- Merging Photoredox Catalysis with Transition Metal Catalysis: Direct C4-H Sulfamidation of 1-Naphthylamine Derivatives
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A mild and efficient protocol for the copper(I)-catalyzed C4-H sulfamidation of 1-naphthylamine derivatives with diphenylsulfonimide (NHSI) was explored at room temperature, affording the desire produces in moderate to good yields. The control experiments indicated that this visible-light-promoted reaction might proceed via a single-electron-transfer process. In addition, preliminary DFT studies for the intermediates in the catalytic cycle were also explored, indicating that the C4 site in the naphthyl ring is the most likely electrophilic reactive site and providing some exact basis for the plausible mechanism.
- Pei, Mengxue,Zu, Conghui,Liu, Zhen,Yang, Fan,Wu, Yangjie
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p. 11324 - 11332
(2021/09/02)
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- Cobalt-catalyzed Divergent Markovnikov and Anti-Markovnikov Hydroamination
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Catalytic hydroamination of the readily available alkenes is among the most straightforward means to construct diverse alkyl amines. To this end, the facile access to both regioselectivity, i.e., Markovnikov or anti-Markovnikov hydroamination, with minimum reaction-parameter alternation, remains challenging. Herein, we report a cobalt-catalyzed highly selective and divergent Markovnikov and anti-Markovnikov hydroamination of alkenes, in which the switch of regioselectivity is achieved simply by the variation of the addition sequence of 9-BBN.
- Chen, Zheng,Guo, Peng,He, Zi-Xin,Ye, Ke-Yin,Zhang, Xiang-Gui
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supporting information
(2022/01/04)
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- Copper-Catalyzed Radical N-Demethylation of Amides Using N-Fluorobenzenesulfonimide as an Oxidant
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An unprecedented N-demethylation of N-methyl amides has been developed by use of N-fluorobenzenesulfonimide as an oxidant with the aid of a copper catalyst. The conversion of amides to carbinolamines involves successive single-electron transfer, hydrogen-atom transfer, and hydrolysis, and is accompanied by formation of N-(phenylsulfonyl)benzenesulfonamide. Carbinolamines spontaneously decompose to N-demethylated amides and formaldehyde, because of their inherent instability.
- Yi, Xuewen,Yi, Xuewen,Lei, Siyu,Liu, Wangsheng,Che, Fengrui,Yu, Chunzheng,Liu, Xuesong,Wang, Zonghua,Zhou, Xin,Zhang, Yuexia
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supporting information
p. 4583 - 4587
(2020/05/05)
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- A Novel Synthesis of N -Sulfonylformamidines from N Sulfonyl sulfonamides
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N -Sulfonylformamidines were synthesized from N -sulfonylsulfonamides by reacting with p -toluenesulfonyl chloride (TsCl) and N, N - disubstituted formamides. In this reaction, it was expected that mixing TsCl with the N, N -disubstituted formamide would generate an iminium salt (Vilsmeier reagent). The reaction avoids the use of metal catalysts and hazardous reagents, and the desired N -sulfonylformamidines were obtained in 60% to quantitative yields.
- Jeong, Yuri,Ban, Jaeyoung,Lim, Minkyung,Rhee, Hakjune
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supporting information
p. 1867 - 1874
(2018/02/26)
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- Method for preparing dibenzenesulfonimide by solvent-free grinding method
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The invention relates to a method for preparing dibenzenesulfonimide by a solvent-free grinding method. According to the method, firstly, benzsulfamide and pure benzene sulfonyl chloride are put into a ball mill to be ground, so that the benzsulfamide and the benzene sulfonyl chloride are sufficiently and uniformly mixed at room temperature; then, solid NaOH is fed into the ball mill in different batches; the grinding is continuously performed; the temperature of a reactant is maintained to be lower than 60 DEG C; after the reaction is completed, the reactant is moved out from the ball mill; the reactants are dissolved by organic solvents; filtering is performed for removing generated NaCl; filter liquid is obtained; finally, the filter liquid is subjected to concentration crystallization, filtering and drying; a product is obtained. In the whole reaction process, the solvent is not needed; the environment pollution is reduced; the production cost is reduced. The atom utilization rate of the whole preparation process is high; the atom economic green and environment-friendly ideal is met; the method is suitable for industrial production.
