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A general method is described for the coupling of (hetero)aryl bromides with O-alkyl sulfamate esters. The protocol relies on catalytic amounts of nickel and photoexcitable iridium complexes and proceeds under visible light irradiation at ambient temperature. This technology engages a broad range of simple and complex O-alkyl sulfamate ester substrates under mild conditions. Furthermore, it is possible to avoid undesirable N-alkylation, which was found to plague palladium-based protocols for N-arylation of O-alkyl sulfamate esters. These investigations represent the first use of sulfamate esters as nucleophiles in transition metal-catalyzed C-N coupling processes.

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Annulative pi-extension (APEX) reactions of heteroarenes are described herein. A catalytic system comprising a cationic palladium species and o-chloranil using dimethyldibenzosiloles as pi-extending agents enabled the extension of the pi-system of benzo[b]thiophenes. pi-Extended dibenzofurans and carbazoles could also be obtained from benzofuran and N-tosylindole, respectively, with dimethyldibenzogermole as a germanium-based pi-extending agent. Mechanistic investigations indicated two possible reaction pathways involving carbopalladation-based double C-H arylation of benzothiophene or formal cycloaddition/oxidation cascades.

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The present invention is a method for the treatment or prevention of migraine comprising administering to a subject in need thereof a therapeutically effective amount of one or more novel benzo-heteroaryl sulfamide derivatives of formula (I) as herein defined. The present invention is directed to a method for the treatment and/or prevention of migraine, which includes mono-therapy and alternatively, co-therapy with at least anti-migraine agent

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A series of selected benzo[b]thiophene-5- and 6-sulfonamide derivatives previously reported to show cytotoxic activity and some others newly synthesized has been tested for the interactions with several CA isozymes, some of which are known to be involved in tumorigenesis (hCA IX), whereas others are ubiquitously found in many normal tissues (the cytosolic isoforms hCA I and II). The unsubstituted sulfonamides inhibited hCA I with inhibition constants in the range of 63-138 nM, hCA II with inhibition constants in the range of 6.3-8.8 nM, and hCA IX with inhibition constants in the range of 2.8-15 nM, being thus more active than clinically used inhibitors such as acetazolamide, methazolamide, ethoxzolamide, dichlorophenamide or indisulam (E 7070). Some of these derivatives also showed some selectivity for the inhibition of the tumor-associated (hCA IX) over the cytosolic isozyme hCA II. Although these derivatives may act on many targets other than the CAs (such as the NADH oxidase) or may induce apoptosis by accumulation of reactive oxygen species, it is quite important to try to decipher as many as possible of the potential mechanisms that lead to derivatives with potent antitumor activity in order to develop novel therapeutic strategies for the management of cancer.

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Awesome Chemistry Experiments For C10H9NO2S

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The invention relates to thiazine derivatives of the formula STR1 wherein R1 is lower alkyl and R2 is the residue of an aromatic heterocycle containing 1 to 4 hetero atoms optionally substituted by one or two lower alkyl groups, or a phenyl or benzyl group optionally substituted by halogen, hydroxy, lower alkyl, trifluoromethyl, nitro or lower alkoxy, and pharmaceutically acceptable salts thereof. The compounds of formula I are useful for the control or prevention of inflammation, pains, rheumatics and thromboses.

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The object of the invention relates to the salts of encenicline formed with inorganic and organic acids of general formula (I), as well as to the use of these for the production of pharmaceutical preparations primarily suitable for the treatment of diseases involving cognitive disorder (schizophrenia, Alzheimer’s disease).

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This communication describes an efficient one-pot procedure for the synthesis of 2-arylbenzo[b]thiophene derivatives via reaction of o-halo or nitro aryl carbonyl compounds with benzyl mercaptans in the presence of an excess of anhydrous K2CO3 at elevated temperature.

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Symmetric ethenyldithiophenes are important intermediates for synthesis of photochromic materials and organic conductors. When acetonitrile is used as a solvent, 3-methylthiophenylphosphonium salts form symmetric ethenyldithiophenes in the presence of a strong base (e.g., NaH, tBuOK) in moderate to high yields. This homocoupling reaction is faster than a Wittig reaction with aromatic ketones in acetonitrile. Our study shows that the presence of polar aprotic solvents promotes the homocoupling reaction.

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Reaction conditions for the three-component synthesis of aryl 1,3-diketones are reported applying the palladium-catalyzed carbonylative alpha-arylation of ketones with aryl bromides. The optimal conditions were found by using a catalytic system derived from [Pd(dba)2] (dba=dibenzylideneacetone) as the palladium source and 1,3-bis(diphenylphosphino)propane (DPPP) as the bidentate ligand. These transformations were run in the two-chamber reactor, COware, applying only 1.5 equivalents of carbon monoxide generated from the CO-releasing compound, 9-methylfluorene-9-carbonyl chloride (COgen). The methodology proved adaptable to a wide variety of aryl and heteroaryl bromides leading to a diverse range of aryl 1,3-diketones. A mechanistic investigation of this transformation relying on 31P and 13C NMR spectroscopy was undertaken to determine the possible catalytic pathway. Our results revealed that the combination of [Pd(dba)2] and DPPP was only reactive towards 4-bromoanisole in the presence of the sodium enolate of propiophenone suggesting that a [Pd(dppp)(enolate)] anion was initially generated before the oxidative-addition step. Subsequent CO insertion into an [Pd(Ar)(dppp)(enolate)] species provided the 1,3-diketone. These results indicate that a catalytic cycle, different from the classical carbonylation mechanism proposed by Heck, is operating. To investigate the effect of the dba ligand, the Pd0 precursor, [Pd(eta3-1-PhC 3H4)(eta5-C5H5)], was examined. In the presence of DPPP, and in contrast to [Pd(dba)2], its oxidative addition with 4-bromoanisole occurred smoothly providing the [PdBr(Ar)(dppp)] complex. After treatment with CO, the acyl complex [Pd(CO)Br(Ar)(dppp)] was generated, however, its treatment with the sodium enolate led exclusively to the acylated enol in high yield. Nevertheless, the carbonylative alpha-arylation of 4-bromoanisole with either catalytic or stoichiometric [Pd(eta3-1-PhC3H4) (eta5-C5H5)] over a short reaction time, led to the 1,3-diketone product. Because none of the acylated enol was detected, this implied that a similar mechanistic pathway is operating as that observed for the same transformation with [Pd(dba)2] as the Pd source. CO-operation is the key! The first palladium-catalyzed carbonylative alpha-arylation of aryl bromides is described. A wide array of different aryl 1,3-diketones can be isolated in good-to-excellent yields using only stoichiometric amounts of CO (see scheme). A mechanistic study is presented that suggests the need for enolate coordination prior to oxidative addition when [Pd(dba)2] is employed as the precatalyst. Copyright

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A rhodium-catalyzed 1,1-hydroacylation of thioacyl carbenes with alkynyl and alkenyl aldehydes and subsequent 6-endo-trig/dig cyclization are realized, giving structurally diverse 4H-thiopyran-4-ones and 2,3-dihydro-4H-thiopyran-4-ones in moderate to good yields. The oxidative addition of Rh(I) to aldehydes is proposed to be the turnover-limiting step. Manipulations of estrones demonstrate the applications of our formal (3 + 3) transannulations in the structural modifications of natural products.

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Benzothiophene – Wikipedia,
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