch retarder N-phenyl-N-trichloromethylthio benzene sulfonamide. The synthesis method comprises the following steps: controlling the temperature, dropwise adding benzene sulfonyl chloride into a mixed solution of aniline, alkali, TBAB and water, heating in stages to prepare an intermediate; after the reaction, extracting theintermediate by using an organic solvent, mixing the organic mother liquor containing the intermediate with alkali, TBAB and water, controlling the temperature, dropwise adding perchloromethyl mercaptan into the mixed solution, and heating in stages to obtain the final product. A sectional heating mode is adopted in the synthesis process of the intermediate and the product; meanwhile, alkali and aphase transfer catalyst are combined; the reaction conversion rate is increased, side reactions are reduced, the obtained product is pure white in appearance, high in purity and stable in quality, the domestic technical blank is filled up, the COD and total nitrogen content of the wastewater are sharply reduced, the strong pungent smell of perchloromethyl mercaptan in the wastewater is greatly reduced, the wastewater treatment difficulty is reduced, and the effect of clean production is achieved.
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Paragraph 0031-0043
(2020/08/27)
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- Efficient and Practical Synthesis of Sulfonamides Utilizing SO2 Gas Generated on Demand
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A simple and practical protocol was developed for the synthesis of sulfonamides by reacting organometallic reagents with SO2 gas generated on demand. SO2 was generated from readily available reagents safely in a highly contained and controlled fashion. The protocol allows the synthesis of sulfonamides without using either atom-inefficient SO2 surrogates or a SO2 cylinder that requires stringent storage regulations in the laboratory. The protocol was successfully applied to the synthesis of sildenafil.
- Chung Leung, Gulice Yiu,Ramalingam, Balamurugan,Loh, Gabriel,Chen, Anqi
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p. 546 - 554
(2020/04/22)
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- A Strategy for the Synthesis of Sulfonamides on DNA
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An efficient method is reported to synthesize sulfonamides on DNA from sulfinic acids or sodium sulfinates and amines in the presence of iodine under mild conditions. This method demonstrates a major expansion of scope of sulfonamide formation on DNA through the utilization of a novel sodium carbonate-sodium sulfinate bifunctional reagent class.
- Liu, Wei,Deng, Wei,Sun, Saisai,Yu, Chunyan,Su, Xubo,Wu, Aliang,Yuan, Youlang,Ma, Zhonglin,Li, Ke,Yang, Hongfang,Peng, Xuanjia,Dietrich, Justin
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supporting information
p. 9909 - 9913
(2019/12/24)
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- Method for coupling nitroaromatic compound and boric acid compound to synthesize sulfonamide compound
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The invention belongs to the field of organic synthesis, and specifically discloses a method for coupling a nitroaromatic compound and a boric acid compound to synthesize a sulfonamide compound. The method for coupling the nitroaromatic compound and the boric acid compound to synthesize the sulfonamide compound comprises the steps that in an organic solvent, pyrosulfite is used as a source of SO2,and heating is carried out for a coupling reaction, and then after the post-treatment, the sulfonamide compound is obtained. The method for coupling the nitroaromatic compound and the boric acid compound to synthesize the sulfonamide compound is simple in operation, does not require nitrogen protection, and can be carried out under air. The nitroaromatic compound and the boric acid compound are abundant in source, relatively low in price, high in reaction yield, wide in applicability of a substrate and free in metal residual. The method for coupling the nitroaromatic compound and the boric acid compound to synthesize the sulfonamide compound can be used for synthesizing a series of sulfonamide compounds, and the synthesized compounds have wide application value in the fields of pesticidesand medicines.
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Paragraph 0032-0036
(2019/11/12)
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- Multicomponent synthesis of sulfonamides from triarylbismuthines, nitro compounds and sodium metabisulfite in deep eutectic solvents
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A sustainable synthesis of sulfonamides using a copper-catalysed process starting from triarylbismuthines, Na2S2O5 and nitro compounds in a Deep Eutectic Solvent (DES) as a reaction medium is described. Thus, triarylbismuthines are used as reagents for the incorporation of SO2 into organic motifs. The bismuth salts formed as by-products can be easily removed from the crude reaction mixture by precipitation with water, while the use of volatile organic compounds (VOCs) as solvents can be avoided in the entire process. The eutectic mixture employed as the solvent is fully characterised, with the preliminary results proving its low toxicity. The designed DES also allows for a novel multicomponent reaction which saves time and reduces purification steps, energy and cost.