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Paragraph 0018; 0019; 0020; 0021; 0022; 0023; 0024-0027
(2017/08/28)
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- Synergistic copper-TEMPO catalysis of intermolecular vicinal diamination of styrenes
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A copper-catalyzed, 2,2,6,6-tetramethyl piperidine N-oxy radical-assisted intermolecular diamination of styrenes with N-fluorobenzenesulfonimide has been developed. The current protocol proved amenable to a diverse array of styrenes via cascade radical addition to readily afford synthetically useful aromatic vicinal diamines with exclusive diastereoselectivity.
- Weng, Shiue-Shien,Hsieh, Kun-Yi,Zeng, Zih-Jian,Zhang, Jia-Wei
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supporting information
p. 670 - 673
(2017/01/25)
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- Preparation method of dibenzenesulfonimide
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The invention discloses a preparation method of dibenzenesulfonimide. The preparation method comprises the following steps: (1) preparing dibenzenesulfonimide sodium salt: adding benzene sulfonamide and benzene sulfonyl chloride into an isopropanol-sodium alcoholate system in different steps to carry out reactions; (2) purifying dibenzenesulfonimide sodium salt: adding sodium hydroxide into the isopropanol-sodium alcoholate system in different steps, adjusting the pH value to 10-12, making the system go through anion exchange resin, then cooling to precipitate crystals, and carrying out centrifugal separation to obtain dibenzenesulfonimide sodium salt; (3) preparing dibenzenesulfonimide: dissolving dibenzenesulfonimide sodium salt into hot water, making the solution go through cation exchange resin, cooling to precipitate crystals, carrying out centrifugal separation, and drying to obtain dibenzenesulfonimide. The preparation method has the advantages that raw materials are fully and effectively converted into the target product, the side reactions are avoided, the purification and separation mode is reasonable, the product purity is high, the yield is high, and moreover, the method is economic and environment-friendly and can be easily applied to industrial production.
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Paragraph 0032; 0033
(2017/02/09)
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- PROCESS FOR THE PREPARATION OF DIBENZENESULFONIMIDE
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The present invention provides a process for the preparation of dibenzenesulfonimide.
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Page/Page column 6
(2016/02/26)
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- N-Trifluoromethylthio-dibenzenesulfonimide: A Shelf-Stable, Broadly Applicable Electrophilic Trifluoromethylthiolating Reagent
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The super electrophilicity of a shelf-stable, easily prepared trifluoromethylthiolating reagent N-trifluoromethylthio-dibenzenesulfonimide 7 was demonstrated. Consistent with the theoretical prediction, 7 exhibits reactivity remarkably higher than that of other known electrophilic trifluoromethylthiolating reagents. In the absence of any additive, 7 reacted with a wide range of electron-rich arenes and activated heteroarenes under mild conditions. Likewise, reactions of 7 with styrene derivatives can be fine-tuned by simply changing the reaction solvents to generate trifluoromethylthiolated styrenes or oxo-trifluoromethylthio or amino-trifluoromethylthio difunctionalized compounds in high yields.
- Zhang, Panpan,Li, Man,Xue, Xiao-Song,Xu, Chunfa,Zhao, Qunchao,Liu, Yafei,Wang, Haoyang,Guo, Yinlong,Lu, Long,Shen, Qilong
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p. 7486 - 7509
(2016/09/09)
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- TRANSITION METAL-CATALYZED IMIDATION OF ARENES
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The present invention provides novel transition metal complexes (e.g., complexes of any one of Formulae (C1) to (C25)) that include an amine-N-oxide motif. The invention also provides methods of using these transition metal complexes in preparing N-aryl or N- heteroaryl sulfonimides (e.g., compounds of Formula (I)) and aryl or heteroaryl amines (e.g., compounds of Formula (II)). The inventive methods involve imidation of arenes and heteroarenes (e.g., compounds of Formula (A)) using an imidating agent (e.g., a compound of Formula (B), such as N-fluorobenzenesulfonimide (NFBS or NFSI)) in the presence of a single-electron reductant (e.g., an Ag(I) or Ru(II) salt).
