- Synthesis of N-allyl and N-acyl-2-vinylindoline
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Heating a mixture of (2R*,3R*)- and (2R*,3S*)-2- [(1S*)-1-iodoethyl]-3,5-dimethyl-1-[(2-nitrophenyl) sulfonyl]indolines with N-isopropylpiperidine in xylene resulted in (2S*,3R*)-3,5- dimethyl-1-[(2-nitrophenyl) sulfonyl]-2-vinylindoline. The latter reacted with thiophenol to afford (2S*,3R*)-3,5-dimethyl-2-vinylindoline, whose reaction with allyl halides or acetyl bromide gave rise to N-allyl-, N-propenyl-, or N-acetyl derivatives. Nitration of 1-acetyl-3,5-dimethyl-2- vinylindoline yielded ortho-nitro derivative.
- Mazgarova,Gataullin
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Read Online
- 2-Sulfoximidoyl acetic acids from multicomponent petasis reactions and their use as building blocks in syntheses of sulfoximine benzodiazepine analogues
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Upon application of a multicomponent Petasis reaction, a broad range of NH-sulfoximines and boronic acids react with glyoxalic acid to afford the corresponding 2-substituted acetic acids with N-bound sulfoximidoyl groups. The protocol features excellent y
- Hommelsheim, Renè,Nú?ez Ponce, Heliana Michaela,Truong, Khai-Nghi,Rissanen, Kari,Bolm, Carsten
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supporting information
p. 3415 - 3420
(2021/05/04)
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- Synthesis of thioethers, arenes and arylated benzoxazoles by transformation of the C(aryl)-C bond of aryl alcohols
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Transformation of aryl alcohols into high-value functionalized aromatic compounds by selective cleavage and functionalization of the C(aryl)-C(OH) bond is of crucial importance, but very challenging by far. Herein, for the first time, we report a novel and versatile strategy for activation and functionalization of C(aryl)-C(OH) bonds by the cooperation of oxygenation and decarboxylative functionalization. A diverse range of aryl alcohol substrates were employed as arylation reagents via the cleavage of C(aryl)-C(OH) bonds and effectively converted into corresponding thioether, arene, and arylated benzoxazole products in excellent yields, in a Cu based catalytic system using O2 as the oxidant. This study offers a new way for aryl alcohol conversion and potentially offers a new opportunity to produce high-value functionalized aromatics from renewable feedstocks such as lignin which features abundant C(aryl)-C(OH) bonds in its linkages.
- Chen, Bingfeng,Han, Buxing,Liu, Mingyang,Meng, Qinglei,Song, Jinliang,Zhang, Pei,Zhang, Zhanrong
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p. 7634 - 7640
(2020/08/14)
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- An Iodide-Mediated Transition-Metal-Free Strategy towards Unsymmetrical Diaryl Sulfides via Arylhydrazines and Thiols
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A mild, scalable iodine-mediated oxidative cross-coupling reaction of arylhydrazines and thiols for construction of thioethers (sulfides) in the absence of any transition metals or photocatalysts is disclosed. A variety of unsymmetrical diaryl sulfides with broad substrate scope both on thiols and hydrazines were synthesized in high yields in water at room temperature. Furthermore, to demonstrate the utility of the protocol, the above C-S bond formation was applied in the synthesis of the key structure of vortioxetine as an antidepressant drug. The gram-scale outcome also added to the potential utility of this protocol.
