- Lewis Acid Regulated Divergent Catalytic Reaction between Quinone Imine Ketals (QIKs) and 1,3-Dicarbonyl Compounds: Switchable Access to Multiple Products Including 2-Aryl-1,3-Dicarbonyl Compounds, Indoles, and Benzofurans
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A catalytic Lewis acid regulated reaction between quinone imine ketals (QIKs) and 1,3-dicarbonyl compounds provides a divergent and tunable approach to a variety of skeletons, including a series of 2-aryl-1,3-dicarbonyl compounds, indoles, and benzofurans. The use of lithium chloride and ferrous bromide gives C3- or C2-alkylation products of the QIKs. The combination of ferrous bromide and trifluoromethanesulfonic acid delivers indole derivatives. Sequential hydrolysis and C3-alkylation occur in the presence of ytterbium (III) trifluoromethanesulfonate and stoichiometric amounts of water. When the reaction is performed with trifluoromethanesulfonic acid and stoichiometric amounts of water, benzofuran is obtained. This protocol utilizes mild conditions, exhibits regio- and chemoselectivity, and has broad functional group tolerance. (Figure presented.).
- Chen, Xingyu,Lu, Sixian,Deng, Ping,Chang, Xiaoqiang,Zhao, Yifan,Ma, Yue,Zhang, Dong,Xia, Fei,Yang, Lan,Wang, Jigang,Sun, Peng
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supporting information
p. 94 - 102
(2021/10/05)
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- Visible Light-Driven Synthesis of Amine–Sulfonate Salt Derivatives: A Step towards Green Approach
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In this work, a novel strategy for the straightforward visible-light-driven synthesis of biologically active, industrially important, and stable amine–sulfonate salts have been reported from p-Toluenesulfonic acid and amines, which provide extremely high yield without side product formation. The reaction was performed without catalyst under visible light irradiation and had an excellent functional group tolerance. The structure of the prepared compounds were confirmed through 1H NMR, 13C NMR, and Mass spectroscopic studies, and similarly, the molecular structure of compound 3b was established through single-crystal XRD-analysis. The advantages of this method meet the requirements of sustainable and green synthetic chemistry, and it provides a direct way to create valuable amine-sulfonate salt.
- Kamal, Arsala,Kumari, Savita,Kushwaha, Ambuj Kumar,Maury, Suresh Kumar,Singh, Himanshu Kumar,Singh, Sundaram,Srivastava, Vandana
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- Ligand-Regulated Palladium-Catalyzed Regiodivergent Hydroarylation of the Distal Double Bond of Allenamides with Aryl Boronic Acid
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The ligand-regulated regiodivergent hydroarylation of the distal double bond of allenamides with aryl boronic acid was achieved in the presence of palladium(II) catalysts, delivering a variety of functionalized enamide with excellent E selectivity and Markovnikov/anti-Markovnikov selectivity. Two possible coordination intermediates were proposed to be responsible for the regiodivergent hydroarylation: (1) The coordination Intermediate I, which was proposed to be formed through the coordination of MeCN, distal double bond, phenyl to palladium, led to the aryl group away from the Intermediate I, inducing excellent E selectivity and anti-Markovnikov selectivity. (2) A switch of regioselectivity to 1,2-Markovnikov hydroarylation was obtained using bidentate phosphine ligand (dppf or Xantphos). The formed coordination Intermediate II led to the N-tether away from the Intermediate II and at the trans position of aryl, resulting in excellent E selectivity and Markovnikov selectivity. Meanwhile, tentative investigation on the mechanism proved that the hydron source of this hydroarylation is more likely to be boronic acid. The transmetallation between aryl boronic acid and palladium catalyst was the initial step of this transformation.
