- Synthetic Strategies towards Imidazopyridinones and 7-Azaoxindoles and their Evaluation as Antibacterial Agents
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Imidazopyridinones and 7-azaoxindoles are two classes of heterocyclic compounds with only limited previous use in organic and medicinal chemistry. Various synthetic methods and routes have been evaluated to identify safe and robust chemistry to advanced i
- Blindheim, Fredrik Heen,Hoff, B?rd Helge,Krogh S?gaard, Caroline,Olsen, Cecilie Elisabeth,Otterlei, Marit,Sundby, Eirik
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supporting information
p. 2701 - 2712
(2021/06/26)
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- Electro-Oxidative Selective Esterification of Methylarenes and Benzaldehydes
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A mild and green electro-oxidative protocol to construct aromatic esters from methylarenes and alcohols is herein reported. Importantly, the reaction is free of metals, chemical oxidants, bases, acids, and operates at room temperature. Moreover, the design of the electrolyte was found critical for the oxidation state and structure of the coupling products, a rarely documented effect. This electro-oxidative coupling process also displays exceptional tolerance of many fragile easily oxidized functional groups such as hydroxy, aldehyde, olefin, alkyne, as well as neighboring benzylic positions. The enantiomeric enrichment of some chiral alcohols is moreover preserved during this electro-oxidative coupling reaction, making it overall a promising synthetic tool.
- Yu, Congjun,?zkaya, Bünyamin,Patureau, Frederic W.
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supporting information
p. 3682 - 3687
(2021/02/01)
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- Ni-NiO heterojunctions: a versatile nanocatalyst for regioselective halogenation and oxidative esterification of aromatics
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Herein, we report a facile method for the synthesis of Ni-NiO heterojunction nanoparticles, which we utilized for the nuclear halogenation reaction of phenol and substituted phenols usingN-bromosuccinimide (NBS). A remarkablepara-selectivity was achieved for the halogenated products under semi-aqueous conditions. Interestingly, blocking of thepara-position of phenol offeredortho-selective halogenation. In addition, the Ni-NiO nanoparticles catalyzed the oxidative esterification of carbonyl compounds with alcohol, diol or dithiol in the presence of a catalytic amount of NBS. It was observed that the aromatic carbonyls substituted with an electron-donating group favoured nuclear halogenation, whereas an electron-withdrawing group substitution in carbonyl compounds facilitated the oxidation reaction. In addition, the catalyst was magnetically separated and recycled 10 times. The tuned electronic structure at the Ni-NiO heterojunction controlled selectivity and activity as no suchpara-selectivity was observed with commercially available NiO or Ni nanoparticles.
- Bhardwaj, Nivedita,Goel, Bharat,Indra, Arindam,Jain, Shreyans K.,Singh, Ajit Kumar,Tripathi, Nancy
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p. 14177 - 14183
(2021/08/16)
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- A convenient and efficient H2SO4-promoted regioselective monobromination of phenol derivatives using N-bromosuccinimide
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A convenient, rapid H2SO4-promoted regioselective monobromination reaction with N-bromosuccinimide was developed. The desired para-monobrominated or ortho-monobrominated products of phenol derivatives were obtained in good to excellent yields with high selectivity. Regioselective chlorination and iodination were also achieved in the presence of H2SO4 using N-chlorosuccinimide and N-iodosuccinimide, respectively.
- Wu, Yong-Qi,Lu, Hai-Jia,Zhao, Wen-Ting,Zhao, Hong-Yi,Lin, Zi-Yun,Zhang, Dong-Feng,Huang, Hai-Hong
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supporting information
p. 813 - 822
(2020/02/15)
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- Stepwise mechanism for the bromination of arenes by a hypervalent iodine reagent
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A mild, metal-free bromination method of arenes has been developed using the combination of bis(trifluoroacetoxy)iodobencene and trimethylsilyl bromide. In situ-formed dibromo(phenyl)-λ3-iodane (PhIBr2) is proposed as the reactive intermediate. This methodology using PIFA/TMSBr has been applied with success to a great number of substrates (25 examples). The treatment of mono-substituted activated arenes led to para-brominated products (2u-z) in excellent 83-96% yields. Density functional theory calculations indicate a stepwise mechanism involving a double bromine addition followed by a type II dyotropic reaction with concomitant re-aromatization of the six-membered ring.
