- A new practical one-pot access to sulfonimidates
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(matrix presented) Sulfonimidates were prepared from sulfinamides and iodosobenzene in a very mild one-pot procedure in good to excellent yields. This reaction allows quick and efficient access to a class of molecules of important synthetic as well as biological and industrial interest.
- Leca, Dominique,Fensterbank, Louis,Lacote, Emmanuel,Malacria, Max
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- Reactivity of cage-like amines toward p-toluenesulfonyl chloride and diphenyl chlorophosphate in acetonitrile
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The nucleophilic reactivity of amines of the norbornane, norbornene, and adamantane series toward p-toluenesulfonyl chloride and diphenyl chlorophosphate in acetonitrile at 25°C is determined mainly by the steric factor. Parameters characterizing spatial accessibility of the reaction center in the amine molecule have been determined. Cage-like substituents show no appreciable effect on the amine reactivity, as compared to common alkyl groups.
- Sadovskii,Solomoichenko,Kas'yan,Golodaeva,Anikanova,Kas'yan,Savelova
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- Synthesis, crystal structure, optical, electrochemical and thermal properties of the ynamide: Bis-(N-4-methylbenzenesulfonyl, N-n-butyl)-1,3-butadiyne-1,4-diamide
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The novel ynamide compound, bis-(N-4-methylbenzenesulfonyl, N-n-butyl)-1,3-butadiyne-1,4-diamide (3), was synthesized and characterized by single crystal X-ray diffraction, 1H and 13C NMR, UV-fluorescence spectroscopy, cyclic voltammetry, TGA and DSC techniques. This first reported X-ray structure of a 1,3-butadiyne-1,4-diamide revealed that the amido substituents of 3 adopt a twisted conformation in the crystal with a torsion angle of 76.6° resulting in a molecule with axial chirality. The crystal structure of compound 3 is stabilized by intermolecular CH-π interactions that give pairs of stacked bis-alkyne-3 units. HOMO/LUMO energy levels of 3 were experimentally determined by means of electrochemical and optical methods to be??5.87/?1.98?eV respectively. The solid state polymerization of the title compound was investigated by differential scanning calorimetry (DSC) revealing that polymerization proceeded simultaneously to the phase transition assigned to the melting of 3. The solid state polymerization of 3 is discussed of being a topochemically initiated polymer chain reaction that proceeds with a non-topochemical chain growth.
- Doan, Thu-Hong,Talbi, Imen,Lohier, Jean-Fran?ois,Touil, Soufiane,Alayrac, Carole,Witulski, Bernhard
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- Chemoselective Cleavage of Acylsulfonamides and Sulfonamides by Aluminum Halides
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The chemoselective cleavage of C-N bonds of amides, sulfonamides, and acylsulfonamides by aluminum halides is described. AlCl3and AlI3display complementary reactivities toward N-alkyl and N-acyl moieties. N-Alkylacylsulfonamides, sec
- Sang, Dayong,Dong, Bingqian,Liu, Yunfeng,Tian, Juan
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p. 3586 - 3595
(2022/02/25)
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- Direct conversion of sulfinamides to thiosulfonates without the use of additional redox agents under metal-free conditions
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Direct conversion of sulfinamides to thiosulfonates is described. Without the use of additional redox agents, the reaction proceeds smoothly in the presence of TFA under metal-free conditions. This protocol possesses many advantages such as odourless and stable starting materials, broad substrate scope, selective synthesis, and mild reaction conditions. This journal is
- Ji, Yuan-Zhao,Li, Hui-Jing,Wang, Jun-Hu,Wu, Yan-Chao,Zhang, Chi
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p. 9291 - 9298
(2021/11/13)
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- Au(I)-Catalyzed Oxidative Functionalization of Yndiamides
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Yndiamides, underexplored cousins of ynamides, offer rich synthetic potential as doubly nitrogenated two carbon building blocks. Here we report a gold-catalyzed oxidative functionalization of yndiamides to access unnatural amino acid derivatives, using a wide range of nucleophiles as a source of the amino acid side chain. The transformation proceeds under mild conditions, is highly functional group tolerant, and displays excellent regioselectivity through subtle steric differentiation of the yndiamide nitrogen atom substituents.
- Tong, Zixuan,Garry, Olivia L.,Smith, Philip J.,Jiang, Yubo,Mansfield, Steven J.,Anderson, Edward A.
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supporting information
p. 4888 - 4892
(2021/06/28)
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- Electrochemical C?H Amidation of Heteroarenes with N-Alkyl Sulfonamides in Aqueous Medium
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The construction of C?N bonds by free radical reactions represents a powerful synthetic approach for direct C?H amidations of arenes or heteroarenes. Developing efficient and more environmentally friendly synthetic methods for C?H amidation reactions remains highly desirable. Herein, metal-free electrochemical oxidative dehydrogenative C?H amidations of heteroarenes with N-alkylsulfonamides have been accomplished. The catalyst- and chemical-oxidant-free C?H amidation features an ample scope and employs electricity as the green and sole oxidant. A variety of heteroarenes, including indoles, pyrroles, benzofuran and benzothiophene, thereby underwent this C(sp2)?H nitrogenation. Cyclic voltammetry studies and control experiments provided evidence for nitrogen-centered radicals being directly generated under metal-free electrocatalysis.
