- Aromatic iodination with iodine monochloride by using a catalytic amount of ferrocenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate
-
Direct iodination reaction of several aromatic compounds with 1.1-2.0 molar amounts of iodine monochloride (IC1) proceeded smoothly to afford the corresponding aromatic iodides in good to excellent yields by using 5 mol% of Cp2FeB[3,5-(CF3)2C6H3]4 (1) in the coexistence of DDQ or ZnO. (C) 2000 Published by Elsevier Science Ltd.
- Mukaiyama,Kitagawa,Matsuo
-
-
Read Online
- In pursuit of a selective hepatocellular carcinoma therapeutic agent: Novel thalidomide derivatives with antiproliferative, antimigratory and STAT3 inhibitory properties
-
Advanced stage liver cancer is predominantly treated with the multi-kinase inhibitor sorafenib; however, this therapeutic agent lacks selectivity in its cytotoxic actions and is associated with poor survival outcomes. Herein we report the design and preparation of several thalidomide derivatives, including a variety of novel thioether-containing forms that are especially rare in the literature. Importantly, two of the derivatives described are potent antiproliferative agents with dose-dependent selectivity for tumorigenic liver progenitor cells (LPC) growth inhibition (up to 36% increase in doubling time at 10 μM) over non-tumorigenic cells (no effect at 10 μM). Furthermore, these putative anti-liver cancer agents were also found to be potent inhibitors of tumorigenic LPC migration. This report also describes these derivatives’ effects on several key signalling pathways in our novel liver cell lines by immunofluorescence and AlphaLISA assays. Aryl thioether derivative 7f significantly reduced STAT3 phosphorylation (23%) and its nuclear localisation (16%) at 10 μM in tumorigenic LPCs, implicating the IL-6/JAK/STAT3 axis is central in the mode of action of our derivatives.
- Nutt, Michael J.,Yee, Yeung Sing,Buyan, Amanda,Andrewartha, Neil,Corry, Ben,Yeoh, George C.T.,Stewart, Scott G.
-
-
- Photochemically Activated Dimagnesium(I) Compounds: Reagents for the Reduction and Selective C?H Bond Activation of Inert Arenes
-
The photochemical activation of dimagnesium(I) compounds, and subsequent high yielding, regioselective reactions with inert arenes are reported. Irradiating benzene solutions of [{(ArNacnac)Mg}2] (ArNacnac=[HC(MeCNAr)2]?; Ar=2,6-diisopropylphenyl (Dip) or 2,4,6-tricyclohexylphenyl (TCHP)) with blue or UV light, leads to double reduction of benzene and formation of the “Birch-like” cyclohexadienediyl bridged compounds, [{(ArNacnac)Mg}2(μ-C6H6)]. Irradiation of [{(DipNacnac)Mg}2] in toluene, and each of the three isomers of xylene, promoted completely regio- and chemo-selective C?H bond activations, and formation of [(DipNacnac)Mg(Ar′)] (Ar′=meta-tolyl; 2,3-, 3,5- or 2,5-dimethylphenyl), and [{(DipNacnac)Mg(μ-H)}2]. Fluorobenzene was cleanly defluorinated by photoactivated [{(DipNacnac)Mg}2], leading to biphenyl and [{(DipNacnac)Mg(μ-F)}2]. Computational studies suggest all reactions proceed via photochemically generated magnesium(I) radicals, which reduce the arene substrate, before C?H or C?F bond activation processes occur.
- Jones, Dafydd D. L.,Douair, Iskander,Maron, Laurent,Jones, Cameron
-
supporting information
p. 7087 - 7092
(2021/03/01)
-
- Disulfide-Catalyzed Iodination of Electron-Rich Aromatic Compounds
-
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
-
-
- Disulfide-Catalyzed Iodination of Electron-Rich Aromatic Compounds
-
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
-
p. 7411 - 7417
(2019/06/18)
-
- Mild and selective organocatalytic iodination of activated aromatic compounds
-
We describe an organocatalytic iodination of activated aromatic compounds using 1,3-diiodo-5,5-dimethylhydantoin (DIH) as the iodine source with thiourea catalysts in acetonitrile. The protocol is applicable to a number of aromatic substrates with significantly different steric and electronic properties. The iodination is generally highly regioselective and provides high yields of isolated products. NMR kinetic investigations conducted in THF-d 8indicate the role of sulfur in the thiourea motif as a nucleophile that is assisted by H-bonding in the key steps of the reaction. Georg Thieme Verlag Stuttgart . New York.