- Arrieta, Ana,Cossío, Fernando P.,Granados, Albert,Shafir, Alexandr,Vallribera, Adelina
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p. 2142 - 2150
(2020/03/11)
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- Aromatic Halogenation Using N-Halosuccinimide and PhSSiMe3 or PhSSPh
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We developed a mild aromatic halogenation reaction using a combination of N-halosuccinimide and PhSSiMe3 or PhSSPh. Less reactive aromatic compounds, such as methyl 4-methoxybenzoate, were brominated with PhSSiMe3 or PhSSPh and N-bromosuccinimide in high yields. No reaction was observed in the absence of PhSSiMe3 or PhSSPh. This method is also applicable to chlorination reactions using N-chlorosuccinimide and PhSSPh.
- Hirose, Yuuka,Yamazaki, Mirai,Nogata, Misa,Nakamura, Akira,Maegawa, Tomohiro
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p. 7405 - 7410
(2019/06/14)
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- HETEROCYCLIC-IMIDAZOLE COMPOUNDS, PHARMACEUTICAL COMPOSITIONS THEREOF, PREPARATION METHOD THEREFOR AND USE THEREOF
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The present invention relates to a heterocyclic-imidazole derivative, a preparation method therefor, and a medical use thereof, and particularly to a new heterocyclic-imidazole derivative of general Formula (I), a preparation method therefor, a pharmaceutical composition comprising the same, and use thereof as a therapeutic agent, particularly as a poly(ADP-ribose)polymerase (PARP) inhibitor.
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Paragraph 0154
(2018/03/09)
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- Heterocycle and imidazole compounds, pharmaceutical composition comprising heterocycle and imidazole derivatives as well as preparation method and application of heterocycle and imidazole compounds
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The invention relates to heterocycle and imidazole derivatives as well as a preparation method and a pharmaceutical application of heterocycle and imidazole derivatives, in particular to novel heterocycle and imidazole derivatives as shown in the general formula (I), a preparation method of the heterocycle and imidazole derivatives, pharmaceutical composition comprising the heterocycle and imidazole derivatives as well as an application of the heterocycle and imidazole derivatives as a therapeutic agent and particularly as a PARP (poly (ADP-ribose) polymerase) inhibitor.
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Paragraph 0219; 0220; 0221; 0222; 0223
(2017/07/20)
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- A facile color-tuning strategy for constructing a library of Ir(III) complexes with fine-tuned phosphorescence from bluish green to red using a synergetic substituent effect of -OCH3 and -CN at only the C-ring of C∧N ligand
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By simply grafting a -CN group and/or a -OCH3 group onto the meta- and/or para-site of the C-ring, a series of Ir(iii) complexes bearing a similar molecular platform of bis(1,2-diphenyl-1H-benzimidazolato-N,C2′)iridium(iii)(acetylacetonate), but showing fine-tuned phosphorescence covering nearly the whole window of the visible spectrum with a wide color-tuning range of 109 nm was acquired. With the help of DFT calculations, it was revealed that if the C-related arene moiety of the C∧N ligand (C-ring) contributes substantially to both the HOMO and LUMO of an Ir(iii) complex, the concurrent introduction of an electron-donating -OCH3 and an electron-withdrawing -CN groups on the C-ring at the meta- and para-sites relative to the Ir atom may lead to a favorable synergetic substituent effect on the color-tuning direction. This may represent a facile yet effective molecular design strategy for Ir(iii) complexes with a desirous emission color. A bluish green organic light-emitting diode (OLED) based on one of the objective complexes displayed a maximum current efficiency of 62.1 cd A-1, an external quantum efficiency of 19.8%, and a brightness of 48-040 cd m-2, implying that high-performance red and blue OLED phosphors as well as libraries of Ir(iii) complexes bearing similar molecular platforms may be developed through this -OCH3 and -CN synergetic substitution strategy.