- Zhang, Yan,Lin, Zhipeng,Ackermann, Lutz
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supporting information
p. 242 - 246
(2020/11/30)
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- Direct Synthesis of α-Amino Nitriles from Sulfonamides via Base-Mediated C-H Cyanation
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Herein, we disclose a transition-metal-free reaction system that enables α-cyanation of sulfonamides through C-H bond cleavage for the preparation of α-amino nitriles, including difficult-to-access all-alkyl α-tertiary scaffolds. More than 50 substrate examples prove a wide functional group tolerance. Additionally, its synthetic practicality is highlighted by gram-scalability and the late-stage modification of natural compounds. Mechanistic experiments suggest that this process involves in situ formation of an imine intermediate via base-promoted elimination of HF.
- Shi, Shasha,Yang, Xianyu,Tang, Man,Hu, Jiefeng,Loh, Teck-Peng
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p. 4018 - 4022
(2021/05/26)
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- Nickel/Photoredox Dual Catalytic Cross-Coupling of Alkyl and Amidyl Radicals to Construct C(sp3)-N Bonds
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The construction of C(sp3)-N bonds via direct radical-radical cross-coupling under benign conditions is a desirable but challenging approach. Herein, the cross-coupling of alkyl and amidyl radicals to build aliphatic C-N bonds in a concise, mild, and oxid
- Zhou, Shaofang,Lv, Kang,Fu, Rui,Zhu, Changlei,Bao, Xiaoguang
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p. 5026 - 5034
(2021/05/07)
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- Catalyst-free one-pot, four-component approach for the synthesis of di- And tri-substituted: N -sulfonyl formamidines
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A straightforward one-pot, multicomponent approach was developed to synthesize di- and tri-substituted N-sulfonyl formamidines from sulfonyl chlorides, NaN3, ethyl propiolate, and primary/secondary amines under mild conditions without catalysts or additives. Structural analysis of the di-substituted sulfonyl formamidines indicated formation of the E-syn/anti isomeric form. Tri-substituted analogues only formed E-isomers.
- Liu, Ai-Ran,Zhang, Lei,Li, Jiao,Wusiman, Abudureheman
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p. 15161 - 15166
(2021/05/19)
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- Electrochemical synthesis of sulfonamides in a graphite powder macroelectrode
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The electrochemical generation of sulfinyl radicals from commercially available and non-expensive sodium salts of sulfinic acids is described. Electrooxidation reactions were carried out in a graphite powder macroelectrode using an aqueous electrolyte and cavity cell. Further reaction with primary or secondary amines gave the corresponding sulfonamides, a unit present in several biologically active compounds and pharmaceuticals, in good yields.
- Galdino, Danilo,Menezes, Paulo H.,Navarro, Marcelo,Vicente, Dmistocles A.
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supporting information
p. 5262 - 5266
(2020/09/17)
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- KCC-1 aminopropyl-functionalized supported on iron oxide magnetic nanoparticles as a novel magnetic nanocatalyst for the green and efficient synthesis of sulfonamide derivatives
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A new magnetic nanocatalyst (Fe3O4@KCC-1-npr-NH2) was synthesized directly through the reaction of Fe3O4@KCC-1 with (3-aminopropyl) triethoxysilane (APTES) using a hydrothermal protocol. Prepared nanocomposite was used as a magnetically reusable nanocatalyst for an efficient synthesis of a broad range of sulfonamide derivatives in water as a green solvent at room temperature and the products are collected by filtration with excellent yields (85–97%). The nanocatalyst could be remarkably recovered and reused after ten times without any significant decrease in activity. This mild and simple synthesis method offers some advantages including short reaction time, high yield and simple work-up procedure.
- Azizi, Sajjad,Shadjou, Nasrin,Hasanzadeh, Mohammad
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- Catalytic Access to Functionalized Allylic gem-Difluorides via Fluorinative Meyer–Schuster-Like Rearrangement
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An unprecedented approach for efficient synthesis of functionalized allylic gem-difluorides via catalytic fluorinative Meyer–Schuster-like rearrangement is disclosed. This transformation proceeded with readily accessible propargylic fluorides, and low-cost B–F reagents and electrophilic reagents by sulfide catalysis. A series of iodinated, brominated, and trifluoromethylthiolated allylic gem-difluorides that were difficult to access by other methods were facilely produced with a wide range of functional groups. Importantly, the obtained iodinated products could be incorporated into different drugs and natural products, and could be expediently converted into many other valuable gem-difluoroalkyl molecules as well. Mechanistic studies revealed that this reaction went through a regioselective fluorination of alkynes followed by a formal 1,3-fluorine migration under the assistance of the B–F reagents to give the desired products.
- An, Rui,Li, Huimin,Liao, Lihao,Wu, Jin-Ji,Xu, Yang,Zhao, Xiaodan
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supporting information
p. 11010 - 11019
(2020/05/18)
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- Photoinduced site-selective C(sp3)-H chlorination of aliphatic amides
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Herein, we report a new photochemical method for C(sp3)-H chlorination of amides which employs tert-butyl hypochlorite as the chlorinating agent and a household compact fluorescent lamp as the light source. The reaction proceeds via N-heterocyclic carbene SIPr·HCl-promoted N-H chlorination and subsequent photoinduced Hofmann-L?ffler-Freytag chlorine atom transfer. The latter process is facilitated by (diacetoxyiodo)benzene. This protocol exhibits a broad scope and is suitable for site-selective chlorination of methyl hydrogen as well as methylene and methine hydrogen.