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Paragraph 00277-00280
(2015/03/13)
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- Highly regioselective radical amination of allenes: Direct synthesis of allenamides and tetrasubstituted alkenes
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The first controllable, regioselective radical amination of allenes with N-fluoroarylsulfonimide is described to proceed under very mild reaction conditions. With this methodology, a general and straightforward route for the synthesis of both allenamides and fluorinated tetrasubstituted alkenes was realized from a wide range of terminal and internal allenes. Radical highway: By employing N-fluoroarylsulfonimide as a nitrogen source, a facile, mild, and highly regioselective copper-catalyzed oxidative radical amination of various allenes was developed. In addition, a protocol involving nitrogen radical addition/fluorine-atom transfer affords fluorinated tetrasubstituted alkenes by using silver as catalyst.
- Zhang, Ge,Xiong, Tao,Wang, Zining,Xu, Guoxing,Wang, Xuedan,Zhang, Qian
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supporting information
p. 12649 - 12653
(2015/10/28)
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- Pd-catalyzed aryl C-H imidation with arene as the limiting reagent
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An amine-N-oxide-ligated palladium complex, in conjunction with a silver cocatalyst, catalyzes imidation of arenes by the reagent N- fluorobenzenesulfonimide. The reaction enables imidation of a variety of arenes at or below room temperature, requires no coordinating directing group on the substrate, and gives synthetically useful yields with only 1 equiv of arene. Mechanistic data implicate an unusual mechanism devoid of commonly invoked organometallic intermediates: oxidation of the Pd catalyst occurs as the turnover-limiting step, while C-H bond functionalization occurs subsequently at a high oxidation state of the catalyst.
- Boursalian, Gregory B.,Ngai, Ming-Yu,Hojczyk, Katarzyna N.,Ritter, Tobias
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supporting information
p. 13278 - 13281
(2013/09/24)
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- Copper-catalyzed trifluoromethylation and cyclization of aromatic-sulfonyl-group-tethered alkenes for the construction of 1,2-benzothiazinane dioxide type compounds
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A multi-talented system: An efficient copper-catalyzed tandem trifluoromethylation/annulation of an electron-deficient aromatic ring has been developed. This method provides a powerful and straightforward way to synthesize trifluoromethylated 1,2-benzothiazinane dioxides under mild conditions (see scheme). The mechanism was investigated by a series of kinetic experiments and isotopic labeling studies.
- Dong, Xiang,Sang, Rui,Wang, Qiang,Tang, Xiang-Ying,Shi, Min
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supporting information
p. 16910 - 16915
(2014/01/06)
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- Fluorine transfer to alkyl radicals
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The development of new synthetic technologies for the selective fluorination of organic compounds has increased with the escalating importance of fluorine-containing pharmaceuticals. Traditional methods potentially applicable to drug synthesis rely on the use of ionic forms of fluorine (F - or F+). Radical methods, while potentially attractive as a complementary approach, are hindered by a paucity of safe sources of atomic fluorine (F?). A new approach to alkyl fluorination has been developed that utilizes the reagent N-fluorobenzenesulfonimide as a fluorine transfer agent to alkyl radicals. This approach is successful for a broad range of alkyl radicals, including primary, secondary, tertiary, benzylic, and heteroatom-stabilized radicals. Furthermore, calculations reveal that fluorine-containing ionic reagents are likely candidates for further expansion of this approach to polar reaction media. The use of these reagents in alkyl radical fluorination has the potential to enable powerful new transformations that otherwise would take multiple synthetic steps.