- Dong, Yunhui,Du, Xin,Li, Xinling,Liu, Hui,Liu, Qing,Wang, Ping,Zhang, Daopeng,Zhang, Lizhi,Zhao, Huan
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p. 13276 - 13288
(2021/10/12)
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- A Broad-Spectrum Catalytic Amidation of Sulfonyl Fluorides and Fluorosulfates**
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A broad-spectrum, catalytic method has been developed for the synthesis of sulfonamides and sulfamates. With the activation by the combination of a catalytic amount of 1-hydroxybenzotriazole (HOBt) and silicon additives, amidations of sulfonyl fluorides and fluorosulfates proceeded smoothly and excellent yields were generally obtained (87–99 %). Noticeably, this protocol is particularly efficient for sterically hindered substrates. Catalyst loading is generally low and only 0.02 mol % of catalyst is required for the multidecagram-scale synthesis of an amantadine derivative. In addition, the potential of this method in medicinal chemistry has been demonstrated by the synthesis of the marketed drug Fedratinib via a key intermediate sulfonyl fluoride 13. Since a large number of amines are commercially available, this route provides a facile entry to access Fedratinib analogues for biological screening.
- Wei, Mingjie,Liang, Dacheng,Cao, Xiaohui,Luo, Wenjun,Ma, Guojian,Liu, Zeyuan,Li, Le
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supporting information
p. 7397 - 7404
(2021/02/16)
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- Facile synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazides
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A simple and rapid method for efficient synthesis of sulfonyl chlorides/bromides from sulfonyl hydrazide with NXS (X = Cl or Br) and late-stage conversion to several other functional groups was described. A variety of nucleophiles could be engaged in this transformation, thus permitting the synthesis of complex sulfonamides and sulfonates. In most cases, these reactions are highly selective, simple, and clean, affording products at excellent yields.
- Chen, Rongxiang,Xu, Shaohong,Shen, Fumin,Xu, Canran,Wang, Kaikai,Wang, Zhanyong,Liu, Lantao
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- Immobilization of copper(II) into polyacrylonitrile fiber toward efficient and recyclable catalyst in Chan-Lam coupling reactions
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A series of polyacrylonitrile fiber (PANF)-supported copper(II) catalysts were prepared through the immobilization of Cu(II) into prolinamide-modified PANF (PANPA-2F) and subsequently used for the synthesis of diverse N-arylimidazoles from arylboronic acids and imidazole. The prepared Cu(II)@PANPA-2Fs were well characterized by mechanical strength, FT-IR, XRD, XPS and SEM. Among them, CuCl2@PANPA-2F exhibited excellent catalytic performance, and its activity was significantly affected by the Cu loading. This catalytic system also displayed good activity in the synthesis of N-arylsulfonamides from arylboronic acids and tosyl azide. It was highly efficient in gram-scale reactions and could be reused five times. The advantages of low cost, easy preparation, good durability and facile recovery make the fiber catalyst attractive.
- Zhang, Chenlu,Zhu, Hai,Gang, Kaiyue,Tao, Minli,Ma, Ning,Zhang, Wenqin
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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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- 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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- Metal-free synthesis of biaryls from aryl sulfoxides and sulfonanilides via sigmatropic rearrangement
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Treatment of aryl sulfoxides and sulfonanilides with trifluoroacetic anhydride resulted in the dehydrative metal-free construction of the corresponding unsymmetrical biaryls. The reaction would proceed via (1) the activation of aryl sulfoxide with the anhydride, (2) interrupted Pummerer reaction of the resulting arylsulfonium with sulfonanilide, (3) [3,3] sigmatropic rearrangement to cleave the transient S–N bond and to form the prospective biaryl C–C bond, and (4) global aromatization. The choice of the amino protecting group is crucial, and only N-sulfonylanilines, i.e., sulfonanilides, could participate in the formation of biaryls.
- Yoshida, Akira,Okamoto, Koichi,Yanagi, Tomoyuki,Nogi, Keisuke,Yorimitsu, Hideki
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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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- Nitrosoarenes as Nitrogen Source for Generation of Sulfonamides with the Insertion of Sulfur Dioxide under Metal-Free Conditions?
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A metal-free reaction of nitrosoarenes, aryldiazonium tetrafluoroborates, and sulfur dioxide under mild conditions is developed, giving rise to sulfonamides in moderate to good yields. This transformation proceeds efficiently at room temperature in the presence of cyclohexa-1,4-diene with a broad reaction scope. Good functional group compatibility is observed, including cyano, halo, and ester. A plausible mechanism involving a radical process with the insertion of sulfur dioxide is proposed, and cyclohexa-1,4-diene serves as the reductant during the transformation.