- Asadpour, Mohammad,Azizzade, Meysam,Ghasemi, Mehran,Jafarpour, Farnaz,Rajai-Daryasarei, Saideh
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supporting information
p. 727 - 734
(2020/02/25)
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- Intermediacy of Copper(I) under Oxidative Conditions in the Aerobic Copper-Catalyzed Decarboxylative Thiolation of Benzoic Acids
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An experimental mechanistic study of the aerobic copper-catalyzed decarboxylative thiolation of benzoic acids with arenethiols is reported. For the model reaction, the findings support the corresponding disulfide (PhSSPh) of the arenethiol (PhSH) as the active thiolating source under reaction conditions. Synthesis and reactivity studies along with kinetic measurements support the chemical and kinetic competence of catalytically active well-defined Cu complexes: (phen)CuI(O2CC6H4-o-NO2) (2), [(phen)CuI(μ-SC6H5)]2 (3), (phen)CuI(C6H4-o-NO2) (4), and (phen)CuII(O2CC6H4-o-NO2)2 (5) (phen = 1,10-phenanthroline). The presence of an induction period in the stoichiometric reaction of the copper(II) complex (phen)CuII(O2CC6H4-o-NO2)2 (5) with PhSSPh and the absence of an induction period in the analogous stoichiometric reaction of the copper(I) complex (phen)CuI(O2CC6H4-o-NO2) (2) suggest that a copper(I) carboxylate is a more likely intermediate than a copper(II) carboxylate. The observation of in situ reduction of CuII to CuI further supports CuI as the primary active catalytic species, and spectroscopic studies also indicate the catalyst resting state to be a CuI species. The catalytic reaction exhibits a first-order dependence on [CuI] and [2-nitrobenzoic acid] and a zero-order dependence on [PhSSPh] and p(O2), suggestive of turnover-limiting decarboxylation of a copper(I) carboxylate. Oxygen was found to promote the essential oxidative cleavage of the copper(I) thiolate intermediate [(phen)CuI(μ-SC6H5)]2 (3) to regenerate a catalytically active [(phen)CuII] (Cuox) species with concomitant formation of PhSSPh. On the basis of these findings, a reaction pathway is proposed for the C-S coupling reaction that includes the key CuI-based intermediates (phen)CuI(O2CC6H4-o-NO2) (2) and (phen)CuI(C6H4-o-NO2) (4). The pathway accounts for the role of O2 in generating the active thiolating source, PhSSPh, as well as enabling catalytic turnover of in situ generated [(phen)CuI(μ-SC6H5)]2 (3).
- Green, Kerry-Ann,Hoover, Jessica M.
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p. 1769 - 1782
(2020/02/06)
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- Homoleptic and heteroleptic Zn(ii) selone catalysts for thioetherification of aryl halides without scrubbing oxygen
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Five new mononuclear tetra-coordinated zinc(ii) selones, [Zn(L1)2Cl2] (1), [Zn(L1)2Br2] (2), [{Zn(L2)4}{BF4}2] (3), [{Zn(L2)4}{ClO4}2] (4), and [Zn(L2)2Br2] (5), have been isolated from a one-pot reaction between the corresponding zinc(ii) salt and selone ligand, 1-methyl 3-naphthylmethylimidazoline-2-selone (L1) or 1-isopropyl 3-methylimidazoline-2-selone (L2). All these complexes were characterized by CHN analysis, FT-IR, NMR studies, and single-crystal X-ray crystallography techniques. The Zn(ii) center in 1-5 exhibits a distorted tetrahedral geometry. Besides, 1-5 were employed as catalysts in the thioetherification of aryl halides. The first zinc(ii) catalyst-mediated thioetherification of aryl halides without scrubbing oxygen was demonstrated. Catalysts 1-5 are highly active towards the cross-coupling reaction between aryl halides and thiophenols. The catalytic ability of 1-5 was explored in THF, toluene, and CH3CN solvents with different bases such as K2CO3, Cs2CO3, and NaOtBu. Interestingly, the zinc(ii) center attached to two selone ligands is much more catalytically active than that attached to four selone ligands.
