- Focused ortho-Lithiation and Functionalization of p-Bromo- and p-Iodoanisole
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By use of the strategy for ortho-lithiation (DoM) that conceptually diminishes the pKA difference between the ortho-H of the substrate and the conjugate acid of the metalating agent, effective metalation of bromine and iodine bearing aryl substrates can be carried out. As a set of prototypes, p-bromoanisole (p-BrA) and p-iodoanisole (p-IA) have been successfully ortho-metalated in promoted hydrocarbon media using ortho-lithiodimethylbenzylamine (o-LiDMBA) as the metalating agent. No hint of exchange of either halogen was noted using these conditions. These studies add to the emerging evidence of a hitherto unidentified acidifying effect on the proton(s) ortho- to a directing metalation group (DMG) by both a p-iodo and a p-bromo substituent.
- Slocum,Jennings, John A.,Reinscheld, Thomas K.,Whitley, Paul E.
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p. 4400 - 4406
(2018/09/10)
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- Silver(I)-catalyzed iodination of arenes: Tuning the lewis acidity of N-iodosuccinimide activation
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A mild and rapid method for the iodination of arenes that utilizes silver(I) triflimide as a catalyst for activation of N-iodosuccinimide has been developed. The transformation was found to be general for a wide range of anisole, aniline, acetanilide, and phenol derivatives and allowed the late-stage iodination of biologically active compounds such as PIMBA, a SPECT imaging agent of breast cancer, and (a?)-IBZM, a dopamine D2 receptor antagonist. The method was also modified for the radioiodination of arenes using a one-pot procedure involving the in situ generation of [125I]-N-iodosuccinimide followed by the silver(I)-catalyzed iodination.
- Racys, Daugirdas T.,Sharif, Salaheddin A. I.,Pimlott, Sally L.,Sutherland, Andrew
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p. 772 - 780
(2016/02/18)
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- Highly Regioselective Iodination of Arenes via Iron(III)-Catalyzed Activation of N-Iodosuccinimide
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An iron(III)-catalyzed method for the rapid and highly regioselective iodination of arenes has been developed. Use of the powerful Lewis acid, iron(III) triflimide, generated in situ from iron(III) chloride and a readily available triflimide-based ionic liquid allowed activation of N-iodosuccinimide (NIS) and efficient iodination under mild conditions of a wide range of substrates including biologically active compounds and molecular imaging agents.
- Racys, Daugirdas T.,Warrilow, Catherine E.,Pimlott, Sally L.,Sutherland, Andrew
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supporting information
p. 4782 - 4785
(2015/10/12)
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- Gold(I)-catalyzed iodination of arenes
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A wide variety of electron-rich arenes were efficiently converted into the corresponding iodinated compounds via a gold(I)-catalyzed reaction under mild conditions. Georg Thieme Verlag Stuttgart. New York.
- Leboeuf, David,Ciesielski, Jennifer,Frontier, Alison J.
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supporting information
p. 399 - 402
(2014/03/21)
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- ANTIPROLIFERATIVE BENZO [B] AZEPIN- 2 - ONES
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Disclosed are compounds of Formula (I) or pharmaceutically acceptable salts thereof, wherein W, X, Y, Z, R1, R2, R3 and R4 are described in this application, and methods of using said compounds in the treatment of cancer.
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Page/Page column 43
(2014/02/15)
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- A direct and mild formylation method for substituted benzenes utilizing dichloromethyl methyl ether-silver trifluoromethanesulfonate
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A silver trifluoromethanesulfonate (AgOTf)-promoted direct and mild formylation of benzenes has been developed. The reaction utilizing dichloromethyl methyl ether (Cl2CHOMe) and AgOTf powerfully formylated various substituted benzenes under temperature conditions as low as -78 C without losing the protecting groups on the phenolic hydroxyl group.