- Marset, Xavier,Torregrosa-Crespo, Javier,Martínez-Espinosa, Rosa M.,Guillena, Gabriela,Ramón, Diego J.
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supporting information
p. 4127 - 4132
(2019/08/07)
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- Cu-Mediated Synthesis of Indolines and Dihydroisoquinolinones through Arylperfluoroalkylation of Unactivated Alkenes
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The copper-mediated fluroalkylation/cyclization of N-allyl anilines has been described using fluoroalkyl iodides as fluoroalkylation reagents for the first time. The reaction provides an efficient and direct access to 3-fluoroalkyl indolines in moderate to good yields with unactivated double bonds as the radical acceptor. This protocol combines a simple experimental procedure with low-costing fluoroalkylated sources and excellent functional group tolerance.
- Li, Dandan,Wang, Yan,Jia, Zhenzhen,Ou, Zhaocheng,Dong, Yongrui,Lv, Cunjie,Fu, Guangbin,Liang, Deqiang
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p. 4797 - 4804
(2019/08/12)
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- Copper-catalyzed denitrogenative N-arylation of sulfoximines and sulfonamides with arylhydrazines
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A Cu-mediated ligand-free arylation of NH-sulfoximines and sulfonamides by arylhydrazine hydrochlorides was herein demonstrated. The oxidative transformation provided an easy access towards N-aryl sulfoximines and sulfonamides in high yields (up to 93% yields) with broad functional groups tolerance (up to 36 examples). The protocol was proposed to take place through the free radical pathway based on the results of control reactions and EPR analysis.
- Dong, Wanrong,Liu, Chaoyang,Ma, Xinchi,Zhang, Yingjun,Peng, Zhihong,Xie, Dexun,An, Delie
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p. 3886 - 3893
(2019/06/18)
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- Sulfonyl imide or sulfonamide of the denitrification arylation method and product and application
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A sulfonyl imide or sulfonamide of the denitrification arylation method and product and application, sulfonimide or sulfonamide of the denitrification arylation method, comprises the following steps: to arylhydrazine and sulfonyl imide or sulfonamide as raw material, the catalyst palladium salt, alkali, solvent and oxidizing agent in the presence of, prepared N - aryl sulfonyl imide or N - aryl sulfonamides. The sulfonimide or sulfonamide of the denitrification arylation method, by adopting the arylhydrazine and sulfonimide or sulfonamide as raw materials used to prepare N - aryl sulfonyl imide or N - aryl sulfonamides, arylhydrazine because of having low cost, high reactivity and easy accessibility and the like, can make the sulfonyl imide or a sulfonamide for the arylation of the method cost is relatively low. The arylhydrazine as aryl group donor, the reaction by-product is N2 And H2 O, so it has the characteristics of green and environmental protection.
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Paragraph 0066-0073
(2019/03/31)
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- High yielding protocol for direct conversion of thiols to sulfonyl chlorides and sulfonamides
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In this paper, a new method for oxidative chlorination of thiols to sulfonyl chlorides and sulfonamides using H2O2 in the presence of TMSCl is reported. The excellent yields, short reaction times, excellent efficiencies, low costs, and easy separation of products are the most important advantages of this method.
- Sohrabnezhad, Samira,Bahrami, Kiumars,Hakimpoor, Farahman
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p. 256 - 264
(2019/02/06)
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- Characteristic Hydrogen Bonding Observed in the Crystals of Aromatic Sulfonamides: 1D Chain Assembly of Molecules and Chiral Discrimination on Crystallization
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N-Phenylbenzenesulfonamides exist preferentially in (+)- or (-)-synclinal conformations, which place the aromatic rings at both ends in the same direction with a twist. We have systematically analyzed the crystal structure of secondary aromatic sulfonamides bearing methyl, ethyl, and/or methoxy groups on the benzene rings. Intermolecular hydrogen bonding between the sulfonamide protons and sulfonyl oxygens was observed in 81 out of 85 crystals. The intermolecular hydrogen-bonding patterns could be classified into four types, i.e. Dimeric, Zigzag, Helical, and Straight patterns, with retention of the synclinal conformation of the sulfonamide moiety. We investigated the relationship between the hydrogen-bonding pattern and the proportion of the compounds that show chiral crystallization. On the basis of our classification of the intermolecular hydrogen bonds of aromatic sulfonamides, the crystals with Dimeric and Zigzag patterns, which both have enantiomeric synclinal conformers, intrinsically become achiral, except for kryptoracemates. In contrast, a high proportion of compounds with Helical or Straight patterns in the crystals showed chiral crystallization. Our classification is useful for discussion regarding the chirality of molecular assemblies, on the basis of the conformational chirality of the molecules in the crystal.
