- Solvent-Free and Liquid-Phase Iodination of Thiophene Derivatives with Potassium Dichloroiodate Monohydrate
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Iodination of a series of benzene and thiophene derivatives by potassium dichloroiodate monohydrate was studied with and without a solvent. The liquid substrates tend to be more reactive in water while the solid substrates afford better yields in dichloromethane or under the solvent-free conditions. The 2-substituted thiophenes show good to excellent yields whereas the yield for 3-substituted and 3,4- or 2,4-disubstituted thiophenes and benzene derivatives are significantly lower. The mechanochemical reaction of 5-carbaldehyde-2,2′-bithiophene shows excellent yields, while 2,2′-bithiophene gives practical yields only in dichloromethane. In the case of thiophene and N -acetyl- p -toluidine, electrophilic iodination is accompanied by a small extent of chlorination.
- Hussain, Anwar,Sarkar, Akash Mamon,Sereda, Grigoriy,Zefirov, Nikolai
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p. 1140 - 1146
(2020/04/01)
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- Disulfide-Catalyzed Iodination of Electron-Rich Aromatic Compounds
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Herein, a disulfide-catalyzed electrophilic iodination of aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH) has been developed. The disulfide activates DIH as a Lewis base to promote the iodination reaction in acetonitrile under mild conditions. This system is applicable to a wide range of electron-rich aromatic compounds, including acetanilide, anisole, imidazole, and pyrazole derivatives.
- Iida, Keisuke,Ishida, Shunsuke,Watanabe, Takamichi,Arai, Takayoshi
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- Disulfide-Catalyzed Iodination of Electron-Rich Aromatic Compounds
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Herein, a disulfide-catalyzed electrophilic iodination of aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH) has been developed. The disulfide activates DIH as a Lewis base to promote the iodination reaction in acetonitrile under mild conditions. This system is applicable to a wide range of electron-rich aromatic compounds, including acetanilide, anisole, imidazole, and pyrazole derivatives.
- Iida, Keisuke,Ishida, Shunsuke,Watanabe, Takamichi,Arai, Takayoshi
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p. 7411 - 7417
(2019/06/18)
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- Palladium-catalyzed ortho-halogenations of acetanilides with N-halosuccinimides via direct sp2 C–H bond activation in ball mills
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A solvent-free palladium-catalyzed ortho-iodination of acetanilides using N-iodosuccinimide as the iodine source has been developed under ball-milling conditions. This present method avoids the use of hazardous organic solvents, high reaction temperature,
- Liu, Zi,Xu, Hui,Wang, Guan-Wu
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supporting information
p. 430 - 435
(2018/02/27)
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- Cobalt(II)-catalyzed regioselective C-H halogenation of anilides
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A cobalt-catalyzed regioselective C-H halogenation methodology is reported herein. The highlight of this work is the highly selective C-H functionalization of anilides, which results in high-yielding, versatile, and practical halogenated products. Thereby, brominations, chlorinations and iodinations of many electron-rich and electron-deficient anilides were achieved in a highly selective fashion. Mechanistic studies with respect to the pathway of the reaction are also described.
- Li, Ze-lin,Sun, Kang-kang,Cai, Chun
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supporting information
p. 5433 - 5440
(2018/08/12)
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- PtCl4-catalyzed cyclization of N-acetyl-2-alkynylanilines: A mild and efficient synthesis of N-acetyl-2-substituted indoles
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An efficient synthesis of N-acetyl-2-substituted indole derivatives via direct intramolecular hydroamination of N-acetyl-2-alkynylaniline derivatives was developed. The reaction could be applied to a wide range of substrates employing only 1–2 mol% of PtCl4 as the catalyst to furnish the desired indole products in moderate to excellent yields. The current protocol is efficient, reliable and scalable, and could serve as an important tool for convenient and rapid access to this important class of N-heterocyclic skeleton from readily available substrates.