- Vaddamanu, Moulali,Velappan, Kavitha,Prabusankar, Ganesan
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p. 3574 - 3583
(2020/03/17)
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- Highly active mesoionic chalcogenone zinc(II) derivatives for C-S cross-coupling reactions
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The first mesoionic heavier chalcogenones, L1-L3 [L1 = 1-(2-mesitylene)-3-methyl-4-phenyltriazolin-5-selone; L2 = 1-(2-mesitylene)-3-methyl-4-phenyltriazolin-5-thione; L3 = 1-(benzyl)-2-3(methyl)-4-phenyltriazolin-5-selone], were isolated and characterised. Density functional theory was used to obtain insights into the σ donor and π accepting nature of mesoionic chalcogenones. Using these new ligands, a series of the first zinc(ii) mesoionic chalcogenone complexes were isolated. Three mono nuclear zinc(ii) chalcogenone complexes, [(L1)Zn(Cl)2(HOMe)] (1), [(L2)Zn(Cl)2(HOMe)] (3) and [(L2)Zn(Br)2(HOMe)] (4), and two dinuclear zinc complexes, [(L1)Zn(Br)(μ2-Br)]2 (2) and [(L3)Zn(Br)(μ2-Br)]2 (5), containing mesoionic thione and selone ligands were synthesized and characterised. These new complexes 1-5 represent the first structurally characterized mesoionic chalcogenone supported metal derivatives. Furthermore, all zinc complexes were characterized by thermogravimetric analysis and UV-vis spectroscopy. The solid-state structures of all zinc complexes were determined by single-crystal X-ray diffraction. The catalytic activities of the zinc(ii) complexes in thioetherification reactions were investigated without scrubbing of oxygen. The scope of the catalytic reactions was explored with a wide range of thiophenols and aryl halides. The diaryl thioethers were obtained in very good yield under mild conditions. The present protocol furnishes a synthetic route for the C-S cross-coupling of thiophenols and aryl halides without scrubbing oxygen and moisture.
- Vaddamanu, Moulali,Prabusankar, Ganesan,Velappan, Kavitha
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p. 129 - 140
(2019/12/26)
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- Cerium catalyst promoted C-S cross-coupling: Synthesis of thioethers, dapsone and RN-18 precursors
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In this work, we present a novel, efficient and green methodology for the synthesis of thioethers by the C-S cross-coupling reaction with the assistance of [Ce(l-Pro)2]2Ox as a heterogeneous catalyst in good to excellent yields. A scale-up of the protocol was explored using an unpublished methodology for the synthesis of a dapsone-precursor, which proved to be very effective over a short time. The catalyst [Ce(l-Pro)2]2Ox was recovered and it was shown to be effective for five more reaction cycles.
- Tavares Junior, José M. Da C.,Da Silva, Caren D. G.,Dos Santos, Beatriz F.,Souza, Nicole S.,De Oliveira, Aline R.,Kupfer, Vicente L.,Rinaldi, Andrelson W.,Domingues, Nelson L. C.
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supporting information
p. 10103 - 10108
(2019/12/23)
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- Anionic Bismuth(III) chloride cluster with diselenide countercations: Application in C-S cross coupling reactions
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The first weakly coordinating anion (WCA) with reactive p-block cation (rPBC) type of [(Bi4Cl16)4-{(LSeSeL)2+}2], L = 1,3-bis(2-benzhydryl-4,6-dimethylphenyl)-1H-imidazole-2(3H), ion pair is reported. The tetranuclear anionic bismuth(III) cluster shows a new type of ladder structure with two different types of Bi(III) coordination modes. In the solid state structure, the tetranuclear bismuth(III) cluster is sandwiched by two diselenide cations through hydrogen bonding interactions. Besides, this ion pair has been efficaciously employed as catalyst in C-S cross-coupling reactions under optimized reaction condition. This ion pair depicted a wide range of substrate scope with different thiols and aryl halides.
- Ganesan, Prabusankar,Mannem, Adinarayana,Muthukumaran, Nirmala
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supporting information
p. 29 - 35
(2019/02/08)
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- Visible-light-promoted organic dye-catalyzed sulfidation and phosphorylation of arylhydrazines toward aromatic sulfides and diarylphosphoryl hydrazides
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Visible-light-promoted sulfidation and phosphorylation of arylhydrazines for the synthesis of aromatic sulfides and diarylphosphoryl hydrazides were developed using the organic dyes rose bengal and Na2-eosin Y as photocatalysts, respectively. This strategy offers an efficient and mild transition-metal-free synthetic protocol for the formation of C-S and N-P bonds from arylhydrazines.