- Zhu, Yanshuo,Shi, Jingcheng,Yu, Wei
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supporting information
p. 8899 - 8903
(2020/11/30)
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- Metal-free synthesis of activated ynesulfonamides and tertiary enesulfonamides
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An operationally simple synthesis of activated ynesulfonamides and enesulfonamides is described. Ynesulfonamides can be obtained through reaction of sulfonylamides with activated bromoalkynes and Triton B in a short time at room temperature. Likewise, terminal alkynes react with sulfonylamides to provide enesulfonamides. Z/E enesulfonamides can be transformed exclusively into E enesulfonamides.
- Andna, Lucile,Miesch, Laurence
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supporting information
p. 5688 - 5692
(2019/06/19)
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- Transition-Metal-Free One-Step Synthesis of Ynamides
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A robust transition-metal-free one-step strategy for the synthesis of ynamides from sulfonamides and (Z)-1,2-dichloroalkenes or alkynyl chlorides is presented. This method is not only effective for internal ynamides but also amenable for terminal ynamides. Various functional groups, even the vinyl moiety, are compatible, and thus, this strategy offers the opportunity for further functionalization.
- Zeng, Xianzhu,Tu, Yongliang,Zhang, Zhenming,You, Changming,Wu, Jiao,Ye, Zhiying,Zhao, Junfeng
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p. 4458 - 4466
(2019/03/26)
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- A Micellar Catalysis Strategy for Amidation of Alkynyl Bromides: Synthesis of Ynamides in Water
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Copper-catalyzed amidation of alkynyl bromides can be carried out in water for the first time, which is made possible by a micellar catalysis strategy using rosin-based surfactant APGS-550-M. The surfactant can be easily prepared from natural abundant biomass, resin acids. Studies as to substrate scope and reaction aqueous medium recycling showcase the ease and sustainability of this technology.
- Yang, Yunqin,Meng, Xiangtai,Zhu, Baolong,Jia, Ying,Cao, Xiaoji,Huang, Shenlin
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supporting information
p. 1166 - 1169
(2019/01/04)
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- One-pot approach to access 2H-pyran-2-ones bearing an amino group via the Pd-catalyzed Sonogashira coupling of (Z)-3-iodovinylic esters followed by intramolecular iodocyclization
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A one‐pot sequence of Sonogashira coupling and iodocyclization afforded novel amino-containing trisubstituted 2H-pyran-2-ones in good yields. This transformation proceeds via 1) synthesis of an ynenoic ester intermediate by a Sonogashira coupling reaction with an N-substituted (Z)-3-iodovinylic ester; 2) intramolecular iodocyclization of the latter intermediate under mildly basic conditions. The flexibility of this strategy enables the efficient syntheses of a variety of substituted 2H-pyran-2-ones.
- Mayooufi, Atef,Romdhani-Younes, Moufida,Jacquemin, Johan,Thibonnet, Jér?me
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supporting information
(2019/09/03)
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- Tandem One-Pot Approach to N-Substituted Lactones by Carbon–Carbon Coupling Followed by 5-exo-dig or 6-endo-dig Cyclization: DFT Studies and Cyclization Mode
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A one-pot approach has been developed for the preparation of a five or six-membered ring of unsaturated lactones bearing an amino group through a tandem coupling oxacyclization reaction. This tandem process involves Sonogashira-like cross-coupling followed by 5-exo-dig or 6-endo-dig intramolecular oxacyclization, according to the nature of the alkynes substituent. Furthermore, DFT calculations were performed to analyze the origin of this regioselectivity of cyclization.
- Mayooufi, Atef,Jacquemin, Johan,Petrignet, Julien,Thibonnet, Jér?me
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supporting information
p. 7439 - 7447
(2019/11/28)
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- Efficient N-acylation of sulfonamides using cesium salt of Wells–Dawson heteropolyacid as catalyst: Synthesis of new N-acyl sulfonamides and cyclic imides
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N-acylation of substituted sulfonamides with different anhydrides in the presence of Cesium salt of Wells–Dawson heteropolyacid (Cs5HP2W18O62) as an efficient and reusable catalyst was investigated for the first time. ?Cs5HP2W18O62 was used with a catalytic amount in water as a green solvent. At room temperature, a series of N-acylsulfonamides were synthesized, while under refluxing conditions, new cyclic imides containing sulfonyl group were obtained. Atom-economy, high yields, easy work-up, as well as simple catalyst recovery and reusability are the key features of this procedure.
- Benali, Nesma,Bougheloum, Chafika,Alioua, Sabrina,Belghiche, Robila,Messalhi, Abdelrani
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p. 3099 - 3112
(2018/12/04)
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- Enantioselective Synthesis of trans-Vicinal Diamines via Rhodium-Catalyzed [2+2] Cycloaddition of Allenamides
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An efficient protocol for the enantioselective Rh-catalyzed intermolecular head-to-head [2+2] cycloaddition of allenamides was developed. A variety of enantio-enriched cyclobutane-1,2-diamine derivatives were achieved in good yields with good to excellent enantioselectivities. (Figure presented.).