- Ohsawa, Kosuke,Yoshida, Masahito,Doi, Takayuki
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p. 3438 - 3444
(2013/06/26)
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- General copper-catalyzed transformations of functional groups from arylboronic acids in water
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A simple and general copper-catalyzed method has been developed for transformations of various functional groups (i I, i N3, i SO2R, i OH, i NH2, and i NO 2) on aromatic rings from arylboronic acids in water under air. The protocol uses cheap and readily available inorganic salts (KI, NaN3, NaSO2R, NaOH, NaNO2) and aqueous ammonia as the functional-group sources, simple Cu2O/NH3 as the catalyst system, environmentally friendly water as the solvent, and oxygen in air as the oxidant. Importantly, the copper catalyst system in water was recyclable. This study should provide a useful strategy for interconversions of the functional groups on aromatic rings.
- Yang, Haijun,Li, Yong,Jiang, Min,Wang, Junmei,Fu, Hua
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experimental part
p. 5652 - 5660
(2011/06/23)
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- Biphenomycin B and derivatives: Total synthesis and translation inhibition
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A full account on the synthesis of the antibiotic natural product biphenomycin B and several derivatives is reported, which employs a Suzuki coupling reaction of a free carboxylic acid and macrolactam formation as key transformations. Liberal exchange of
- He, Yu-Peng,Tan, Hao,Arve, Lars,Baumann, Sascha,Waldmann, Herbert,Arndt, Hans-Dieter
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p. 1546 - 1556
(2013/01/11)
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- A general route to cyclopeptide alkaloids: total syntheses and biological evaluation of paliurines e and F, ziziphines N and Q, abyssenine A, mucronine E, and analogues
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A full account of the total syntheses of the cyclopeptide alkaloids paliurine E and F, ziziphine N and Q, abyssenine A, and mucronine E is provided. A key feature of the syntheses involves an intramolecular amidation of a vinyl iodide, which allows us sim
- Toumi, Mathieu,Rincheval, Vincent,Young, Ashley,Gergeres, Danielle,Turos, Edward,Couty, Francois,Mignotte, Bernard,Evano, Gwilherm
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experimental part
p. 3368 - 3386
(2011/02/28)
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- Total synthesis of paliurine F
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A couple of coppers: An efficient, asymmetric synthesis of the sedative cyclopeptide alkaloid paliurine F has been achieved. The strategy employs two copper(I)-mediated coupling reactions as key steps to install the aryl ether linkage as well as to form t
- Toumi, Mathieu,Couty, Francois,Evano, Gwilherm
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p. 572 - 575
(2008/02/02)
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- Comparison of iodination of methoxylated benzaldehydes and related compounds using iodine/silver nitrate and iodine/periodic acid
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Iodination of the three methoxybenzaldehydes, four dimethoxybenzaldehydes, vanillin, and piperonal by two methods were compared. Iodine and periodic acid gave better yields for iodination for the methoxybenzaldehydes, whereas iodine and silver nitrate generally gave better yields for the rest of the compounds. Copyright Taylor & Francis Group, LLC.
- Hathaway, Bruce A.,White, Kristen L.,McGill, Mark E.
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p. 3855 - 3860
(2008/02/10)
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- PURINE DERIVATIVES AS A3 AND A1 ADENOSINE RECEPTOR AGONISTS
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Disclosed are (N)-methanocarba adenine nucleosides of the formula: [Formula] as highly potent A3 adenosine receptor agonists, pharmaceutical compositions comprising such nucleosides, and a method of use of these nucleosides, wherein R1-R6 are as defined in the specification. These nucleosides are contemplated for use in the treatment a number of diseases, for example, inflammation, cardiac ischemia, stroke, asthma, diabetes, and cardiac arrhythmias. The invention also provides compounds that are agonists of both A1 and A3 adenosine receptors for use in cardioprotection.