- Kikkawa, Shoko,Masu, Hyuma,Katagiri, Kosuke,Okayasu, Misaki,Yamaguchi, Kentaro,Danjo, Hiroshi,Kawahata, Masatoshi,Tominaga, Masahide,Sei, Yoshihisa,Hikawa, Hidemasa,Azumaya, Isao
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p. 2936 - 2946
(2019/05/10)
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- Tert -Butyl nitrite mediated nitrogen transfer reactions: Synthesis of benzotriazoles and azides at room temperature
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A conversion of o-phenylenediamines into benzotriazoles was achieved at room temperature using tert-butyl nitrite. The optimized conditions are also well suited for the transformation of sulfonyl and acyl hydrazines into corresponding azides. This protocol does not require any catalyst or acidic medium. The desired products were obtained in excellent yields in a short span of time.
- Azeez, Sadaf,Chaudhary, Priyanka,Sureshbabu, Popuri,Sabiah, Shahulhameed,Kandasamy, Jeyakumar
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supporting information
p. 6902 - 6907
(2018/10/02)
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- Transition-metal-free synthesis of aromatic amines via the reaction of benzynes with isocyanates
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An unexpected reaction between benzynes and isocyanates to generate aromatic amines has been developed under transition-metal-free conditions. The in situ prepared anions formed through cleavage of the N–C bond in isocyanates, reacted with aryne precursor
- Seo, Jeong Hoon,Ko, Haye Min
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supporting information
p. 671 - 674
(2018/01/19)
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- Fe-based metal-organic frameworks for the synthesis of N-arylsulfonamides via the reactions of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes in water
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A newly developed chemoselective reaction of sodium arylsulfinates or arylsulfonyl chlorides with nitroarenes has been disclosed. The chemistry, in which non-toxic water and recyclable iron-based metal-organic frameworks are employed as the solvent and catalyst, respectively, provides an efficient approach for the generation of N-arylsulfonamides, which are widely present in biologically active compounds and drugs, rendering this methodology attractive to both synthetic and medicinal chemistry.
- Li, Xinxin,Chen, Fei,Lu, Guo-Ping
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p. 4226 - 4230
(2018/10/26)
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- Method for ultrasound-assisted synthesis of N-arylsulfonamide
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The invention discloses a method for ultrasound-assisted synthesis of N-arylsulfonamide. N-arylsulfonamide compound is synthesized by series reaction of nitro reduction/sulfonyl chloride reduction/sulfonamidation with taking aromatic nitro compounds, sulfonyl chloride and iron powder as raw materials under ultrasonic stirring conditions. Water is used as a reaction medium and a hydrogen source inthe reaction. The method has the advantages of cheap and easily obtained raw materials, simple and mild reaction conditions, environmental friendliness, saving energy, high reaction selectivity and high yield, excellent compatibility of substrate functional groups and high application value.
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Paragraph 0050; 0051; 0052; 0055-0065; 0069-0097
(2018/11/27)
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- Synthesis of: N -arylsulfonamides via Fe-promoted reaction of sulfonyl halides with nitroarenes in an aqueous medium
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A fascinating Fe-promoted protocol for the synthesis of N-arylsulfonamides has been developed. Starting from commercially available nitroarenes and sulfonyl chlorides, moderate to excellent yields of the corresponding N-arylsulfonamides can be obtained. In particular, Fe dust serves as the sole reductant in the transformation and it can be easily performed on a large scale.