- Rueda-Becerril, Montserrat,Chatalova Sazepin, Claire,Leung, Joe C. T.,Okbinoglu, Tulin,Kennepohl, Pierre,Paquin, Jean-Francois,Sammis, Glenn M.
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supporting information; experimental part
p. 4026 - 4029
(2012/04/10)
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- Remote amide-directed palladium-catalyzed benzylic C-H amination with N-fluorobenzenesulfonimide
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An unprecedented remote amide-directed palladium-catalyzed intermolecular highly selective benzylic C-H amination with N-fluorobenzenesulfonimide is developed, which represents the first direct benzylic C-H amination with a non-nitrene nitrogen source. This methodology provides a novel approach to circumvent the common ortho aromatic C-H selectivity in directed palladium catalyzed C-H functionalization.
- Xiong, Tao,Li, Yan,Lv, Yunhe,Zhang, Qian
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body text
p. 6831 - 6833
(2010/10/21)
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- Interaction in molecular crystals, 162 [1, 2]. Di(arylsulfonyl)amines - Ligands for lipophilically wrapped polyion aggregates with Cs⊕-layers of variable thickness
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Di(arylsulfonyl)amides are presented as novel anionic ligands for polycation aggregates. Starting from the structures of Ag⊕ and Na⊕ salts registered in the Cambridge Structural Database, the largest alkali cation Cs⊕ with high coordination number has been selected and in extreme low gradient crystallisation single crystals of both cesium-di(benzenesulfonyl)amide and cesium-di(4-toluenesulfonyl)amide were grown. Their structure determinations revealed that both polymeric salts contain cation layers (Cs⊕)∞: The one lipophilically wrapped by di(benzenesulfonyl)amide ligands exhibits hexagonal (Cs⊕)6 subunits, whereas the methyl-substituted di(4-toluenesulfonyl)amide ligands of the other one are interspersed within (Cs⊕)∞ layers. The resulting lipophilically wrapped sheets with Cs⊕ cations of ten- and twelve-fold coordination to disulfonyl O and C centers vary in their overall thickness of 1.77 nm and 1.39 nm because the toluene substituents in the thinner one are tilted. The remarkable effects caused by the 4-methyl substitution of the phenyl rings determine the structures of the parent di(arylsulfonyl)amines as well: Contrary to the polymeric phenyl substituted derivative, the toluene homologue crystallizes in dimers. The single crystals grown of the closely related di(arylsulfonyl)amides with or without para methyl substituents and their poly(Cs⊕) aggregates without any solvent inclusion show hitherto unknown structural motifs and, therefore, further improve our knowledge of alkali salt self-organisation phenomena in crystals.
- Bock, Hans,Heigel, Erik
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p. 1053 - 1066
(2007/10/03)
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- Effects of medium and substituents on dissociation of 4,4′-disubstituted bis(benzenesulfon)imides
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Ten 4,4′-disubstituted bis(arenesulfon)imides of the general formula XC6H4SO2NHSO2C6H 4X have been synthesized and their structures confirmed by their 1H NMR spectra. Elemental analyses are presented for the compounds not yet described. The dissociation constants of these model substances have been measured potentiometrically in pyridine, dimethylformamide, methanol, ethanol, propylene carbonate, acetone, acetonitrile, 1,2-dichloroethane and tetramethylene sulfone. The pKHA values obtained have been correlated with three sets of the Hammett substituent constants and the results have been used to discuss the solvent and substituent effects on the dissociation of the compounds studied. Sulfonimides with electron-acceptor substituents behave as rather strong acids in some solvents (pyridine, dimethylformamide, methanol and ethanol), whereas normal substituent dependences are found in other solvents. The experimental data have also been interpreted with the help of the statistical methods based on latent variables. From the calculations it follows that only the first principal component, which correlates well with the substituent constant sets adopted, is statistically significant in describing the substituent effect on the acid-base process studied.
- Ludwig, Miroslav,Stverka, Pavel
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p. 1205 - 1214
(2007/10/03)
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