- Wang, Xuefeng,Lin, Yanmei,Liu, Jin-Biao,He, Fu-Sheng,Kuang, Yunyan,Wu, Jie
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supporting information
p. 1098 - 1102
(2020/07/06)
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- Copper iodide nanoparticles-decorated porous polysulfonamide gel: As effective catalyst for decarboxylative synthesis of N-Arylsulfonamides
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A porous cross-linked poly (ethyleneamine)-polysulfonamide (PEA-PSA) as a novel organic support system is synthesized in the presence of silica template by nanocasting technique. The paper demonstrates immobilization of CuI nanoparticles inside the pores (PEA-PSA?CuI) for the facile recovery and recycling of these nanoparticles. The presence of porous PEA-PSA and PEA-PSA?CuI nanocomposites was confirmed using FT-IR spectroscopy, FE-SEM, EDX, TGA, XRD, TEM, BET, XPS, WDX, 1H NMR, and ICP-OES techniques. The PEA-PSA?CuI along with Ag(I)/K2S2O8 was implemented as a reusable cooperative catalyst-oxidant system in the N-arylation of p-toluenesulfonamide with substituted carboxylic acids in mild condition. So, the novel decarboxylative cross-coupling catalyzed by copper and silver has been developed. Aromatic, secondary and tertiary aliphatic acids underwent high efficient decarboxylative processes with p-toluenesulfonamide to afford the corresponding products. This method provides a practical approach for the flexible synthesis of sulfonamides from the readily affordable substrates. The catalyst is highly reusable and efficient, especially in terms of time and yield of the desired product.
- Alavinia, Sedigheh,Ghorbani-Vaghei, Ramin,Rakhtshah, Jamshid,Yousefi Seyf, Jaber,Ali Arabian, Iman
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- Copper-catalyzed redox coupling of nitroarenes with sodium sulfinates
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A simple copper-catalyzed redox coupling of sodium sulfinates and nitroarenes is described. In this process, abundant and stable nitroarenes serve as both the nitrogen sources and oxidants, and sodium sulfinates act as both reactants and reductants. A variety of aromatic sulfonamides were obtained in moderate to good yields with broad substrate scope. No external additive is employed for this kind of transformation.
- Liu, Saiwen,Chen, Ru,Zhang, Jin
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- Synthesis, Characterization, and Reactivity of an Ethynyl Benziodoxolone (EBX)-Acetonitrile Complex
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The synthesis of a crystalline ethynyl-1,2-benziodoxol-3(1H)-one (EBX)-acetonitrile complex is described. EBX has been widely used as an active species for a variety of reactions; however, its high instability has so far prevented its isolation. The EBX-acetonitrile is self-assembled into a double-layered honeycomb structure through weak hypervalent iodine secondary interactions and hydrogen bonding. The N-ethynylation of a variety of sulfonamides using the EBX-acetonitrile complex as a substrate under mild conditions is also described.
- Yudasaka, Masaharu,Shimbo, Daisuke,Maruyama, Toshifumi,Tada, Norihiro,Itoh, Akichika
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supporting information
p. 1098 - 1102
(2019/05/16)
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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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- Aryltrifluoromethylative cyclization of unactivated alkenes by the use of PhICF3Cl under catalyst-free conditions
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A concise and catalyst-free aryltrifluoromethylative cyclization of unactivated alkenes has been developed herein. The use of PhICF3Cl as a powerful trifluoromethylating agent allows easy transformations. A set of trifluoroethylated carbocycles and aza-hereocycles were efficiently synthesized in good yield and selectivity. A broad substrate scope, mild reaction conditions, and easy operation would make this method well-suited for applications.
- Guo, Jia,Xu, Cong,Liu, Xiaowei,Wang, Mang
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supporting information
p. 2162 - 2168
(2019/02/27)
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- A palladium-catalyzed regiocontrollable hydroarylation reaction of allenamides with B2pin2/H2O
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A novel palladium-catalyzed regiocontrollable hydroarylation reaction of allenamides with B2pin2/H2O has been disclosed. H2O as an ideal hydrogen source was activated by B2pin2 to furnish allylamines or enamines with a broad functional group tolerance. The regioselectivity for both of the two products was up to 99:1 for most of the examples, which was achieved by adjusting the addition order of the catalyst and iodobenzene derivatives. The tentative investigation of the mechanism proved the reaction to be a non-radical process and the deuterium-labeled experiments indicated that the hydrogen was from H2O.