- Zheng, Wei-Feng,Sun, Gui-Jun,Chen, Liang,Kang, Qiang
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supporting information
p. 1790 - 1794
(2018/04/02)
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- Anionic Ring-Opening Polymerization of N-(tolylsulfonyl)azetidines to Produce Linear Poly(trimethylenimine) and Closed-System Block Copolymers
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The anionic ring-opening copolymerization of N-(p-tolylsulfonyl)azetidine (pTsAzet) and N-(o-tolylsulfonyl)azetidine (oTsAzet) produces poly(pTsAzet-co-oTsAzet) as a statistical copolymer. The pTsAzet/oTsAzet copolymerization is living and allows for the synthesis of poly(sulfonylazetidine) of target molecular weights with narrow dispersities. 1H NMR spectroscopy was used to monitor the kinetics of the polymerization and estimate the monomer reactivity ratios. It was found that the reactivity ratios for oTsAzet and pTsAzet at 180 °C are 1.66 and 0.60, respectively. The tosyl groups of p(pTsAzet-co-oTsAzet) were reductively removed to produce linear poly(trimethylenimine) (LPTMI). This represents the first route to LPTMI of controlled molecular weight and low dispersity. Finally, the slow kinetics of the sulfonylazetidine polymerization facilitated the synthesis of a block copolymer without requiring the sequential addition of monomer. Specifically, pTsAzet, oTsAzet, and (N-p-toluenesulfonyl-2-methylaziridine) (pTsMAz) were combined in solution. pTsMAz selectively polymerizes to form the first block at moderate temperature. After consumption of pTsMAz, the temperature was increased to copolymerize pTsAzet and oTsAzet and produce the block copolymer p(pTsMAz)-b-p(pTsAzet-co-oTsAzet).
- Reisman, Louis,Rowe, Elizabeth A.,Jackson, Enrique M.,Thomas, Christian,Simone, Tomekia,Rupar, Paul A.
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supporting information
p. 15626 - 15630
(2018/12/11)
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- Method of synthesis of N-alkyl p-toluene sulfonamide
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The invention relates to a method of synthesis of N-alkyl p-toluene sulfonamide. In the presence of a PIMs supported solid super acid catalyst, a reaction between anhydrous p-toluene sulfonamide and a primary amine is carried out in the presence of a water absorber 5A-type molecular sieve to obtain a target product. The conversion rate of the anhydrous p-toluene sulfonamide reaches 81.90%, and the yield of the N-alkyl p-toluene sulfonamide can reach 70.53%. The method has high catalyst yield and mild reaction conditions. The catalyst is easy to recycle. The method is low in environment pollution.
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Paragraph 0012; 0014; 0015
(2017/08/28)
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- Preparation N - alkyl toluene sulfonamide method
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The invention discloses a method for preparing N-alkyl-p-toluenesulfonamide. The method comprises the following steps: (1) dissolving anhydrous p-toluenesulfonic acid in a dichloromethane solvent, adding a catalyst and a molecular sieve 5A, and controlling the temperature to be 0-40 DEG C; (2) adding primary amine for a reaction, wherein the reaction temperature is 0-40 DEG C; (3) after the reaction is finished, carrying out suction filtration to remove the molecular sieve 5A; (4) washing a filtrate with an acid solution, then carrying out washing with an alkali solution and a salt solution in sequence, carrying out separation to obtain an organic phase, removing a drying agent after drying the organic phase with anhydrous sodium sulfate, and carrying out distillation to recover dichloromethane and obtain a crude product of N-alkyl-p-toluenesulfonamide; (5) carrying out washing with a 50% ethanol water solution, and carrying out weighing after drying. The method has the advantages that the catalyst is used, so that anhydrous p-toluenesulfonic acid can be directly reacted with primary amine in the dichloromethane organic solvent at low temperature; the molecular sieve 5A is added in the reaction between anhydrous p-toluenesulfonic acid and primary amine as a water absorbent, so that water generated in the reaction can be absorbed to ensure a smooth reaction process. According to liquid chromatography analysis, the purity and the yield of N-alkyl-p-toluenesulfonamide exceeds 98% and reaches about 40% respectively.
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Paragraph 0018; 0019; 0021; 0023; 0025; 0037
(2017/08/25)
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- Metal-free I2O5-mediated direct construction of sulfonamides from thiols and amines
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A simple and convenient method has been developed for the construction of sulfonamides via I2O5-mediated sulfonylation of amines with arylthiols. The present protocol provides an attractive approach to sulfonamides in moderate to good yields from readily accessible and easy to handle starting materials under mild and metal-free conditions.
- Zhu, Minghui,Wei, Wei,Yang, Daoshan,Cui, Huanhuan,Wang, Leilei,Meng, Guoqing,Wang, Hua
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supporting information
p. 4789 - 4793
(2017/07/10)
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- Preparation method of sulfonamides compound
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The invention discloses a reparation method of a sulfonamides compound. The preparation method includes: using thiophenol and amine which are simple and easy to get as raw materials; enabling the raw materials to be in direct oxidation coupling reaction under mediation of safe and stable iodine pentoxide to prepare sulfonamide. The preparation method has the advantages that reaction conditions are mild (60 DEG C), the raw materials are simple and easy to get and low in price, reaction environment is friendly, a substrate is wide in application range, and metal catalysts and harsh reaction conditions like low or high temperature and zero water and zero oxygen are not needed, so that metal pollution related to common synthesis methods is avoided; the preparation method further has the advantages of simple, convenient and safe operation, stable process condition and easiness in product purification and is suitable for large-scale production.