- Jakab, Gergely,Hosseini, Abolfazl,Hausmann, Heike,Schreiner, Peter R.
-
supporting information
p. 1635 - 1640
(2013/07/27)
-
- Synthesis of complex ortho-allyliodoarenes by employing the reductive iodonio-claisen rearrangement
-
The reductive iodonio-Claisen rearrangement (RICR), involving complex aromatic λ3-iodanes and allyltrimethylsilane, was investigated. The RICR reaction of complex substituted aromatic hypervalent iodine (III) compounds and an allylmetal partner was conducted. The anionic oxy Cope rearrangement was found to be approximately 1010 to 1017 times faster than the neutral oxy Cope rearrangement due to weakening of the adjacent C-C bond by the oxygen anion. The results also indicate that the steric and electronic nature of the aromatic λ3-iodanes is the dominant factor influencing the [3,3]-sigmatropic rearrangement reaction. The removal of tert-butyl ether protecting group by using trifluroacetic acid in dichloromethane in the presence of triisopropylsilane gives the natural product broussin in 39% yield.
- Khatri, Hem Raj,Zhu, Jianglong
-
supporting information
p. 12232 - 12236
(2012/11/07)
-
- New thalidomide analogues derived through Sonogashira or Suzuki reactions and their TNF expression inhibition profiles
-
A library of new thalidomide C4/5 analogues containing either a phenyl or alkyne tether were synthesized using Sonogashira or Suzuki cross coupling reactions from their aryl halogenated precursors. All thalidomide analogues were tested for their ability to inhibit the expression of the proinflammatory cytokine Tumor Necrosis Factor (TNF). More explicitly the use of a novel reporter system utilizing the promoter region of the TNF gene in a human T-cell line provided a rapid and effective measure of NFκB transcriptional activity. Several compounds either containing either an aryl-isobutyl or aryl-isopropoxy group were the most effective in inhibiting TNF expression, and were several times more active than thalidomide itself. Five of the more active derivatives indicated an apoptotic response while one of these compounds, containing an aldehyde tether, showed possible influence of cell cycling effects.
- Stewart, Scott G.,Braun, Carlos J.,Ng, Sze-Ling,Polomska, Marta E.,Karimi, Mahdad,Abraham, Lawrence J.
-
experimental part
p. 650 - 662
(2010/04/26)
-
- METHOD OF PRODUCING IODIZING AGENT, AND METHOD OF PRODUCING AROMATIC IODINE COMPOUND
-
A method of the present invention, for producing an iodizing agent, includes the step of electrolyzing iodine molecules in a solution by using an acid as a supporting electrolyte. This realizes (i) a method of producing an iodine cation suitable for use as an iodizing agent that does not require a sophisticated separation operation after iodizing reaction is completed, and (ii) an electrolyte used in the method. Further, a method of the present invention, for producing an aromatic iodine compound, includes the step of causing an iodizing agent, and an aromatic compound whose nucleus has one or more substituent groups and two or more hydrogen atoms, to react with each other under the presence of a certain ether compound. This realizes such a method of producing an aromatic iodine compound that position selectivity in iodizing reaction of an aromatic compound is improved.
- -
-
Page/Page column 11
(2010/05/13)
-
- Iodination of activated aromatic compounds using sodium peroxodisulfate and iodine: An efficient way to iodinate alkylated calix[4]arenes
-
A simple method for the iodination of activated arenes, using molecular iodine and sodium peroxodisulfate as the oxidant, is presented. The reaction is conducted in the presence of catalytic amounts of tetramethylammonium iodide as a phase-transfer catalyst in acetonitrile. For non-polar substances, which are not soluble in pure acetonitrile such as calix[4]arenes bearing long alkyl chains, a modified reaction is introduced. In this case the phase-transfer catalyst is changed to methyltriphenylphosphonium peroxodisulfate. Chloroform as a cosolvent mediates solubility. Furthermore, we show that the slightly basic conditions obtained upon the addition of sodium bicarbonate have a beneficial effect on the yield. Georg Thieme Verlag Stuttgart.