- Cui, Jie,Meng, Long,Chi, Xiaochen,Liu, Qing,Zhao, Pingping,Zhang, Dao-Peng,Chen, Lei,Li, Xinjin,Dong, Yunhui,Liu, Hui
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supporting information
p. 4355 - 4358
(2019/04/26)
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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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- Selective C(sp2)-H Amination Catalyzed by High-Valent Cobalt(III)/(IV)-bpy Complex Immobilized on Silica Nanoparticles
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High-valent cobaltIV-bpy complex stabilized in silica matrix was detected as catalytically active form and intermediate in cobalt-mediated oxidative C?H/NH cross-coupling reaction. These CoIV species prepared by electrooxidation of CoIII(bpy)3-doped silica nanoparticles (SNs) at relatively low anodic potentials have demonstrated high catalytic activity. Both size and architecture of the SNs are highlighted as the factors beyond the complex structure affecting its oxidation potential and catalytic efficiency. The factors have been optimized for the catalyst with high efficiency, easy separation and reusability for 7 times at least. The optimal nanocatalyst (1 mol%) provides 100 % conversion of reactants in a single step of ligand-directed coupling of H2NTs with arenes under electrochemical regeneration conditions. The results emphasize both synthetic route for efficient embedding of CoIII(bpy)3 into silica support and the electrochemical generation of CoIV complexes as a facile route for developing the efficient nanocatalyst of oxidative functionalization. The observed reactivity has the potential in development of Co-catalyzed coupling reactions.
- Budnikova, Yulia,Bochkova, Olga,Khrizanforov, Mikhail,Nizameev, Irek,Kholin, Kirill,Gryaznova, Tatyana,Laskin, Artem,Dudkina, Yulia,Strekalova, Sofia,Fedorenko, Svetlana,Kononov, Aleksandr,Mustafina, Asia
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p. 5615 - 5624
(2019/11/11)
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- Synergistic combination of visible-light photo-catalytic electron and energy transfer facilitating multicomponent synthesis of β-functionalized α,α-diarylethylamines
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A synthetic strategy with the visible-light photo-catalytic synergistic combination of electron and energy transfer processes has been developed. The mild reaction conditions allow the radical-radical cross-coupling phenomenon for the multicomponent synthesis of β-arylsulfonyl(diarylphosphinoyl)-α,α-diarylethyl-amines from readily available arylsulfinic acids (diarylphosphine oxides), 1,1-diarylethylenes and arylazides.
- Wu, Yanan,Zhang, Yipin,Jiang, Mingjie,Dong, Xunqing,Jalani, Hitesh B.,Li, Guigen,Lu, Hongjian
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p. 6405 - 6408
(2019/06/07)
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- Corrigendum to “Transition-metal-free synthesis of aromatic amines via the reaction of benzynes with isocyanates” [Tetrahedron Lett. 59 (2018) 671–674](S0040403918300352)(10.1016/j.tetlet.2018.01.022)
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The authors regret that the structure of Scheme 3 is shown incorrectly. The structure of the compound 3e' is shown correctly here.[Figure presented] The penultimate paragraph of the “Results and Discussion” section should read as follows: During the investigation of several substrates, we observed the unexpected product 3e' which had a diphenyl backbone with a tosyl amine in 45% yield (Scheme 3). This structure was confirmed by 1H NMR, 13C NMR, and high-resolution mass spectroscopy. The diphenyl scaffold is useful to develop new ligands, or synthesize materials, pharmaceuticals, and natural products.The Authors also note corrections needed to the data of compound 3j in the Supplementary Data files. This should be re-written as follows: 13C NMR (125 MHz, CDCl3) δ 150.4 (dd, 1C, JC–F = 242.8, 8.2 Hz), 148.3 (dd, 1C, JC–F = 240.6, 7.3 Hz), 144.4, 135.6, 133.0 (dd, 1C JC–F = 8.1, 3.3 Hz), 129.9, 127.3, 118.1 (q, 1C, JC-F = 3.3 Hz), 117.8 (dd, 1C, JC–F = 18.2, 1.3 Hz), 111.8 (d, 1C, JC–F = 20.3 Hz), 21.6.The updated Supplementary Data files have been published online with this Corrigendum. The authors would like to apologise for any inconvenience caused.