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Paragraph 0038; 0039
(2017/09/02)
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- Ligand-Controlled Cobalt-Catalyzed Transfer Hydrogenation of Alkynes: Stereodivergent Synthesis of Z- and E-Alkenes
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Herein, we report a novel cobalt-catalyzed stereodivergent transfer hydrogenation of alkynes to Z- and E-alkenes. Effective selectivity control is achieved based on a rational catalyst design. Moreover, this mild system allows for the transfer hydrogenation of alkynes bearing a wide range of functional groups in good yields using catalyst loadings as low as 0.2 mol %. The general applicability of this procedure is highlighted by the synthesis of more than 50 alkenes with good chemo- and stereoselectivity. A preliminary mechanistic study revealed that E-alkene product was generated via sequential alkyne hydrogenation to give Z-alkene intermediate, followed by a Z to E alkene isomerization process.
- Fu, Shaomin,Chen, Nan-Yu,Liu, Xufang,Shao, Zhihui,Luo, Shu-Ping,Liu, Qiang
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p. 8588 - 8594
(2016/07/27)
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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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- Electrosynthesis of Arylsulfonamides from Amines and Sodium Sulfinates Using H2O-NaI as the Electrolyte Solution at Room Temperature
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With H2O as the solvent and NaI as the supporting electrolyte, a green and efficient electrochemical route has been developed to synthesize arylsulfonamides via I2electrogenerated in situ at a graphite anode to promote the reaction of sodium sulfinates with aromatic or aliphatic primary and secondary amines. The target products could be obtained in good to excellent yields at room temperature.
- Zhang, Chen,Chen, Yibin,Yuan, Gaoqing
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p. 1277 - 1282
(2016/12/27)
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- A synthetic N-alkyl sulfonamide derivatives
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The invention discloses a method for synthesizing a N-alkyl sulfonamide derivative. The method comprises the following steps: adding a sulfonamide derivative, a water-soluble catalyst, an alkali, alcohol and a solvent into a reaction container; reacting the reaction mixture at 100-120 DEG C for several hours, cooling to room temperature; performing rotary evaporation to remove the solvent, and then separating by a column to obtain the target compound. The method of the invention starts from the sulfonamide derivative, and obtains the N-alkyl sulfonamide derivative through reaction with alcohol. The method of the invention adopts a water-soluble iridium complex as a catalyst; the reaction is carried out in water; and the target compound is obtained with a high yield. Therefore, the reaction meets the requirements for green chemistry, and the method has wide development prospects.
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Paragraph 0098-0101
(2016/10/10)
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- The mechanism of alkene elimination from protonated toluenesulphonamides generated by electrospray ionisation
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The positive ion electrospray mass spectra of a range of sulphonamides of general structure CH3C6H4SO2NHR1 [R1 = CnH2n+1 (n = 1-7), CnH2n-1 (n = 3, 4), C6H5, C6H5CH2 and C6H5CH(CH3)] and CH3C6H4SO2NR1R2 [R1, R2 = CnH2n+1 (n = 1-8)] are reported and discussed. The protonated sulphonamides derived from saturated primary and secondary aliphatic amines generally fragment to only a limited extent unless energised by collision. Two general fragmentations are observed: firstly, elimination of an alkene, CnH2n, obtained by hydrogen abstraction from one of the CnH2n+1 alkyl groups on nitrogen; secondly, cleavage to form CH3C6H4SO2+. The mechanism by which an alkene is lost has been probed by studying the variation of the intensity of the [M + H - CnH2n]+ signal with the structure of the alkyl substituent(s) on nitrogen and by monitoring the competition between the loss of different alkenes from protonated unsymmetrical sulphonamides in which two different alkyl groups are attached to nitrogen. This fragmentation is favoured by branching of the alkyl group at the carbon atom directly attached to nitrogen, thus suggesting that it involves a mechanism in which the stability of the cation obtained by stretching the bond connecting the nitrogen atom to the alkyl group is critical. This interpretation also explains the competition between alkene elimination and cleavage to form CH3C6H4SO2+ (and, in some cases, cleavage to form C6H5CH2+ or [C6H5CHCH3]+).
- Saidykhan, Amie,Ebert, Jenessa,Martin, William H.C.,Gallagher, Richard T.,Bowen, Richard D.
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p. 165 - 173
(2016/11/09)
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- Sulfonyl Azides as Precursors in Ligand-Free Palladium-Catalyzed Synthesis of Sulfonyl Carbamates and Sulfonyl Ureas and Synthesis of Sulfonamides
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(Chemical Equation Presented). An efficient synthesis of sulfonyl carbamates and sulfonyl ureas from sulfonyl azides employing a palladium-catalyzed carbonylation protocol has been developed. Using a two-chamber system, sulfonyl azides, PdCl2, and CO gas, released ex situ from Mo(CO)6, were assembled to generate sulfonyl isocyanates in situ, and alcohols and aryl amines were exploited as nucleophiles to afford a broad range of sulfonyl carbamates and sulfonyl ureas. A protocol for the direct formation of substituted sulfonamides from sulfonyl azides and amines via nucleophilic substitution was also developed.
- Chow, Shiao Y.,Stevens, Marc Y.,Odell, Luke R.