- Li, Rui,Shi, Tao,Chen, Xiao-Lan,Lv, Qi-Yan,Zhang, Yin-Li,Peng, Yu-Yu,Qu, Ling-Bo,Yu, Bing
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supporting information
p. 13642 - 13646
(2019/09/06)
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- Diaryl sulfide compounds and preparation method thereof
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The invention discloses diaryl sulfide compounds and a preparation method thereof. The method uses an organic dye as a photosensitizer, an equivalent weight of an oxidant is added, an aryl hydrazine and a diaryl disulfide are used as reactants, dimethyl sulfoxide is used as a solvent, a temperature is controlled at 25-45 DEG C, a reaction is performed for 5-12 h under visible light irradiation, column chromatography separation is performed, and therefore the product sulfide compounds are obtained. The invention provides the novel method for synthesizing the diaryl sulfide target compounds by using the cheap readily-available aryl hydrazine and diaryl disulfide compounds as starting raw materials for the first time. The method provided by the invention has the advantages of mild reaction conditions, simple operation and the like, and can also conveniently synthesize the asymmetric diaryl sulfide compounds; in drug synthesis, a metal catalyst is difficult to remove, so that drug production and applications are limited; therefore, in the method provided by the invention, the metal-free catalytic system shows huge potential application value.
- -
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Paragraph 0020; 0021
(2019/05/15)
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- Recyclable imidazolium ion-tagged nickel catalyst for microwave-assisted C-S cross-coupling in water using sulfonyl hydrazide as the sulfur source
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Herein, we report the facile and convenient synthesis of aryl sulfides through the sulfenylation of aryl halides with arylsulfonyl hydrazides, which is catalyzed by a simple and water-soluble Ni(ii) complex. The nickel complex based on the imidazolium ion-tagged salen architecture is synthesized and well characterized using various analytical techniques. The green solvent water is used as the solvent medium and moderate to good yields of aryl sulfides are obtained using 5 mol% of the catalyst under microwave irradiation. The incorporation of the ion-tag functionality helps in the recycling of the catalyst and successful reuse for up to five runs without appreciable change in its activity.
- Saini, Vaishali,Khungar, Bharti
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p. 12796 - 12801
(2018/08/04)
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- Primary sulfonamide as a coupling partner: Copper(I)-catalyzed regioselective cross-coupling of 2-nitro benzenesulfonamides with thiol through the cleavage of Ar–SO2NH2 bonds
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In this article, we have presented a novel and efficient method for the direct synthesis of unsymmetrical sulfides through the copper(I)-catalyzed cross-coupling of 2-nitro benzenesulfonamides with thiols in the presence of catalytic amount of CuI in DMF as solvent at 100 °C. In addition, the products were obtained in high to excellent yields. More importantly, the novel system showed the primary 2-nitro benzenesulfonamides as a new coupling partner and regioselectively promoted C–S bond-forming transformations through the cleavage of Ar–SO2NH2 bonds.
- Chen, Junmin,Zhang, Kuo,Zhao, Yongli,Pu, Shouzhi
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p. 1316 - 1323
(2018/04/05)
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- Design, synthesis and anticancer activity of N-(1-(4-(dibenzo[b,f][1,4]thiazepin-11-yl)piperazin-1-yl)-1-oxo-3-phenylpropan-2-yl derivatives
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Novel N-(1-(4-(dibenzo[b,f][1,4]thiazepin-11-yl)piperazin-1-yl)-1-oxo-3-phenylpropan-2-yl derivatives were designed, synthesized and their chemical structures were confirmed by 1H NMR, 13C NMR and Mass spectra. The anticancer activities of the newly synthesized compounds were evaluated in vitro against three human cancer cell lines including K562, Colo-205 and MDA-MB 231 by MTT assay. The screening results showed that five compounds (16b, 16d, 16i, 16p and 16q) exhibited potent cytotoxic activities with IC50 values between 20 and 40 μM. Further in vitro studies revealed that inhibition of sirtuins could be the possible mechanism of action of these molecules.