- Jiang, Jun,Zeng, Sheng,Chen, De,Cheng, Chaozhihui,Deng, Wei,Xiang, Jiannan
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supporting information
p. 5016 - 5020
(2018/07/25)
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- Palladium-catalyzed desulfitative arylation of sulfonamides with sodium arylsulfinates
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A Pd(II)-catalyzed desulfitative arylation protocol between sulfonamides and sodium arylsulfinates was herein reported. The direct arylation reaction was successfully achieved by a Pd(II)/Ag(I)-mediated system without participation of any external ligands with a release of SO2. And different N-aryl sulfonamides were obtained readily in up to 86% yields, exhibiting good functional groups tolerance (25 examples).
- Zhao, Zijian,Lian, Yan,Zhao, Chang,Wang, Bing
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supporting information
p. 1436 - 1442
(2018/06/01)
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- Sulfonamide Synthesis via Calcium Triflimide Activation of Sulfonyl Fluorides
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A method using calcium triflimide [Ca(NTf2)2] as a Lewis acid to activate sulfonyl fluorides toward nucleophilic addition with amines is described. The reaction converts a wide array of sterically and electronically diverse sulfonyl fluorides and amines into the corresponding sulfonamides in good yield.
- Mukherjee, Paramita,Woroch, Cristian P.,Cleary, Leah,Rusznak, Mark,Franzese, Ryan W.,Reese, Matthew R.,Tucker, Joseph W.,Humphrey, John M.,Etuk, Sarah M.,Kwan, Sabrina C.,Am Ende, Christopher W.,Ball, Nicholas D.
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supporting information
p. 3943 - 3947
(2018/07/15)
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- Selective cleavage of the N-propargyl group from sulfonamides and amides under ruthenium catalysis
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The selective cleavage of the N-propargyl group from sulfonamides and amides under ruthenium catalysis is described. The reaction tolerates a broad range of functional groups, and the desired products were obtained in 10–95% yield.
- Wang, Jingjing,Li, Feng,Pei, Wenlong,Yang, Mixue,Wu, Yidan,Ma, Danyang,Zhang, Furong,Wang, Jianhui
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supporting information
p. 1902 - 1905
(2018/04/19)
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- Synthesis of N-arylsulfonamides through a Pd-catalyzed reduction coupling reaction of nitroarenes with sodium arylsulfinates
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A novel one-step direct reductive coupling reaction between nitroarenes and sodium arylsulfinates was realized in the presence of an inexpensive Pd/C catalyst. In this procedure, readily available nitroarenes are employed as the nitrogen sources, and sodium arylsulfinates serve as both coupling partners and reductants. The method features high efficiency by using cheap Pd/C with low catalyst loading and good functional group tolerance in the absence of any additional reductants or ligands. This facile and mild synthetic method enables the high efficiency synthesis of functionalized N-arylsulfonamides from readily available substrates.
- Yang, Bo,Lian, Chang,Yue, Guanglu,Liu, Danyang,Wei, Liyan,Ding, Yi,Zheng, Xiancai,Lu, Kui,Qiu, Di,Zhao, Xia
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supporting information
p. 8150 - 8154
(2018/11/23)
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- Sulfonamidation of Aryl and Heteroaryl Halides through Photosensitized Nickel Catalysis
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Herein we report a highly efficient method for nickel-catalyzed C?N bond formation between sulfonamides and aryl electrophiles. This technology provides generic access to a broad range of N-aryl and N-heteroaryl sulfonamide motifs, which are widely represented in drug discovery. Initial mechanistic studies suggest an energy-transfer mechanism wherein C?N bond reductive elimination occurs from a triplet excited NiII complex. Late-stage sulfonamidation in the synthesis of a pharmacologically relevant structure is also demonstrated.
- Kim, Taehoon,McCarver, Stefan J.,Lee, Chulbom,MacMillan, David W. C.
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supporting information
p. 3488 - 3492
(2018/03/05)
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- Synthesis of 3-Amino-1-benzothiophene-1,1-diones by Alkyne Directed Hydroarylation and 1/N→3/C-Sulfonyl Migration
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A completely regioselective and highly stereoselective palladium-catalyzed intramolecular hydroarylation of arenesulfonyl ynamines to benzothiazoles was developed. The presence of an electron-withdrawing group on the triple bond of the sulfonyl ynamine was crucial for the success of the reaction and our mechanistic studies suggest an alkyne-directed 5-exo-dig cyclization pathway. The products easily underwent photoinduced rearrangement to 3-amino-1-benzothiophene-1,1-diones (up to 35 % yields after two steps).