- Jiao, Yan,Li, Ming,Wang, Ning,Lu, Tao,Zhou, Liang,Huang, Yan,Lu, Zhiyun,Luo, Daibing,Pu, Xuemei
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supporting information
p. 4269 - 4277
(2016/06/01)
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- Extended structure-activity study of thienopyrimidine-based EGFR inhibitors with evaluation of drug-like properties
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Thieno[2,3-d]pyrimidines are attractive derivatives for cancer treatment, among others through regulation of the epidermal growth factor receptor tyrosine kinase (EGFR-TK). In an extended SAR study, 44 new compounds of this class have been evaluated as inhibitors, while simultaneously focussing on ADME properties. Through the application of bioisosters, hybrid structures, solubilizing tails, and a combination approach several successful alterations in terms of activity and physiochemical properties were accomplished. Compounds based on benzylamines were found superior to aniline hybrid structures with respect to activity and ADME profile. Exploration of the former class revealed meta-and para amides as favourable 6-aryl substituents, contributing to an increase in activity and acting as a linker for solubilizing tails. Next, combinations of activity-inducing groups on the same scaffold resulted in new drug candidates. Compounds containing 6-aryls with the (2-(dimethylamino)ethyl)carbamoyl substituent were found equipotent to Erlotinib. Compared to this commercial drug, improved solubility and metabolic stability were observed. However, the thieno[2,3-d]pyrimidines with a solubilizing tail was by Caco-2 experiments found to have permeability issues, making further drug development difficult. Selected compounds were further analysed for toxicity and teratogenicity in zebrafish embryos. Two thienopyrimidines were both found to be less lethal than Erlotinib and to perform as well in terms of teratogenicity. Finally, the most promising thienopyrimidine drug was evaluated in a panel of human cancer cell lines, showing a clear potential for thienopyrimidines as anti-cancer agents.
- Bugge, Steffen,Buene, Audun Formo,Jurisch-Yaksi, Nathalie,Moen, Ingri Ullestad,Skj?nsfjell, Ellen Martine,Sundby, Eirik,Hoff, B?rd Helge
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p. 255 - 274
(2015/11/27)
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- Highly efficient dehydrogenative cross-coupling of aldehydes with amines and alcohols
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A common protocol for the synthesis of amides, esters and α-ketoesters via cross dehydrogenative coupling of aldehydes and amines/alcohols has been developed. The method is applicable to a wide variety of alcohols and amines as well as aliphatic and aromatic aldehydes. Also, the use of acetaldehyde for acetylation and ethyl glyoxalate to access 2-oxo-amino esters is presented for the first time.
- Deshidi, Ramesh,Rizvi, Masood Ahmad,Shah, Bhahwal Ali
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p. 90521 - 90524
(2015/11/11)
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- Selective and efficient oxidation of benzylic alcohols to benzaldehydes and methyl benzoates by dibromo-5,5-dimethylhydantoin
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A selective and efficient method of oxidizing benzyl alcohols to benzaldehydes and methyl benzoates by using 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) as oxidant is developed. One-step conversion of benzyl alcohols to methyl benzoates in methanol at room temperature for 12 hours is achieved without any catalysts. Moreover, para-substituted benzyl alcohols are obtained in 86-98% yield. When dichloromethane is used as solvent, further oxidation of benzaldehydes to esters is well controlled, selectively affording benzaldehydes in 89-99% yield within 30 minutes.