- Gudisela, Mura Reddy,Srinivasu,Mulakayala, Chaitanya,Bommu, Praveen,Rao, M.V. Basaveswara,Mulakayala, Naveen
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p. 4140 - 4145
(2017/08/23)
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- Formation of C-C, C-S and C-N bonds catalysed by supported copper nanoparticles
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Transition-metal catalysed cross-coupling reactions are still dominated by palladium chemistry. Within the recent past, copper has gained ground against palladium by virtue of its cheaper price and equivalent function in certain reactions. Four catalysts consisting of copper nanoparticles on zeolite, titania, montmorillonite and activated carbon have been tested in three palladium- and ligand-free cross-coupling reactions to form carbon-carbon, carbon-sulfur and carbon-nitrogen bonds. CuNPs/zeolite has been found to be the best one in the Sonogashira reaction of aryl iodides and arylacetylenes, as well as in the coupling of aryl halides with aryl and alkyl thiols, being reusable in both cases. However, the arylation of nitrogen-containing heterocycles (imidazole, pyrazole, benzimidazole and indole) has been better accomplished with CuNPs/titania, albeit CuNPs/activated carbon showed better recycling properties. The catalytic activity of the nanostructured catalysts has been compared with that of twelve commercial copper catalysts, with the former outperforming the latter in the three types of reactions studied.
- Mitrofanov, Alexander Yu.,Murashkina, Arina V.,Martín-García, Iris,Alonso, Francisco,Beletskaya, Irina P.
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p. 4401 - 4412
(2017/10/13)
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- Copper nanoparticles supported on polyaniline-functionalized multiwall carbon nanotubes: An efficient and recyclable catalyst for synthesis of unsymmetric sulfides using potassium ethyl xanthogenate in water
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A new and powerful polyaniline-functionalized carbon nanotube-supported copper(II) nanoparticle catalyst was successfully prepared and evaluated as a heterogeneous catalyst for the one-pot synthesis of unsymmetric thioethers by coupling of aryl, alkyl and benzyl halides using potassium ethyl xanthogenate as source of sulfur in water. All of these reactions gave the desired products in good to excellent yields. The catalyst is available, air-stable and can be reused several times without significant loss in its catalytic activity.
- Hajipour, Abdol R.,Jajarmi, Saeideh,Khorsandi, Zahra
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- Probing the hydrolytic reactivity of 2-difluoromethyl pyrroles
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α-Difluoromethyl pyrroles were found to be stable while N-protected with an electron-withdrawing group. Due to the propensity of pyrroles to access azafulvenium-like intermediates, the C-F bonds of an α-difluoromethyl substituent are labile under hydrolytic conditions. The presence of certain electron-withdrawing substituents about the pyrrolic ring can accelerate this process, as determined through a kinetic comparison of the deprotection and subsequent hydrolysis reactions of N-protected β-aryl α-difluoromethyl pyrroles.
- Melanson, Jennifer A.,Figliola, Carlotta,Smithen, Deborah A.,Kajetanowicz, Aleksandra K.,Thompson, Alison
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supporting information
p. 144 - 152
(2016/12/27)
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- A method for preparing [...]
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The invention discloses a preparation method of quetiapine hemifumarate. The preparation method of quetiapine hemifumarate comprises the following steps: etherifying, hydrogenating, condensing and carrying out chlorination by taking o-chloronitrobenzene and thiophenol as raw materials, and finally salifying with fumaric acid, thereby obtaining quetiapine hemifumarate. The production technology is simple to operate and convenient for large-scale production, the cost is saved and the high-purity high-yield quetiapine hemifumarate can be obtained.