- Bernar, Ivan,Blanco-Ania, Daniel,Stok, Sophie J.,Sotorríos, Lia,Gómez-Bengoa, Enrique,Rutjes, Floris P. J. T.
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supporting information
p. 5435 - 5444
(2018/10/20)
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- Synthesis of CF3CH2-Containing Indolines by Transition-Metal-Free Aryltrifluoromethylation of Unactivated Alkenes
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With an unactivated double bond as the radical acceptor, allyl amines underwent a metal-free trifluoromethylation/cyclization cascade with CF3SO2Na (Langlois' reagent), affording CF3CH2-containing indolines and tetrahydroisoquinolines, whose practical syntheses are significant challenges. This protocol features mild conditions, low cost, and a broad substrate scope.
- Liang, Deqiang,Dong, Qishan,Xu, Penghui,Dong, Ying,Li, Weili,Ma, Yinhai
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supporting information
p. 11978 - 11986
(2018/09/27)
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- Synthetic method of CF3-containing indoline and 1,2,3,4-tetrahydroisoquinoline
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The invention discloses a synthetic method of CF3-containing indoline and 1,2,3,4-tetrahydroisoquinoline and relates to the technical field of compound synthesis. The synthetic method herein is basedon metal-free trifluoromethylation/cyclization free radical cascade reaction using a nonactive olefin dual-bond as a free radical receptor; the reaction aforementioned helps synthesize, in one step, CF3-containing indoline and 1,2,3,4-tetrahydroisoquinoline. The synthetic method herein has the significant advantages of mild conditions, good operational simplicity, low cost, wide substrate range, good exo selectivity and the like.
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Paragraph 0027; 0029; 0030; 0031; 0042
(2019/01/14)
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- Rearrangement Reaction Based on the Structure of N-Fluoro- N-alkyl Benzenesulfonamide
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A novel rearrangement reaction based on the structure of N-fluoro-N-alkyl benzenesulfonamide was developed. The reaction proceeded readily at 50 °C in formic acid and generated a variety of benzenesulfonamides and aldehydes or ketones simultaneously. The reaction mechanism is believed to be a concerted mechanism that consist of 1,2-aryl migration with the departure of fluorine anion via an SN2 mechanism. This rearrangement reaction features an interesting reaction mechanism, mild reaction conditions, simple operations, and a broad substrate scope.
- Wang, Han-Ying,Pu, Xiao-Qiu,Yang, Xian-Jin
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p. 13103 - 13110
(2018/10/20)
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- In situ Generation and Utilization of CO: An Efficient Route towards N-Substituted Saccharin via Carbonylative Cyclization of 2-Iodosulfonamides
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The present protocol demonstrates the synthesis of N-substituted saccharines via carbonylative cyclization of 2-iodosulfonamides using a Pd(OAc) 2 /Xantphos catalyst system and phenyl formate as a CO source. A variety of saccharin derivatives is synthesized under milder reaction conditions.
- Chavan, Sujit P.,Adithyaraj,Bhanage, Bhalchandra M.
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p. 2000 - 2003
(2017/09/13)
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- Photocatalytic benzene and benzene derivative direct hydroxylation or amination method
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The invention discloses a photocatalytic benzene and benzene derivative direct hydroxylation or amination method. The method is characterized by comprising the following steps: (1) adding a photo-sensitizer and a cobalt catalyst into a solvent to obtain a solution (A); (2) adding benzene (or benzene derivatives), water, ammonia gas, and amide derivatives (or sulfonamide derivatives) into the solution (A) to obtain a solution (B); and (3) in a N2 (or Ar) environment, radiating the solution (B) by a medium pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, or an LED lamp to obtain phenols or amines and H2. For the first time, a photo-sensitizer and a cobalt catalyst are combined and applied to photocatalytic hydroxylation and amination of benzene. The conditions of the method are mild, light is taken as the driving energy, no oxidant is added, the only byproduct is H2, and the whole process is green, concise, and efficient. High selective benzene one-step hydroxylation to generate phenol or high selective phenol/benzene one-step amination to generate aniline is realized, and the method can be applied to the production of phenol and aniline.