- Barton, Olaf G.,Mattay, Jochen
-
p. 110 - 114
(2008/09/20)
-
- Practical electrochemical iodination of aromatic compounds
-
A practical method for electrochemical iodination of aromatic compounds was developed. The method involves the generation of I+ by electrochemical oxidation of I2 in CH3CN using H 2SO4 as supporting electrolyte followed by the reaction with aromatic compounds. The para/ortho selectivity for the reaction of mono-substituted benzenes was significantly improved using dimethoxyethane as cosolvent in the second step. The reaction with highly reactive aromatic compounds led to the formation of significant amounts of diiodo compounds in a macrobatch reactor. This problem was solved by fast 1:1 mixing of I+ with an aromatic compound using a microflow system consisting of a T-shaped micromixer and a microtube reactor.
- Kataoka, Kazuhide,Hagiwara, Yuji,Midorikawa, Koji,Suga, Seiji,Yoshida, Jun-Ichi
-
p. 1130 - 1136
(2013/01/03)
-
- Synthesis and TNF expression inhibitory properties of new thalidomide analogues derived via Heck cross coupling
-
A library of new thalidomide analogues containing an olefin functionality were synthesised using a Heck cross coupling reaction from their aryl halogenated precursor. All analogues were tested for their ability to inhibit the synthesis of the proinflammatory cytokine Tumour Necrosis Factor (TNF). Compounds 22, 29, 33 and 37 were the most effective in this assay inhibiting TNF expression 50%, 69%, 52% and 50%, respectively. Crown Copyright
- Stewart, Scott G.,Spagnolo, Daniel,Polomska, Marta E.,Sin, Melvin,Karimi, Mahdad,Abraham, Lawrence J.
-
p. 5819 - 5824
(2008/03/13)
-
- Chiral molecular clips control orthogonal crystalline organization
-
Chiral molecular clips constitute a robust system for crystal engineering studies and undergo several levels of orthogonal organization including heterochiral dimerization, H-bond or metal-ligand mediated tape formation, and longitudinal packing of the ta
- Chen, Yunfeng,She, Nengfang,Meng, Xianggao,Yin, Guodong,Wu, Anxin,Isaacs, Lyle
-
p. 1899 - 1902
(2008/02/04)
-
- Efficient method for the preparation of aromatic bromides and iodides by ferrocenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate-catalyzed halogenation with bromine and iodine monochloride
-
Direct iodination and bromination of various aromatic compounds with 1.1-2.0 molar amounts of iodine monochloride (ICl) and 1.1-3.0 molar amounts of bromine proceeded smoothly to afford the corresponding aromatic iodides and bromides, respectively, in good to excellent yields by using 0.05 molar amount of ferrocenium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, Cp2FeB[3,5-(CF3)2C6H 3]4 (1), in the presence of ZnO. Iodination of toluene in the co-existence of 0.5 molar amount of DDQ also proceeded to give iodotoluenes in high yield.
- Kitagawa, Hideo,Shibata, Tsuyoshi,Matsuo, Jun-Ichi,Mukaiyama, Teruaki
-
p. 339 - 345
(2007/10/03)
-
- An efficient and regioselective direct aromatic iodination using iodine and nitrogen dioxide
-
Direct iodination of a variety of aromatic compounds is achieved by using nitrogen dioxide as an oxidant in addition to iodine. The reaction affords aromatic monoidodides m high yields with high para-regioselectivity. 4,4'- Diiodo binuclear compounds are also obtained effectively by controlling the stoichiometry.
- Noda, Yumiki,Kashima, Mikito
-
p. 6225 - 6228
(2007/10/03)
-
- IODINATION OF ALKYLBENZENES WITH IODINE AND SILVER NITRITE
-
Iodination of alkylbenzenes with iodine and silver nitrite at room temperature gives iodoalkylbenzenes in good yield.
- Sy, Wing-Wah,Lodge, Bruce A.
-
p. 3769 - 3772
(2007/10/02)
-
- A Mild and Convenient Procedure for Conversion of Aromatic Compounds into Their Iodides Using Ammonium Hexanitratocerate(IV)
-
Polymethylbenzenes, polymethoxybenzenes, and naphthalene are iodinated with tetrabutylammonium iodide, alkali metal iodides, or molecular iodine in the presence of ammonium hexanitrocerate(IV).Ammonium hexanitrocerate(IV) behaves as a catalyst in the latter system, whereas it is a reagent in the former two.
- Sugiyama, Takashi
-
p. 2847 - 2848
(2007/10/02)
-