- -
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Paragraph 0024; 0025
(2017/03/14)
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- Discovery of Novel Tricyclic Thiazepine Derivatives as Anti-Drug-Resistant Cancer Agents by Combining Diversity-Oriented Synthesis and Converging Screening Approach
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An efficient discovery strategy by combining diversity-oriented synthesis and converging cellular screening is described. By a three-round screening process, we identified novel tricyclic pyrido[2,3-b][1,4]benzothiazepines showing potent inhibitory activity against paclitaxel-resistant cell line H460TaxR (EC50 50 > 100 μM against normal human fibroblasts). The most active hits also exhibited drug-like properties suitable for further preclinical research. This redeployment of antidepressing compounds for anticancer applications provides promising future prospects for treating drug-resistant tumors with fewer side effects.
- Xiang, Jinbao,Zhang, Zhuoqi,Mu, Yan,Xu, Xianxiu,Guo, Sigen,Liu, Yongjin,Russo, Daniel P.,Zhu, Hao,Yan, Bing,Bai, Xu
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supporting information
p. 230 - 235
(2016/06/01)
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- Aerobic copper-catalyzed decarboxylative thiolation
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Copper-catalyzed decarboxylative thiolation using molecular oxygen as the sole oxidant was developed. A variety of aromatic carboxylic acids including 2-nitrobenzoic acids, pentafluorobenzoic acid and several heteroaromatic carboxylic acids undergo efficient thiolation to furnish the aryl sulfides in moderate to excellent yields.
- Li, Minghao,Hoover, Jessica M.
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supporting information
p. 8733 - 8736
(2016/07/15)
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- Synthesis and biological evaluation of optimized inhibitors of the mitotic kinesin Kif18A
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The mitotic spindle, a highly dynamic structure composed of microtubules, mediates the segregation of the previously duplicated genome into the two nascent daughter cells. Errors in this process contribute to pathology including tumor formation. Key for the shape and function of the mitotic spindle are kinesins, molecular motor proteins that convert chemical energy into mechanical work. Due to their fast mode of action, small molecules are valuable tools to dissect the dynamic functions of kinesins during mitosis. In this study, we report the identification of optimized small molecule inhibitors of the mitotic kinesin Kif18A. Using BTB-1, the first identified Kif18A inhibitor, as a lead compound, we synthesized a collection of derivatives. We demonstrate that some of the synthesized derivatives potently inhibited the ATPase activity of Kif18A with a half maximal inhibitory concentration (IC50) value in the low micromolar range. In vitro analysis of a panel of Kif18A-related kinesins revealed that the two most potent compounds show improved selectivity compared to BTB-1. Structure-activity relationship studies identified substituents mediating undesired inhibitory effects on microtubule polymerization. In summary, our study provides key insights into the mechanism of action of BTB-1 and its analogs, which will have a great impact on the further development of highly selective and bioactive Kif18A inhibitors. Since Kif18A is frequently overexpressed in solid tumors, such compounds are not only of great interest for basic research but also have the potential to open up new strategies for the treatment of human diseases.
- Braun, Joachim,M?ckel, Martin M.,Strittmatter, Tobias,Marx, Andreas,Groth, Ulrich,Mayer, Thomas U.
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p. 554 - 560
(2015/04/21)
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- Nucleophilic Aromatic Substitution Reactions in Water Enabled by Micellar Catalysis
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Given the huge dependence on dipolar, aprotic solvents such as DMF, DMSO, DMAc, and NMP in nucleophilic aromatic substitution reactions (SNAr), a simple and environmentally friendly alternative is reported. Use of a "benign-by-design" nonionic surfactant, TPGS-750-M, in water enables nitrogen, oxygen, and sulfur nucleophiles to participate in SNAr reactions. Aromatic and heteroaromatic substrates readily participate in this micellar catalysis, which takes place at or near ambient temperatures.