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Paragraph 0160-0161
(2017/11/29)
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- Palladium-Catalyzed Regioselective Synthesis of 3-Arylindoles from N-Ts-Anilines and Styrenes
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A Pd-catalyzed intermolecular oxidative annulation between N-Ts-anilines and styrenes was developed. This method offers a straightforward and robust approach to a wide range of 3-arylindoles using readily available starting materials with good functional-group tolerance and high regioselectivity and efficiency. Further elaboration of the products obtained from this process provided access to highly functionalized and structurally diverse indoles, for example, 3-(indol-3-yl)carbazoles, 1,9-dihydropyrrolo-[2,3-b]carbazoles, and 3′-aryl-3,5′-biindoles.
- Youn, So Won,Ko, Tae Yun,Jang, Young Ho
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supporting information
p. 6636 - 6640
(2017/05/29)
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- Efficient synthesis of novel 1,3-diyne-based sulfonamides using CuCl2/Et3N as a robust catalytic system
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An efficient and practical synthesis of 1,3-diyne-based sulfonamides using CuCl2/Et3N as a catalytic system is disclosed. Mild reaction conditions, atom-economy and high yields (50–91%) make this method an attractive option for the preparation of 1,3-diyne-based sulfonamide derivatives.
- Mirjafary, Zohreh,Sadighian, Hamed,Piri, Samira,Saeidian, Hamid
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p. 188 - 194
(2017/03/07)
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- Synthesis and anti-cancer activities of new sulfonamides 4-substituted-triazolyl nucleosides
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Nucleoside analogues are among the most known drugs commonly used in antiviral and anticancer chemotherapies. Among them, those featuring a five-membered ring nucleobase are of utmost interest such as the anti-cancer agent AICAR or the anti-viral drug ribavirin. Despite its low activity in vitro in different cell lines, AICAR is under clinical development for several pathologies, thanks to its original mode of action. Indeed, AICAR induced autophagy cell death and is able, following this mechanism, to circumvent resistance to apoptotic drugs including kinase inhibitors currently on the market. To improve the activity of AICAR, we report herein an efficient synthesis of new series of sulfonamide-4-substituted-1,2,3-triazolyl nucleosides using a Cu-catalyzed 1,3-dipolar cycloaddition. All these molecules have been fully characterized and evaluated against two aggressive tumor cell lines, RCC4 and MDA-MB-231. Among them, nucleoside analogue 5i belonging to the ribose series was found to be 19 to 66-fold more active than AICAR. Western blot analyses on RCC4 cells showed that 5i displayed an interesting mode of action by inducing both apoptosis and autophagy cell death, making therefore this class of molecules highly promising for further hit-to-lead optimization.
- Alaoui, Soukaina,Dufies, Maeva,Driowya, Mohsine,Demange, Luc,Bougrin, Khalid,Robert, Guillaume,Auberger, Patrick,Pagès, Gilles,Benhida, Rachid
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supporting information
p. 1989 - 1992
(2017/04/10)
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- Palladium-catalyzed N-arylsulfonamide formation from arylsulfonyl hydrazides and nitroarenes
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A palladium-catalyzed construction for N-arylsulfonamide from nitroarenes and arylsulfonyl hydrazides is developed. In this protocol, abundant and stable nitroarenes serve as the nitrogen sources by in situ reduction reaction of hydrogen released from arylsulfonyl hydrazides. No external oxidants or reductants are needed for this kind of transformation.
- Zhao, Feng,Li, Bin,Huang, Huawen,Deng, Guo-Jun
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p. 13010 - 13013
(2016/02/12)
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- Palladium nanoparticles as reusable catalyst for the synthesis of N-aryl sulfonamides under mild reaction conditions
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An efficient palladium nanoparticles-catalyzed N-arylation of sulfonamides and sulfonyl azides is described. This procedure serves as an active protocol for intermolecular C-N bond formation using Pd(OAc)2 in PEG-400 under air. Aryl bromides and triflates react at 35°C, while aryl chlorides require heating to 50°C and give the desired products only in low yields. This reaction proceeds smoothly in acceptable yields using low catalyst loading.