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p. 2681 - 2691
(2016/04/26)
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- Iodine-catalyzed expeditious synthesis of sulfonamides from sulfonyl hydrazides and amines
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A new synthesis of sulfonamides has been developed via an iodine-catalyzed sulfonylation of amines with arylsulfonyl hydrazides. This metal-free strategy employs readily accessible and easy to handle starting materials, catalysts and oxidants, and can be easily conducted under mild conditions, providing a convenient access to a wide range of sulfonamides in moderate to excellent yields within a short reaction time.
- Yotphan, Sirilata,Sumunnee, Ladawan,Beukeaw, Danupat,Buathongjan, Chonchanok,Reutrakul, Vichai
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p. 590 - 597
(2016/01/12)
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- Iodine-catalyzed oxidative amination of sodium sulfinates: A convenient approach to the synthesis of sulfonamides under mild conditions
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The iodine-catalyzed oxidative amination of sodium sulfinates in the presence of sodium percarbonate as the oxidant has been developed. The reaction shows good substrate scope and tolerates a wide range of functionalities in both amine and sodium sulfinate substrates. Aliphatic amines, heteroaromatic amines and hydrochloride salts of amines canbe employed as the amine sources in this transformation. Mechanistic studies indicated that a radical pathway might be involved in the reaction process. This transition-metalfree protocol offers an alternative and convenient approach for a preparation of a series of sulfonamides in moderate to good yields under mild conditions.
- Buathongjan, Chonchanok,Beukeaw, Danupat,Yotphan, Sirilata
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p. 1575 - 1582
(2015/03/04)
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- N-alkylation of sulfonamides with alcohols by Tf2O
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N-sulfonylpyrrolidines and N-alkyl sulfonamides were efficiently prepared via alkylation of sulfonamides with 1,4- diols or alcohols by Tf2O. The reaction occurred under mild reaction conditions in moderate to high yields and tolerated aryl and aliphatic sulfonamides.
- Yu, Ting Ting,Qi, Lan-Jun,Cui, Dong-Mei,Zhang, Chen,Zhao, Yan
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supporting information
p. 610 - 612
(2015/08/04)
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- Palladium-Catalyzed Regio- and Chemoselective Reactions of 2-Bromobenzyl Bromides: Expanding the Scope for the Synthesis of Biaryls Fused to a Seven-Membered Sultam
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Speedy access to biaryls fused to seven-membered sultams was achieved by starting from readily accessible N-alkylbenzenesulfonamides and 2-bromobenzyl bromides. The protocol features a domino reaction and proceeds through an N-benzylation followed by an intramolecular direct C-H arylation that occurs ortho to the sulfonamide group. A palladium-catalyzed domino reaction of N-alkylbenzenesulfonamides and 2-bromobenzyl bromides gives biaryls fused to a seven-membered sultam. This approach employs readily accessible substrates and provides speedy access to fused-ring compounds.
- Laha, Joydev K.,Sharma, Shubhra,Dayal, Neetu
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p. 7885 - 7891
(2015/12/24)
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- Chemoselective Intramolecular Functionalization of Methyl Groups in Nonconstrained Molecules Promoted by N-Iodosulfonamides
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Mechanistic evidence observed in Hofmann-L?ffler-Freytag-type reactions has been crucial to achieve the chemoselective functionalization of methyl groups under mild conditions. Radical-mediated methyl iodination and subsequent oxidative deiodination are the key steps in this functionalization, where iodine chemistry has a pivotal role on the formation of the C-N bond. The concepts of single hydrogen atom transfer (SHAT) and multiple hydrogen atom transfer (MHAT) are introduced to describe the observed chemoselectivity. (Chemical Equation Presented).
- Paz, Nieves R.,Rodríguez-Sosa, Dionisio,Valdés, Haydee,Marticorena, Ricardo,Melián, Daniel,Copano, M. Belén,González, Concepción C.,Herrera, Antonio J.
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supporting information
p. 2370 - 2373
(2015/06/02)
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- Synthesis of nitromethyl-substituted oxindole derivatives via a desulfonylation cascade
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A cascade reaction giving nitromethyl-substituted oxindole derivatives was developed. The reaction used NaNO2 as the nitro source and potassium peroxydisulfate as an oxidant. This reaction proceeded via a radical mechanism involving substitution-desulfonlylation-cyclization steps in one pot and afforded good yields under mild conditions without using toxic metal catalysts. The resultant nitromethyl-substituted oxindole derivatives are convenient and valuable structures for different derivative syntheses.
- Niu, Ben,Xie, Ping,Bian, Zhaogang,Zhao, Wannian,Zhang, Min,Zhou, Yang,Feng, Lei,Pittman, Charles U.,Zhou, Aihua
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supporting information
p. 635 - 638
(2015/03/14)
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- Palladium-Catalyzed Allylic Amination of Homoallylic Alcohols with Amines via Carbon-Carbon Bond Cleavage
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An efficient approach for palladium(II) acetate catalyzed allylic amination of homoallylic alcohols with various amines via sequential retro-allylation and amination was developed, which afforded the corresponding allylic amines in up to 98% yield.
- Sun, Gui-Jun,Wang, Yong,Kang, Qiang
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supporting information
p. 2931 - 2936
(2015/09/28)
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- Br?nsted acid-assisted N-alkylation of sulfonamides using ethers as the alkylation reagents
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N-Alkylation of sulfonamides using cyclic ethers as alkylation reagents and Br?nsted acid as a catalyst produced pyrrolidine and piperidine derivatives in good yields. When using symmetrical and unsymmetrical ethers as alkylation reagents, mono-N-alkylation of sulfonamides took place to afford the corresponding products.