- Li, Zhongzhou,Zhu, Wei,Bao, Jinlong,Zou, Xinzhuo
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supporting information
p. 1155 - 1164
(2014/04/03)
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- Total synthesis of acerogenins E, G and K, and centrolobol
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The first total synthesis of the diarylheptanoid acerogenins E and K, isolated from Acer nikoense MAXIM., is described. Formation of the 13-membered m,m-cyclophane skeleton was successfully achieved on the basis of a domino process involving a Miyaura arylborylation-intramolecular Suzuki reaction. The cyclization precursor was prepared via a Wittig reaction and Claisen-Schmidt condensation, which proceeded in moderate yields. The total synthesis of acerogenin G and centrolobol was also achieved from a common synthetic intermediate.
- Ogura, Tetsuhiro,Usuki, Toyonobu
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supporting information
p. 2807 - 2815
(2013/03/28)
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- Brominated methanes as photoresponsive molecular storage of elemental Br2
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The photochemical generation of elemental Br2 from brominated methanes is reported. Br2 was generated by the vaporization of carbon oxides and HBr through oxidative photodecomposition of brominated methanes under a 20 W low-pressure mercury lamp, wherein the amount and situations of Br2 generation were photochemically controllable. Liquid CH 2Br2 can be used not only as an organic solvent but also for the photoresponsive molecular storage of Br2, which is of great technical benefit in a variety of organic syntheses and in materials science. By taking advantage of the in situ generation of Br2 from the organic solvent itself, many organobromine compounds were synthesized in high practical yields with or without the addition of a catalyst. Herein, Br2 that was generated by the photodecomposition of CH2Br2 retained its reactivity in solution to undergo essentially the same reactions as those that were carried out with solutions of Br2 dissolved in CH 2Br2 that were prepared without photoirradiation. Furthermore, HBr, which was generated during the course of the photodecomposition of CH2Br2, was also available for the substitution of the OH group for the Br group and for the preparation of the HBr salts of amines. Furthermore, the photochemical generation of Br2 from CH2Br2 was available for the area-selective photochemical bleaching of natural colored plants, such as red rose petals, wherein Br2 that was generated photochemically from CH 2Br2 was painted onto the petal to cause radical oxidations of the chromophoric anthocyanin molecules. The generation of Br 2 from brominated methanes occurred upon photoirradiation under O2. The solutions that contained elemental Br2 were useful for the synthesis of organobromine compounds and the macroscopic photochemical bleaching of colored plants. Copyright
- Kawakami, Kazumitsu,Tsuda, Akihiko
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p. 2240 - 2252
(2012/11/06)
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- In situ acidic carbon dioxide/water system for selective oxybromination of electron-rich aromatics catalyzed by copper bromide
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Carbon dioxide, being one of the major greenhouse gases responsible for global warming, its atmospheric level grows ever faster since the beginning of industrial era. Great efforts have been devoted to developing versatile technologies/processes to adjust and manipulate the rapid growth of CO 2 emission. Besides CO2 capture and storage/sequestration (CCS) to control its emission, chemical utilization of the captured CO 2 (CCU) emerges to be a rational technique for economical benefits as well as environmental concerns. As for the aim of CO2 utilization, an environmentally benign CO2/water reversible acidic system was developed for the copper (II)-catalyzed selective oxybromination of electron-rich aromatics without the need of any conventional acid additive and organic solvent. Notably, up to 95% yields of the bromination products were attained with good regio-selectivity when cupric bromide was used as the catalyst and lithium bromide as a cheap and easy handling bromine source under supercritical CO2. The catalytic system worked well for electron-rich aromatics including ethers, sulfides and mesitylene. Carbonic acid in situ formed from CO2 and water is supposed to act as the proton donator in the Bronsted acid-promoted reaction. Notably, CO2 in this study serves as a reaction medium and a promoter in conjunction with water and also provides safe environment for aerobic reactions. Given with excellent reaction efficiency as well as no need of neutralization disposal, this process thus represents an environmentally friendly approach for aerobic bromination of aromatics with essential reduction of CO2 emission as well as an economically beneficial way for application of captured CO2.