- Seo, Jeong Hoon,Ko, Haye Min
-
supporting information
p. 1213 - 1213
(2019/03/23)
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- Pd-Catalyzed Cross-Coupling Reactions Promoted by Biaryl Phosphorinane Ligands
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We report the use of biaryl phosphorinanes as ligands for Pd-catalyzed cross-coupling reactions. A modular synthesis was developed that employs a double conjugate addition of primary biaryl phosphines into 1,1,5,5-tetraalkyl penta-1,4-diene-3-ones. Notably, this synthesis does not require the use of copper, a known contaminant in structurally related biaryl phosphane ligands. Using the synthetic strategy described above, we synthesized a library of biaryl phosphorinanes, varying their substitution about phosphorus and the steric and electronic nature of the biaryl motif. We then benchmarked their performance as ligands in Pd-catalyzed cross coupling reactions such as aryl sulfonamidation, aryl alkoxylation, and aryl amination in the presence of soluble organic bases. In each reaction studied, many ligands outperformed biaryl phosphanes known to promote the given transformation. Detailed substrate scopes were determined using high-throughput screening technology. Several biaryl phosphorinanes and their corresponding Pd(II) oxidative-addition complexes were extensively characterized using NMR spectroscopy and X-ray crystallography. General observations support that biaryl phosphorinanes promote reductive elimination and form robust catalysts with palladium. In many cases the use of these biaryl phosphorinanes may be advantageous over the use of biaryl phosphanes with respect to lower catalyst loadings, shorter reaction times, and robustness.
- Laffoon, Joshua D.,Chan, Vincent S.,Fickes, Michael G.,Kotecki, Brian,Ickes, Andrew R.,Henle, Jeremy,Napolitano, José G.,Franczyk, Thaddeus S.,Dunn, Travis B.,Barnes, David M.,Haight, Anthony R.,Henry, Rodger F.,Shekhar, Shashank
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p. 11691 - 11708
(2019/12/02)
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- Facile Chan-Lam coupling using ferrocene tethered N-heterocyclic carbene-copper complex anchored on graphene
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Ferrocene tethered N-heterocyclic carbene-copper complex anchored on graphene ([GrFemImi]NHC@Cu complex) has been synthesized by covalent grafting of ferrocenyl ionic liquid in the matrix of graphene followed by metallation with copper (I) iodide. The [GrFemImi]NHC@Cu complex has been characterized by fourier transform infrared (FT-IR), fourier transform Raman (FT-Raman), CP-MAS 13C NMR spectroscopy, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), energy dispersive X-ray (EDX) analysis, X-ray photoelectron spectroscopy (XPS), Brunauer–Emmett–Teller (BET) surface area analysis and X-ray diffractometer (XRD) analysis. This novel complex served as a robust heterogeneous catalyst for the synthesis of bioactive N-aryl sulfonamides from variety of aryl boronic acids and sulfonyl azides in ethanol by Chan-Lam coupling. Recyclability experiments were executed successfully for six consecutive runs.
- Gajare, Shivanand,Jagadale, Megha,Naikwade, Altafhusen,Bansode, Prakash,Rashinkar, Gajanan
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- Ligand-Enabled Gold-Catalyzed C(sp2)-N Cross-Coupling Reactions of Aryl Iodides with Amines
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The first example of ancillary (P,N)-ligand-enabled gold-catalyzed C-N cross-coupling reactions of aryl iodides with amines is reported. The high generality of the reaction in de novo synthesis, late-stage modifications, and cascade processes to access functionalized indolinones and carbazoles underscores the synthetic potential of the presented strategy. Monitoring the reaction with ESI-HRMS and NMR provided strong evidence for the in situ formation of putative high valent Au(III) intermediates.
- Akram, Manjur O.,Das, Avishek,Chakrabarty, Indradweep,Patil, Nitin T.