- Shi, Wei,Bai, Chun-Mei,Zhu, Kai,Cui, Dong-Mei,Zhang, Chen
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p. 434 - 438
(2014/01/06)
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- Metal-free oxidative coupling of amines with sodium sulfinates: A mild access to sulfonamides
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A practical and mild procedure for the preparation of sulfonamides through TBAI-catalyzed oxidative coupling of amines with sodium sulfinates using TBHP as an oxidant was presented. A variety of amines and sodium sulfinates could go through the transformation, without impacting the hydroxyl group. This journal is
- Zhao, Jinwu,Xu, Jingxiu,Chen, Jiaxi,Wang, Xiaoqin,He, Minghua
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p. 64698 - 64701
(2015/04/27)
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- The N-alkylation of sulfonamides with alcohols in water catalyzed by the water-soluble iridium complex {Cp*[6,6'-(OH)2bpy](H 2O)}[OTf]2
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The water-soluble iridium complex {Cp*[6,6'-(OH)2bpy] (H2O)}[OTf]2 (Cp=ν5-pentamethylcyclopentadienyl, bpy=2,2'-bipyridine) was found to be a general and highly efficient catalyst for the Nalkylation of the poor nucleophilic sulfonamides with alcohols as alkylating agents in water. The presence of OH units in the bpy ligand is crucially important for the catalytic activity of the iridium complex. Mechanistic investigations revealed that the catalytically active species is a ligand-metal bifunctional iridium complex bearing an N,N'-chelated 2,2'-bipyridinated ligand and an aqua ligand. Notably, the present catalytic system and the proposed mechanism provide a new horizon and scope for the development of "hydrogen autotransfer (or hydrogen-borrowing) processes".
- Qu, Panpan,Sun, Chunlou,Ma, Juan,Li, Feng
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p. 447 - 459
(2014/05/20)
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- CuI-catalyzed coupling of gem-dibromovinylanilides and sulfonamides: An efficient method for the synthesis of 2-amidoindoles and indolo[1,2-a] quinazolines
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A Cu(I)-catalyzed, intermolecular protocol for the synthesis of 2-amidoindoles and tetrahydroindolo[1,2-a]quinazolines in shorter time and high yields is reported. The key highlight of this disclosure is the formation of 2-amidoindole and tetrahydroindolo[1,2-a]quinazoline moieties directly from gem-dibromovinylanilides and sulfonamides in a one-pot fashion through the in situ formation of ynamides followed by a base-promoted intramolecular hydroamidation.
- Kiruthika, Selvarangam E.,Perumal, Paramasivan Thirumalai
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supporting information
p. 484 - 487
(2014/04/03)
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- Synthesis of pyrrolo-/indolo[1,2-a ]quinolines and naphtho[2,1- b ]thiophenes from gem -dibromovinyls and sulphonamides
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A highly efficient and simple route for the synthesis of pyrrolo-/indolo[1,2-a]quinolines and naphtho[2,1-b]thiophenes from gem-dibromovinyls and sulphonamides is reported. The noteworthy feature of this report is that the methodology involves a two-step protocol to synthesize tri- and tetracyclic heterocycles in a one-pot fashion through the Cu(I)-catalyzed formation of ynamide followed by a Ag(I)-assisted intramolecular hydroarylation. The photophysical properties of representative examples of pyrrolo- and indolo[1,2-a]quinolines in solid and solution states have also been studied.
- Kiruthika, Selvarangam E.,Nandakumar, Avanashiappan,Perumal, Paramasivan Thirumalai
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supporting information
p. 4424 - 4427
(2015/02/05)
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- Copper-catalyzed sulfonamides formation from sodium sulfinates and amines
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A new and convenient method for the construction of sulfonamides via a copper-catalyzed oxidative coupling between sodium sulfinates and amines with 1 atm O2 or DMSO as the oxidant was described. This method provides efficient and robust synthesis of functional sulfonamides in good yields and excellent chemoselectivity. And detailed mechanistic studies showed that this transformation may go through a single electron transfer (SET) pathway.
- Tang, Xiaodong,Huang, Liangbin,Qi, Chaorong,Wu, Xia,Wu, Wanqing,Jiang, Huanfeng
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supporting information
p. 6102 - 6104
(2013/07/11)
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- Sulfonamide synthesis via oxyma-O-sulfonates - Compatibility to acid sensitive groups and solid-phase peptide synthesis
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A milder and more efficient procedure for the synthesis of sulfonamides by activating sulfonic acid groups as the corresponding sulfonate esters of ethyl 2-cyano-2-(hydroxyimino)acetate (Oxyma) is reported. This method is greener than all other existing protocols for the purpose. Other important advantages lie in (a) its applicability to less nucleophilic anilines under ambient and milder conditions and (b) its compatibility with solid phase peptide synthesis and acid-labile groups such as trityl (Trt) and tBu, which empowers the solid phase synthesis of sulfonamides of various peptides. To illustrate this, the syntheses of three sulfonamide derivatives of the peptide GAILG-NH2, which is relevant in the context of drug design against type 2 diabetes, are demonstrated by using Fmoc-based solid-phase peptide synthesis (SPPS). The activation of sulfonic acids as their corresponding O-sulfonate esters facilitates sulfonamide synthesis, which can be applied to those substrates that possess acid-labile functional groups and is compatible with solid phase synthesis. Copyright
- Palakurthy, Nani Babu,Dev, Dharm,Rana, Shubhasmin,Nadimpally, Krishna Chaitanya,Mandal, Bhubaneswar
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p. 2627 - 2633
(2013/06/04)
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- TiCl4-mediated direct N-alkylation of sulfonamides with inactive ethers
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A TiCl4-mediated intermolecular or intramolecular direct N-alkylation reaction of sulfonamides with inactive ethers as alkylating agents was successfully achieved. This method provides a novel approach towards N-alkyl sulfonamides from inactive ethers via an easy workup procedure. Georg Thieme Verlag Stuttgart · New York.