- Isley, Nicholas A.,Linstadt, Roscoe T. H.,Kelly, Sean M.,Gallou, Fabrice,Lipshutz, Bruce H.
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supporting information
p. 4734 - 4737
(2015/10/12)
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- Tridentate hydroxy-functionalised MCM-41-immobilised copper(I) complex as an efficient and recyclable catalyst for coupling of aryl iodides with thiols
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The C-S coupling reaction of aryl iodides with thiols was achieved at 110 °C in DMF/dioxane (V/V, 1:9) in the presence of a tridentate hydroxy-functionalised MCM-41-immobilised copper(I) complex [MCM-41-3OH-CuI] with Cs2CO3 as base to afford a variety of diaryl sulfides in good to excellent yields. The MCM-41-3OH-CuI catalyst can be easily recovered by a simple filtration and reused for at least six times without significant loss of activity.
- Yao, Fang,Zhang, Rongli,Wu, Yichao,Cai, Mingzhong
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p. 612 - 616
(2015/11/27)
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- Ascorbic Acid Promoted Metal-Free Synthesis of Aryl Sulfides with Anilines Nitrosated in Situ by tert -Butyl Nitrite
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A mild, metal-free synthesis of aryl sulfides has been disclosed. Aryl diazonium ion was generated by the in situ nitrosation of aniline, and it was reduced by ascorbic acid (vitamin C) to form aryl radical, which underwent a thiolation with disulfide to yield aryl sulfide. The reaction proceeded smoothly without heating or irradiation. This strategy was also expanded to the synthesis of aryl selenides.
- Bu, Mei-Jie,Lu, Guo-Ping,Cai, Chun
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supporting information
p. 1841 - 1846
(2015/08/06)
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- Ligand-free copper-catalyzed synthesis of asymmetrical thioethers by coupling aryl or alkyl halides using an acetyl thiourea precursor in wet polyethylene glyol (PEG 400)
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Asymmetrical diaryl or aryl alkyl thioethers can be prepared in good to excellent yields by coupling the appropriate aryl iodides and aryl or alkyl bromines using acetyl thiourea as a thiolprecursor, Cu2O as a catalyst, KOH as a base, and PEG 400-H2O as a solvent under ligand-free conditions.
- Zhang, Baohua,Shi, Lanxiang,Guo, Ruixia,Wang, Juan
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p. 561 - 566
(2015/05/20)
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- High activity and stability in the cross-coupling of aryl halides with disulfides over Cu-doped hierarchically porous zeolite ZSM-5
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A Cu-doped zeolite ZSM-5 (Cu-ZSM-5-M) with a micro-meso-macroporous structure was directly synthesized, and it exhibits excellent catalytic activity and good recyclability in the cross-coupling of aryl halides with diphenyl disulfides. This feature should be attributed to the structural characteristics of meso-macropores and homogeneous dispersion of active Cuδ+ (δ 2) species in Cu-ZSM-5-M.
- Fu, Wenqian,Liu, Taotao,Fang, Zhongxue,Ma, Yuli,Zheng, Xiang,Wang, Wenchang,Ni, Xiaojun,Hu, Maolin,Tang, Tiandi
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supporting information
p. 5890 - 5893
(2015/03/30)
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- Nickel-Schiff base complex catalyzed C-S cross-coupling of thiols with organic chlorides
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We report an efficient, mild and convenient synthetic protocol for the C-S cross-coupling reaction of various aryl, benzyl, allyl chlorides and thiols using 5 mol % Nickel-Schiff base catalyst with NaOH as the base, in DMF at 70 °C. Using this protocol, we have shown that a variety of aryl sulfides can be synthesized in excellent yields from readily available organic chlorides and thiols.