- Liu, An-Hua,Ma, Ran,Zhang, Meng,He, Liang-Nian
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- Isolation, synthesis, and biological activity of biphenyl and m-terphenyl-type compounds from Dictyostelium cellular slime molds
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From the fruiting bodies of Dictyostelium polycephalum, we obtained four aromatic compounds: dictyobiphenyl A (1) and B (2) and dictyoterphenyl A (3) and B (4). The synthesis of 1-4 was performed to confirm the structures and obtain sufficient material fo
- Kikuchi, Haruhisa,Matsuo, Yusuke,Katou, Yasuhiro,Kubohara, Yuzuru,Oshima, Yoshiteru
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p. 8884 - 8889
(2012/10/29)
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- Continuous flow oxidation of alcohols and aldehydes utilizing bleach and catalytic tetrabutylammonium bromide
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We report a method for the oxidation of a range of alcohols and aldehydes utilizing a simple flow system of alcohols in EtOAc with a stream of 12.5% NaOCl and catalytic Bu4NBr. Secondary alcohols are oxidized to ketones, aldehydes are oxidized directly to methyl esters in the presence of methanol, and benzylic alcohols are oxidized to either benzaldehydes or methyl esters, depending on the conditions used. The reaction conditions are mild and generally provide complete conversion in 5-30 min.
- Leduc, Andrew B.,Jamison, Timothy F.
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supporting information; experimental part
p. 1082 - 1089
(2012/08/27)
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- In situ acidic carbon dioxide/ethanol system for selective oxybromination of aromatic ethers catalyzed by copper chloride
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An environmentally benign carbon dioxide/ethanol reversible acidic system was developed for the copper(II)-catalyzed regioselective oxybromination of aromatic ethers without the need of any conventional acid additive and organic solvent. Good to excellent yields together with very good regioselectivity were achieved when easily available cupric chloride dihydrate was used as catalyst and lithium bromide as the cheap and easy-to-handle bromine source under supercritical carbon dioxide conditions. Notably, the catalytic system worked well for a wide range of aromatic ethers including sulfides, resulting in the formation of the mono-brominated products in high yields and exclusive regioselectivity. The alkylcarbonic acid in situ formed from ethanol and carbon dioxide is assumed to play the crucial role in the Braonsted acid-promoted reaction, which could probably act as the proton donator, and was studied employing in situ FT-IR technique under carbon dioxide pressure by monitoring the vibration shift of the hydroxy group of ethanol. Given with excellent bromine atom efficiency as well as no need of neutralization in waste disposal, this approach thus represents a greener pathway for the aerobic bromination of aromatic ethers. A possible catalytic cycle for the in situ alkylcarbonic acid-assisted oxybomination and the effect of supercritical carbon dioxide, i.e., activation of alcohol and enhancement of mass transfer are also discussed. Copyright
- Liu, An-Hua,He, Liang-Nian,Hua, Fang,Yang, Zhen-Zhen,Huang, Cheng-Bin,Yu, Bing,Li, Bin
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experimental part
p. 3187 - 3195
(2012/01/06)
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- TETRAHYDROCYCLOPENTA[B]INDOL-3-YL CARBOXYLIC ACID DERIVATIVES USEFUL IN THE TREATMENT OF AUTOIMMUNE AND INFLAMMATORY DISORDERS
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The present invention relates to certain (1,2,4-oxadiazol-3-yl)-1,2,3,4-tetrahydrocyclo-penta[b]indol-3-yl carboxylic acid derivatives of Formula (Ia) and pharmaceutically acceptable salts thereof, which exhibit useful pharmacological properties, for example, as agonists of the S1P1 receptor. Also provided by the present invention are pharmaceutical compositions containing compounds of the invention, and methods of using the compounds and compositions of the invention in the treatment of S1P1 associated disorders, for example, psoriasis, rheumatoid arthritis, Crohn's disease, transplant rejection, multiple sclerosis, systemic lupus erythematosus, ulcerative colitis, type I diabetes, acne, microbial infections or diseases and viral infections or diseases.