- Chaisan, Nattawadee,Kaewsri, Wilailak,Thongsornkleeb, Charnsak,Tummatorn, Jumreang,Ruchirawat, Somsak
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supporting information
p. 675 - 680
(2018/01/18)
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- Highly Chemo- and Stereoselective Catalyst-Controlled Allylic C?H Insertion and Cyclopropanation Using Donor/Donor Carbenes
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The highly chemo-, enantio-, and diastereoselective catalyst-controlled intramolecular allylic C?H insertion and cyclopropanation of donor/donor carbenes are reported. The RuII/Pybox complex selectively catalyzed the intramolecular allylic C?H
- Zhu, Dong,Chen, Lianfen,Zhang, He,Ma, Zhiqiang,Jiang, Huanfeng,Zhu, Shifa
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supporting information
p. 12405 - 12409
(2018/09/18)
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- Monoprotected l-Amino Acid (l-MPAA), Accelerated Bromination, Chlorination, and Iodination of C(sp2)?H Bonds by Iridium(III) Catalysis
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Halogenated arenes are important structural motifs commonly found in biologically active molecules and used for a variety of transformations in organic synthesis. Herein, we report the mono-protected l-amino acid (l-MPAA) accelerated iridium(III)-catalyzed halogenation of (hetero)anilides at room temperature. This reaction constitutes the first example of an iridium(III)/l-MPAA-catalyzed general halogenation of (hetero)arenes through C(sp2)?H activation. Furthermore, we demonstrate the potential utility of our method through its use in the synthesis of a quinolone derivative.
- Kathiravan, Subban,Nicholls, Ian A.
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supporting information
p. 7031 - 7036
(2017/05/29)
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- Synthesis of 2,3-Disubstituted Indoles and Benzofurans by the Tandem Reaction of Rhodium(II)-Catalyzed Intramolecular C-H Insertion and Oxygen-Mediated Oxidation
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A highly effective and straightforward method to construct a wide range of functionalized 2,3-disubstituted indoles has been developed. The method involves the tandem reaction of rhodium(II)-catalyzed denitrogenative annulation of triazole-based benzyl an
- Shen, Hongjuan,Fu, Junkai,Yuan, Hao,Gong, Jianxian,Yang, Zhen
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p. 10180 - 10192
(2016/11/17)
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- Palladium-catalyzed cyclization of 2-alkynyl-N-ethanoyl anilines to indoles: Synthesis, structural, spectroscopic, and mechanistic study
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This study reports a facial regio-selective synthesis of 2-alkyl-N-ethanoyl indoles from substituted-N-ethanoyl anilines employing palladium (II) chloride, which acts as a cyclization catalyst. The mechanistic trait of palladium-based cyclization is also explored by employing density functional theory. In a two-step mechanism, the palladium, which attaches to the ethylene carbons, promotes the proton transfer and cyclization. The gas-phase barrier height of the first transition state is 37kcal/mol, indicating the rate-determining step of this reaction. Incorporating acetonitrile through the solvation model on density solvation model reduces the barrier height to 31kcal/mol. In the presence of solvent, the electron-releasing (-CH3) group has a greater influence on the reduction of the barrier height compared with the electron-withdrawing group (-Cl). These results further confirm that solvent plays an important role on palladium-catalyzed proton transfer and cyclization. For unveiling structural, spectroscopic, and photophysical properties, experimental and computational studies are also performed. Thermodynamic analysis discloses that these reactions are exothermic. The highest occupied molecular orbital-lowest unoccupied molecular orbital gap (4.9-5.0eV) confirms that these compounds are more chemically reactive than indole. The calculated UV-Vis spectra by time-dependent density functional theory exhibit strong peaks at 290, 246, and 232nm, in good agreement with the experimental results. Moreover, experimental and computed 1H and 13C NMR chemical shifts of the indole derivatives are well correlated.
- Hoque, Mohammad Mazharol,Halim, Mohammad A.,Sarwar, Mohammed G.,Khan, Md. Wahab
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p. 732 - 742
(2015/11/09)
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- Highly regioselective indoline synthesis under nickel/photoredox dual catalysis
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Nickel/photoredox catalysis is used to synthesize indolines in one step from iodoacetanilides and alkenes. Very high regioselectivity for 3-substituted indoline products is obtained for both aliphatic and styrenyl olefins. Mechanistic investigations indic
- Tasker, Sarah Z.,Jamison, Timothy F.