- Chen, Jiayan,Dang, Ling,Li, Qiang,Ye, Yong,Fu, Shaomin,Zeng, Wei
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supporting information; experimental part
p. 595 - 600
(2012/03/27)
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- Functionalization of mesoporous carbon with superbasic MgO nanoparticles for the efficient synthesis of sulfinamides
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Highly basic MgO nanoparticles with different sizes have been successfully immobilized over mesoporous carbon with different pore diameters by a simple wet-impregnation method. The prepared catalysts have been characterized by various sophisticated techniques, such as XRD, nitrogen adsorption, electron energy loss spectroscopy, high-resolution TEM, X-ray photoelectron spectroscopy, and the temperature-programmed desorption of CO2. XRD results reveal that the mesostructure of the support is retained even after the huge loading of MgO nanoparticles inside the mesochannels of the support. It is also demonstrated that the particle size and dispersion of the MgO nanoparticles on the support can be finely controlled by the simple adjustment of the textural parameters of the supports. Among the support materials studied, mesoporous carbon with the largest pore diameter and large pore volume offered highly crystalline small-size cubic-phase MgO nanoparticles with a high dispersion. The basicity of the MgO-supported mesoporous carbons can also be controlled by simply changing the loading of the MgO and the pore diameter of the support. These materials have been employed as heterogeneous catalysts for the first time in the selective synthesis of sulfinamides. Among the catalysts investigated, the support with the large pore diameter and high loading of MgO showed the highest activity with an excellent yield of sulfinamides. The catalyst also showed much higher activity than the pristine MgO nanoparticles. The effects of the reaction parameters, including the solvents and reaction temperature, and textural parameters of the supports in the activity of the catalyst have also been demonstrated. Most importantly, the catalyst was found to be highly stable, showing excellent activity even after the third cycle of reaction. Reuse and recycle: Highly basic MgO-functionalized mesoporous carbon with different pore diameters has been prepared (see picture). The material showed a much higher performance in the synthesis of sulfinamides than pure MgO nanoparticles. The catalyst was also highly stable and could be reused several times without affecting its activity. Copyright
- Chakravarti, Rajashree,Mano, Ajayan,Iwai, Hideo,Aldeyab, Salem S.,Kumar, R. Pradeep,Kantam, M. Lakshmi,Vinu, Ajayan
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supporting information; experimental part
p. 6673 - 6682
(2011/08/05)
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- Sulfonamide synthesis using N-hydroxybenzotriazole sulfonate: An alternative to pentafluorophenyl (PFP) and trichlorophenyl (TCP) esters of sulfonic acids
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The N-hydroxybenzotriazole (HOBt) sulfonate esters undergo amidation under ambient conditions in the presence of di-isopropylethyl amine. This method can be applied to varieties of amines including sterically hindered amino acid esters in less time with reasonably good yields. HOBt ester of sulfonic acids can be a replacement for pentafluorophenyl and trichlorophenyl ester as well as chloride moiety of sulfonyl chloride for amidation.
- Palakurthy, Nani Babu,Mandal, Bhubaneswar
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p. 7132 - 7134
(2012/02/01)
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- Borrowing hydrogen methodology for amine synthesis under solvent-free microwave conditions
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Application of microwave heating to the Borrowing Hydrogen strategy to form C-N bonds from alcohols and amines is presented, removing the need for solvent and reducing the reaction times while still yielding results comparable with those using thermal heating.
- Watson, Andrew J. A.,Maxwell, Aoife C.,Williams, Jonathan M. J.
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supporting information; experimental part
p. 2328 - 2331
(2011/05/17)
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- Efficient dehydrative C-N bond formation using alcohols and amides in the presence of silica supported perchloric acid as a heterogeneous catalyst
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Silica supported perchloric acid has been utilized as an efficient heterogeneous recyclable catalyst for N-alkylation of amides (sulfonamides and carboxamides) using alcohols (primary and secondary aliphatic as well as benzylic). The products are formed in high yields within 2-3 h.
- Das, Biswanath,Reddy, Parigi Raghavendar,Sudhakar, Chithaluri,Lingaiah, Maram
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experimental part
p. 3521 - 3522
(2011/06/27)
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- CsF-Celite as an efficient heterogeneous catalyst for sulfonylation and desulfonylation of heteroatoms
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CsF-Celite is found to be as an efficient reusable catalyst for sulfonylation and desulfonylation of heteroatoms. Sulfonamides and N-acylsulfonamides deprotect efficiently in the presence of CsF-Celite under solvent free conditions to give the free amines or amides in good to excellent yields.
- Tamaddon, Fatemeh,Nasiri, Alireza,Farokhi, Somayeh
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experimental part
p. 1477 - 1482
(2012/06/18)
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