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Page/Page column 86
(2009/07/18)
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- NaIO4/LiBr-mediated direct conversion of benzylic alcohols and aromatic aldehydes to aromatic esters
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Aromatic aldehydes or benzylic alcohols are directly converted to the corresponding aromatic esters in high yields on treatment with methanol or ethanol mediated by sodium metaperiodate (NaIO4)/LiBr in an acidic medium. Copyright Taylor & Francis Group, LLC.
- Shaikh, Tanveer Mohammad Ali,Emmanuvel, Lourdusamy,Sudalai, Arumugam
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p. 2641 - 2646
(2008/02/12)
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- Total synthesis of aristogin C in aqueous systems
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Aristogin C (4), a new diaryl either isolated from the leaves of Aristolochia elegans, was synthesized through a three-step procedure with readily available materials. All of the three reactions were carried out in aqueous systems. Copyright Taylor & Francis Group, LLC.
- Gao, Hong-Yun,Ha, Cheng-Yong
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p. 3283 - 3286
(2007/10/03)
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- 2-ARYLOXYETHYL GLYCINE DERIVATIVES AND THEIR USE AS GLYCINE TRANSPORT INHIBITORS
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The present invention relates to certain 2-aryloxyethyl glycine derivatives that exhibit activity as inhibitors of the glycine type-1 transporter, to pharmaceutical compositions containing them and to their use in the treatment of neurological and neuropsychiatric disorder.
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Page/Page column 55
(2010/02/14)
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- Bromodecarbonylation and bromodecarboxylation of electron-rich benzaldehydes and benzoic acids with oxone and sodium bromide
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Benzaldehydes and benzoic acids bearing ortho- and paraelectron donating substituents having unshared electron-pair have undergone bromodecarbonylation or bromodecarboxylation on treatment with sodium bromide in the presence of Oxone in aqueous methanol.
- Koo, Bon-Suk,Kim, Eun-Hoo,Lee, Kee-Jung
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p. 2275 - 2286
(2007/10/03)
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- A simple and practical halogenation of activated arenes using potassium halide and oxone in water-acetonitrile medium
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A simple and practical halogenation of activated arenes using a reagent combination of potassium halide and oxone in water-acetonitrile medium is presented. The halogenated products were obtained with good yields and in high purity.
- Tamhankar,Desai,Mane,Wadgaonkar,Bedekar
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p. 2021 - 2027
(2007/10/03)
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- The Synthesis of Mycophenolic Acid from 2,4-Dihydroxybenzoic Acid
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Mycophenolic acid (1) has been synthesized from 2,4-dihydroxybenzoic acid by regioselective introduction of the three required carbon substituents.A key transformation in this sequence is the introduction of the methyl substituent at position 5 by a rapid, uncatalyzed replacement of the bromide in 8 at low temperature by methyllithium.The scope and mechanism of this methylation reaction are examined.
- Patterson, John W.
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p. 4542 - 4548
(2007/10/02)
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- Marine Bacteria, I. - Synthesis of Pentabromopseudiline, a Cytotoxic Phenylpyrrole from Alteromonas luteo-violaceus
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A new synthesis of 2,3,4-tribromo-5-(3,5-dibromo-2-hydroxyphenyl)pyrrole (1a, pentabromopseudiline), an antibiotic, enzymeinhibitory and cytotoxic active constituent of the marine bacterium Alteromonas luteo-violaceus, is described.For investigation of structure-activity relationships further 2-phenylpyrroles are investigated.Key step in their synthesis is the Grignard reaction of 2-(1,3-dioxan-2-yl)ethylmagnesium bromide (9d) with benzoyl chlorides yielding γ-phenyl-γ-ketoaldehydes 24, and the Paal-Knorr cyclisation of the latter. - Key Words: Alteromonas luteo-violaceus / Bromopyrrole / Marine bacteria / Pentabromopseudiline
- Laatsch, Hartmut,Pudleiner, Heinz
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p. 863 - 882
(2007/10/02)
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