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Page/Page column 28
(2010/10/20)
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- (N)-methanocarba 2,N6-disubstituted adenine nucleosides as highly potent and selective A3 adenosine receptor agonists
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A series of ring-constrained (N)-methanocarba-5′-uronamide 2,N 6-disubstituted adenine nucleosides have been synthesized via Mitsunobu condensation of the nucleobase precursor with a pseudosugar ring containing a 5′-ester functionality. Following appropriate functionalization of the adenine ring, the ester group was converted to the 5′-N-methylamide. The compounds, mainly 2-chloro-substituted derivatives, were tested in both binding and functional assays at human adenosine receptors (ARs), and many were found to be highly potent and selective A3-AR agonists. Selected compounds were compared in binding to the rat A3AR to assess their viability for testing in rat disease models. The N 6-(3-chlorobenzyl) and N6-(3-bromobenzyl) analogues displayed Ki values at the human A3AR of 0.29 and 0.38 nM, respectively. Other subnanomolar affinities were observed for the following N6 derivatives: 2,5-dichlorobenzyl, 5-iodo-2-methoxybenzyl, trans-2-phenyl-1-cyclopropyl, and 2,2-diphenylethyl. Selectivity for the human A3AR in comparison to the A1AR was the following (fold): the N6-(2,2-diphenylethyl) analogue 34 (1900), the N 6-(2,5-dimethoxybenzyl) analogue 26 (1200), the N6-(2,5- dichlorobenzyl) and N6-(2-phenyl-1-cyclopropyl) analogues 20 and 33 (1000), and the N6-(3-substituted benzyl) analogues 17, 18, 28, and 29 (700-900). Typically, even greater selectivity ratios were obtained in comparison with the A2A and A2BARs. The (N)-methanocarba-5′-uronamide analogues were full agonists at the A 3AR, as indicated by the inhibition of forskolin-stimluated adenylate cyclase at a concentration of 10 μM. The N6-(2,2-diphenylethyl) derivative was an A3AR agonist in the (N)-methanocarba-5′- uronamide series, although it was an antagonist in the ribose series. Thus, many of the previously known groups that enhance A3AR affinity in the 9-riboside series, including those that reduce intrinsic efficacy, may be adapted to the (N)-methanocarba nucleoside series of full agonists.
- Tchilibon, Susanna,Joshi, Bhalchandra V.,Kim, Soo-Kyung,Duong, Heng T.,Gao, Zhan-Guo,Jacobson, Kenneth A.
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p. 1745 - 1758
(2007/10/03)
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- AMINOMETHYLENE SUBSTITUTED NON-AROMATIC HETEROCYCLES AND USE AS SUBSTANCE P ANTAGONISTS
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The present invention relates to novel aminomethylene substituted non-aromatic heterocycles and, specifically, to compounds of the formula wherein W, R 1, R 2, R 3, A, X', Y' and Z' are as defined in the specification, and to intermediates used in the synthesis of such compounds. The novel compounds of formulae Ia and Ib are useful in the treatment of inflammatory and central nervous system disorders, as well as other disorders.
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Page column 27
(2010/01/31)
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- Iodination of Methylated Anisoles: Unusual Aryl Methyl Replacement and Oxidations
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The treatment of methylated anisoles with iodine, periodic acid, sulfuric acid, and aqueous acetic acid has resulted in iododemethylations and/or aryl methyl oxidations in addition to the expected mono- and diiodinations of the aromatic ring.Four dimethylanisoles and o-methylanisole were treated under identical conditions.Iododemethylations were observed in three of the four dimethylanisoles and aryl methyl oxidations to benzaldehydes occured with o-methylanisole and two of the dimethylanisoles.No precedence could be found for either of these reactions under the experimental conditions employed.Several possible mechanisms are discussed for these transformations.Some experimental evidence suggests that methyl oxidation to a benzaldehyde could be a prerequisite for an iododemethylation via an iodonium ion-assisted reverse Gatterman-Koch reaction; single-electron-transfer or classical electrophilic mechanisms are also consistent with the iododemethylations.
- Panetta, Charles A.,Fang, Zheng,Mattern, Daniell L.
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p. 7953 - 7958
(2007/10/03)
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- Electron Transfer Mechanism for Periodic Acid Oxidation of Aromatic Substrates
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Evidence for the involvement of cation radicals during the periodic acid oxidation of aromatic substrates like hydrocarbons, phenolic ethers, phenols etc. has been presented.
- Bhatt, M. V.,Hosur, B. M.
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p. 1004 - 1005
(2007/10/02)
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