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supporting information
p. 8101 - 8105
(2019/10/11)
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- Au(i)/Au(iii)-Catalyzed C-N coupling
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Cycling between Au(i) and Au(iii) is challenging, so gold-catalyzed cross-couplings are rare. The (MeDalphos)AuCl complex, which we showed was prone to undergo oxidative addition, is reported here to efficiently catalyze the C-N coupling of aryl iodides and amines. The transformation does not require an external oxidant or a directing group. It is robust and works with a wide scope of aryl iodides and N-nucleophiles under mild conditions. Mechanistic studies, including the NMR and MS characterization of a key aryl amido Au(iii) complex, strongly support a 2e redox cycle in which oxidative addition precedes transmetalation and reductive elimination is the rate-determining step.
- Rodriguez, Jessica,Adet, Nicolas,Saffon-Merceron, Nathalie,Bourissou, Didier
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supporting information
p. 94 - 97
(2019/12/25)
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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
-
supporting information
p. 671 - 674
(2018/01/19)
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- Soft-Hard Acid/Base-Controlled, Oxidative, N-Selective Arylation of Sulfonanilides via a Nitrenium Ion
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In iodine(III)-catalyzed, dehydrogenative arylations of sulfonanilides, the functionalization of C-C bonds is preferred over the functionalization of C-N bonds. Herein, an unprecedented N-selective arylation of sulfonanilides using soft-hard acid-base (SHAB) control by a nitrenium ion over a carbenium ion is reported. Treatment of sulfonanilides with iodine(III) led to the formation of nitrenium ions (soft), which preferentially react with biphenyls (soft) over bimesityl (hard) to generate C-N bonds. The iodine(III) was generated in situ by using PhI and mCPBA at room temperature.
- Maiti, Saikat,Mal, Prasenjit
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p. 1340 - 1347
(2018/02/09)
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- Halogen Bond Catalyzed Bromocarbocyclization
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A halogen bond catalyzed bromo-carbocyclization of N-cinnamyl sulfonamides and O-cinnamyl phenyl ethers has been developed. N-methyl 4-iodopyridinium triflate is used as the halogen-bonding organocatalyst and the reaction is highly chemoselective. This report represents the first proof-of-concept for halogen-bonding organocatalyst-promoted electrophilic halogenation. Mechanistic study suggests the autocatalytic nature of this reaction.
- Chan, Yuk-Cheung,Yeung, Ying-Yeung
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supporting information
p. 3483 - 3487
(2018/02/28)
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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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- Copper-catalyzed cross-coupling of chloramine salts and arylboronic acids in water: A green and practical route to N-arylsulfonamides
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A green and practical method for the synthesis of N-arylsulfonamides from chloramine salts and arylboronic acids is herein developed. The reaction proceeds readily in the presence of 5 mol% of CuI and 2.5 equiv. K2CO3 in water at room temperature, generating a variety of N-arylsulfonamides in moderate to good yields with good functional group tolerance.
- Ouyang, Banlai,Zheng, Yanxia,Liu, Yi,Liu, Fei,Yao, Juying,Peng, Yiyuan
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p. 3694 - 3698
(2018/09/14)
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- Synthesis of N -Arylsulfonamides by a Copper-Catalyzed Reaction of Chloramine-T and Arylboronic Acids at Room Temperature
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A copper-catalyzed Chan-Lam-coupling-like reaction of a (het)arylboronic acid and chloramine-T (or a related compound) has been developed for the synthesis of N -arylsulfonamides at room temperature in moderate to good yields, with good tolerance of functional groups. In this process, it is believed that chloramine-T serves as an electrophile.
- Ouyang, Banlai,Liu, Deming,Xia, Kejian,Zheng, Yanxia,Mei, Hongxin,Qiu, Guanyinsheng
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supporting information
p. 111 - 115
(2017/12/27)
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- NaI-Catalyzed Oxidative Amination of Aromatic Sodium Sulfinates: Synergetic Effect of Ethylene Dibromide and Air as Oxidants
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A novel NaI-catalyzed oxidative amination of sodium sulfinates, employing both ethylene dibromide (EDB) and air as the oxidants, is described. EDB was first demonstrated to be a promising mild organic oxidant that in air, converted NaI into molecular iodine to promote the cross-coupling reactions of aromatic sodium sulfinates with amines to produce arylsulfonamides. Mechanistic studies indicated that a radical pathway might be involved in the reaction process.