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p. 9531 - 9534
(2015/08/18)
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- A highly regioselective synthesis of N-acyl-2-acyl(aroyl)indolium Chloride through Palladium-Copper Catalysis Followed by Friedel-Crafts Reaction
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2-Trimethylsilylethynyl acetanilides, obtained from the palladium-catalyzed reactions of 2-iodoacetanilides with trimethylsilylacetylene, underwent Friedel-Crafts acylation reactions yielding the N-acyl-2-acyl(aroyl)indolium chlorides in good yields. Georg Thieme Verlag Stuttgart New York.
- Khan, Md. Wahab,Akther, Arifa,Alam, Md. Shariful
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p. 831 - 834
(2014/04/17)
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- Synthesis and structural insights of substituted 2-iodoacetanilides and 2-iodoanilines
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This study reports a simple and efficient method for the direct iodination of substituted anilines with molecular iodine and copper acetate in acetic acid producing 2-iodoacetanilies and 2-iodoanilines. Employing density functional theory (B3LYP) and MidiX basis set, computational study is performed to calculate equilibrium geometries, IR vibrational frequencies, and thermodynamic properties including change of energy, enthalpy and Gibbs free energies. The optimized geometries indicated longer C-I bond distance (2.133 ?) which makes iodine slightly positive. The partial atomic charge profile and electrostatic potential further confirmed that most of the iodinated products are capable of forming a distinct halogen bonding . The thermodynamic properties disclosed that all iodination reactions are endothermic. Understanding the substituents' effect, molecular frontier orbital (MO) calculations are conducted finding the HOMO, LUMO and HOMO-LUMO gaps for all compounds. The MO calculations revealed that two electron-withdrawing iodine groups have significant influence on lowering the HOMO-LUMO gap compared to one iodine group in the products.
- Hoque, Mohammad Mazharol,Halim, Mohammad A.,Rahman, Mohammad Mizanur,Hossain, Mohammad Ismail,Khan, Md. Wahab
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p. 367 - 374
(2013/11/19)
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- One product, two pathways: Initially divergent radical reactions reconverge to form a single product in high yield
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The paper describes examples of net diastereotopic-group-selective radical processes having the unusual feature that a single product is formed even though the key reaction of the two diastereotopic radical precursors is nonselective. For example, reactio
- Bruch, Achim,Froehlich, Roland,Grimme, Stefan,Studer, Armido,Curran, Dennis P.
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supporting information; experimental part
p. 16270 - 16276
(2011/11/30)
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- Copper-catalyzed regiospecific synthesis of N-alkylbenzimidazoles
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(Chemical Equation Presented) A copper-catalyzed method is described for the preparation of N-alkylbenzimidazoles in regioisomerically pure form starting from o-haloanilines. The method utilizing CuI and trans-N,N′-dimethyl-1, 2-cyclohexanediamine allows the preparation of N-alkylbenzimidazoles in good to excellent yields.
- Zheng, Nan,Buchwald, Stephen L.
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p. 4749 - 4751
(2008/03/14)
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- Oxidative Iodination of Aromatic Amides Using Sodium Perborate or Hydrogen Peroxide with Sodium Tungstate
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Hydrogen peroxide or sodium perborate in the presence of a sodium tungstate catalyst are shown to be cheap oxidants for the iodination of aromatic amides using potassium iodide as the source of the iodine.
- Beinker, Philipp,Hanson, James R.,Meindl, Nadja,Rodriguez Medina, Inmaculada C.
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p. 204 - 205
(2007/10/03)
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- Halogenation Using Quaternary Ammonium Polyhalides. XVII. Iodination of Acetanilide Derivatives with Benzyltrimethylammonium Dichloroiodate and Zinc Chloride
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The reaction of acetanilide derivatives with benzyltrimethylammonium dichloroiodate in acetic acid in the presence of ZnCl2 at room temperature or at 70 deg C gave iodo-substituted acetanilide derivatives in good yields.
- Kajigaeshi, Shoji,Kakinami, Takaaki,Watanabe, Fumiko,Okamoto, Tsuyoshi
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p. 1349 - 1351
(2007/10/02)
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