- Khalaj, Mehdi,Ghazanfarpour-Darjani, Majid,Talei Bavil Olyai, Mohamad Reza,Shamami, Sakineh Faraji
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p. 211 - 221
(2016/03/30)
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- Diamination of Domino Aryne Precursor with Sulfonamides
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The reaction of a domino aryne precursor with sulfonamides efficiently afforded both 1,3-diaminobenzenes and trisubstituted 1,3-diaminobenzenes by simply varying the reaction conditions. Mechanistic study supports the sequential formation of two transient aryne intermediates involved in the reaction.
- Qiu, Dachuan,He, Jia,Yue, Xiao,Shi, Jiarong,Li, Yang
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supporting information
p. 3130 - 3133
(2016/07/14)
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- Triflic acid–catalyzed rearrangement of unalkylated benzene sulfonanilides
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ABSTRACT: Previous work has demonstrated that alkylated benzene sulfonanilides undergo sulfuric acid (98%)–catalyzed rearrangement to alkylamino diaryl sulfones. Similar treatment of their unalkylated analogs typically leads only to hydrolysis. Surprisingly, when the unalkylated benzene sulfonanilides react with triflic acid, rearrangement to sulfones does occur.
- Newcomer, Rebecca,McKee, James,Zanger, Murray
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supporting information
p. 949 - 955
(2016/07/12)
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- Short-Chain Branched Polar-Functionalized Linear Polyethylene via "tandem Catalysis"
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Cationic PdII complex 1 chelated by an N-fixed phosphine sultam has been synthesized and structurally characterized. Exposure of 1 to ethylene resulted in the formation of short-chain olefins (1-butene: 2-butene: 1-hexene: 1-octene = 86:7:6:1) with a high catalytic activity of 105 molE molPd-1 h-1. By combination of 1 and one of the well-known phosphinesulfonato PdII catalyst precursors 2-5, linear polyethylenes containing methyl, ethyl, and n-butyl branches of up to 100 per 1000 C were generated from the polymerization of ethylene alone in a "tandem catalysis" one-pot approach. In further exploitation of this concept, linear polyethylenes with both various short-chain branches and a choice of different polar functional groups incorporated into the main chain were obtained for the first time from the copolymerization of ethylene and polar vinyl monomers (methyl acrylate, N-isopropylacrylamide, methyl vinyl sulfone, acrylonitrile, ethyl vinyl ether, vinyl acetate, and allyl bromide). All these apolar and polar branches are incorporated into the linear polyethylene backbones to varying degrees, while the type of initiating and terminating chain ends of the resulting polyethylenes depends significantly on the nature of polar vinyl monomer.
- Jian, Zhongbao,Mecking, Stefan
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p. 4057 - 4066
(2016/07/06)
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- Visible Light-Induced Radical Rearrangement to Construct C-C Bonds via an Intramolecular Aryl Migration/Desulfonylation Process
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A highly efficient intramolecular selective aryl migration/desulfonylation of 2-bromo-N-aryl-N-(arenesulfonyl)amide via visible light-induced photoredox catalysis has been accomplished. This approach allows for the construction of a variety of multisubstituted N,2-diarylacetamide under mild reaction conditions.
- Li, Yuyuan,Hu, Bei,Dong, Wuheng,Xie, Xiaomin,Wan, Jun,Zhang, Zhaoguo
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p. 7036 - 7041
(2016/08/30)
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- NH4I-Catalyzed Synthesis of Sulfonamides from Arylsufonylhydrazides and Amines
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A novel and efficient approach to sulfonamides has been developed. Using TBHP as the oxidant and NH4I (20 mol%) as the catalyst, arylsulfonyl hydrazides reacted with amines to provide sulfonamides in moderate to good yields. Possible reaction pathway for the formation of the products was also discussed in this paper. Sulfonimides were synthesized through the oxidation coupling of arylsufonylhydrazides and amines by TBHP/NH4I system in moderate to good yields.
- Yu, Hui,Zhang, Yonghao
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supporting information
p. 359 - 362
(2016/04/26)
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