- Fu, Ying,Li, Quan-Zhou,Xu, Qin-Shan,Hügel, Helmut,Li, Ming-Peng,Du, Zhengyin
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supporting information
p. 6966 - 6970
(2018/11/23)
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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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- An Organic Intermolecular Dehydrogenative Annulation Reaction
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The discovery of a direct method for the synthesis of three-ring heterocyclic carbazoles from unactivated arenes and anilides by a metal-free (organic) intermolecular dehydrogenative annulation reaction under ambient laboratory conditions is reported. Iodine(III) was used as the sole reagent either stoichiometrically from inexpensive phenyliodine diacetate or organocatalytically by in situ generation from PhI-mCPBA. In a single step, three C(sp2)-H bonds and one N(sp3)-H bond are functionalized from two different arenes for tandem C-C and C-N bond formation reactions.
- Maiti, Saikat,Achar, Tapas Kumar,Mal, Prasenjit
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supporting information
p. 2006 - 2009
(2017/04/28)
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- An eco-friendly tandem tosylation/Ferrier N-glycosylation of amines catalyzed by Er(OTf)3 in 2-MeTHF
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Er(OTf)3 in 2-MeTHF provides a new and eco-friendly process for Ferrier glycosylation of sulfonamides and amino acids with various N-nucleophiles. The stereoselective synthesis of 2,3-unsaturated-N-pseudoglycals was carried out with 3,4,6-tri-O-acetyl-D-glucal and different nucleophiles affording good results in a short time.
- Nardi, Monica,Cano, Natividad Herrera,De Nino, Antonio,Di Gioia, Maria Luisa,Maiuolo, Loredana,Oliverio, Manuela,Santiago, Ana,Sorrentino, Diletta,Procopio, Antonio
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supporting information
p. 1721 - 1726
(2017/04/13)
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- Copper-Catalyzed Direct Nitration on Aryl C-H Bonds by Concomitant Azidation-Oxidation with TMS Azide and TBHP under Aerobic Conditions
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An unprecedented copper-catalyzed in situ azidation-oxidation for the nitration of anilides and sulfonamides has been developed by direct CAr-H functionalization. This novel and efficient nitration protocol is achieved employing TMSN3 and TBHP without the exclusion of air or moisture. The synthetic applications of the 2-nitroanilides have been explored.
- Vinayak, Botla,Chandrasekharam, Malapaka
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supporting information
p. 3528 - 3531
(2017/07/17)
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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 0040; 0041
(2017/09/02)
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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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- An efficient practical tosylation of phenols, amines, and alcohols employing mild reagent [DMAPTs]+Cl?
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Efficient exploration of [DMAPTs]+Cl?for base free and chromatography free preparation of sulfonate esters from phenols and alcohols and sulfonamides from amines was achieved in excellent yields. Majority of the phenols irrespective of their substituents electronic nature underwent tosylation nearly at same reaction rate with an average yield of 95%. For amines, ring activating substituents favors rapid sulfonylation while the ring deactivating substituents relatively lowers the rate of tosylation. Furthermore the reagent was employed for Chemoselective sulfonylation as well as solvent free tosylation of phenols and amines.
- Dhonthulachitty, Chiranjeevi,Kothakapu, Sridhar Reddy,Neella, Chandra Kiran
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supporting information
p. 4620 - 4623
(2016/09/23)
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- Sustainable synthesis of sulfonamides using supported ionic liquid phase catalyst containing Keggin-type anion
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A silica-supported ionic liquid phase catalyst containing Keggin-type anion has been prepared by covalent grafting of ferrocene-tagged ionic liquid in a matrix of silica followed by anion metathesis reaction. This novel catalyst served as a robust heterogeneous catalyst for the synthesis of biologically active sulfonamides from 4-toluenesulfonyl chloride and amines. Additionally, recycling experiments showed that the catalyst could be reused five times.
- Jagadale, Megha,Khanapure, Sharanabasappa,Salunkhe, Rajashri,Rajmane, Mohan,Rashinkar, Gajanan
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p. 125 - 131
(2016/02/14)
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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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- 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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- 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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- 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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- Electrochemical Oxidative Amination of Sodium Sulfinates: Synthesis of Sulfonamides Mediated by NH4I as a Redox Catalyst
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An efficient protocol for the synthesis of sulfonamides via the electrochemical oxidative amination of sodium sulfinates has been developed. The chemistry proceeds in a simple undivided cell employing a substoichiometric amount of NH4I that serves both as a redox catalyst and a supporting electrolyte; in this manner additional conducting salt is not required. A wide range of substrates, including aliphatic or aromatic secondary and primary amines, as well as aqueous ammonia, proved to be compatible with the protocol. Scale-up was possible, thereby demonstrating the practicality of the approach. The electrolytic process avoids the utilization of external oxidants or corrosive molecular iodine and therefore represents an environmentally benign means by which to achieve the transformation.
- Jiang, Yang-Ye,Wang, Qing-Qing,Liang, Sen,Hu, Li-Ming,Little, R. Daniel,Zeng, Cheng-Chu
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p. 4713 - 4719
(2016/07/06)
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- A highly efficient heterogeneous copper-catalyzed Chan-Lam coupling reaction of sulfonyl azides with arylboronic acids leading to: N -arylsulfonamides
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A heterogeneous Chan-Lam coupling reaction between sulfonyl azides and arylboronic acids was achieved in MeOH at room temperature in the presence of 10 mol% of an l-proline-functionalized MCM-41-immobilized copper(i) complex [MCM-41-l-proline-CuCl] under air, yielding a variety of N-arylsulfonamides in excellent yields. The new heterogeneous copper complex can be prepared from commercially readily available and inexpensive reagents, and recovered by simple filtration of the reaction solution and recycled at least 8 times without any decreases in activity.
- You, Chongren,Yao, Fang,Yan, Tao,Cai, Mingzhong
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p. 43605 - 43612
(2016/05/24)
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- Highly Chemoselective Iridium Photoredox and Nickel Catalysis for the Cross-Coupling of Primary Aryl Amines with Aryl Halides
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A visible-light-promoted iridium photoredox and nickel dual-catalyzed cross-coupling procedure for the formation C?N bonds has been developed. With this method, various aryl amines were chemoselectively cross-coupled with electronically and sterically diverse aryl iodides and bromides to forge the corresponding C?N bonds, which are of high interest to the pharmaceutical industries. Aryl iodides were found to be a more efficient electrophilic coupling partner. The coupling reactions were carried out at room temperature without the rigorous exclusion of molecular oxygen, thus making this newly developed Ir-photoredox/Ni dual-catalyzed procedure very mild and operationally simple.
- Oderinde, Martins S.,Jones, Natalie H.,Juneau, Antoine,Frenette, Mathieu,Aquila, Brian,Tentarelli, Sharon,Robbins, Daniel W.,Johannes, Jeffrey W.
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supporting information
p. 13219 - 13223
(2016/10/30)
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- Iron-catalyzed N -arylsulfonamide formation through directly using nitroarenes as nitrogen sources
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One-step, catalytic synthesis of N-arylsulfonamides via the construction of N-S bonds from the direct coupling of sodium arylsulfinates with nitroarenes was realized in the presence of FeCl2 and NaHSO3 under mild conditions. In this process, stable and readily available nitroarenes were used as nitrogen sources, and NaHSO3 acted as a reductant to provide N-arylsulfonamides in good to excellent yields. A broad range of functional groups were very well-tolerated in this reaction system. In addition, mechanistic studies indicated that the N-S bond might be generated through direct coupling of nitroarene with sodium arylsulfinate prior to the reduction of nitroarenes by NaHSO3. Accordingly, a reaction mechanism involving N-aryl-N-arenesulfonylhydroxylamine as an intermediate was proposed.
- Zhang, Weixi,Xie, Junyao,Rao, Bin,Luo, Meiming
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p. 3504 - 3511
(2015/04/14)
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- Aqueous MW eco-friendly protocol for amino group protection
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In this paper a new catalyst-free and on-water method for protection of amines and amino acids with di-tert-butyl dicarbonate, 9-fluorenylmethoxycarbonyl chloride, acetyl chloride and tosyl chloride is presented. The protection can be realized in a few minutes under microwave-assistance. The reaction proved to be chemoselective in presence of ambident nucleophiles and water solution of di-tert-butyl carboxylic acid or chloride acid are the only wastes produced.
- Nardi,Cano, N. Herrera,Costanzo,Oliverio,Sindona,Procopio
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p. 18751 - 18760
(2015/06/15)
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