- Gogoi, Prasanta,Hazarika, Sukanya,Sarma, Manas J.,Sarma, Kuladip,Barman, Pranjit
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p. 7484 - 7489
(2014/12/10)
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- Synthesis and characterization of titanium complexes bearing sulfoxide groups and their catalytic behaviors in ethylene homo- and copolymerization
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Titanium complexes derived from 2,4-di-tert-butyl-6-((2-(arylsulfinyl) phenylimino)methyl)phenol are designed and synthesized. X-ray diffraction studies reveal that the complexes adopt distorted octahedral geometry with O(phenol), N(imine), and O(sulfoxide) coordinated with titanium. Combined with modified methylaluminoxane(MMAO), the complexes exhibit moderate to high activity to afford polyethylene even at 120 °C under 1 atm ethylene pressure. The complexes also show excellent capability in copolymerization of ethylene with either 1-hexene or norbornene. Results indicate that the introduction of sulfoxide groups could open the space around central metal and favors the insertion of bulky comonomers.
- Wang, Zheng,Peng, Ai-Qing,Sun, Xiu-Li,Tang, Yong
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p. 1144 - 1149
(2014/08/18)
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- Efficient C-S cross-coupling of thiols with aryl iodides catalyzed by Cu(OAc)2·H2O and 2,2′-biimidazole
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The classical Ullmann C-S cross coupling reaction of aryl iodides with aromatic/alkyl thiols under catalysis of 15 mol% Cu(OAc)2· H2O and 15 mol% 2,2′-biimidazole works at 80°C in DMSO for 3 h to provide a variety of aryl sulfides in good to excellent yields. The classical Ullmann C-S cross coupling reaction of aryl iodides with aromatic/alkyl thiols under catalysis of 15 mol% Cu(OAc)2· H2O and 15 mol% 2,2′-biimidazole works at 80°C in DMSO for 3 h to provide a variety of aryl sulfides in good to excellent yields. Copyright
- Zong, Chenglong,Liu, Jianli,Chen, Shengyan,Zeng, Runsheng,Zou, Jianping
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supporting information
p. 212 - 218
(2014/04/03)
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- An efficient protocol for the carbon-sulfur cross-coupling of sulfenyl chlorides with arylboronic acids using a palladium catalyst
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An efficient protocol for carbon-sulfur bond formation is developed, which involves the cross-coupling of sulfenyl chlorides and arylboronic acids catalyzed by a novel palladium-Schiff base complex. Good to high product yields, short reaction times, and mild reaction conditions are important features of this new method. Georg Thieme Verlag Stuttgart · New York.
- Gogoi, Prasanta,Kalita, Mukul,Barman, Pranjit
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p. 866 - 870
(2014/04/03)
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- Sulfur-silicon bond activation catalysed by Cl/Br ions: Waste-free synthesis of unsymmetrical thioethers by replacing fluoride catalysis and fluorinated substrates in SNAr reactions
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In contrast to conventional activation of Nu-SiR3 reagents by F ion attributed to the strong affinity of Si to F, S-Si activation can now be achieved using Cl/Br ions of TBAX as catalysts via formation of weaker X-Si bonds and Me3Si-X. This led to a waste-free synthesis of unsymmetrical thioethers via F-free SNAr reactions of activated (hetero)aryl halides and RS-SiMe3, with recovery of the useful Me3Si-X reagent in high yields. This journal is the Partner Organisations 2014.
- Jia, Xiaojuan,Yu, Lei,Liu, Jianping,Xu, Qing,Sickert, Marcel,Chen, Lianhui,Lautens, Mark
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supporting information
p. 3444 - 3449
(2014/07/08)
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- KF/clinoptilolite: An efficient promoter for the synthesis of thioethers
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Potassium fluoride impregnated on natural zeolite as a new solid base system effectively catalyzes the coupling of thiophenols with electron-deficient fluoro-, chloro- and bromo-arenes in DMSO. This versatile and efficient solid base has been demonstrated to afford the corresponding desired products in good to excellent yields. This procedure provides a convenient, efficient and practical method for the preparation of diaryl thioethers.
- Salmanpour, Sadegh,Khalilzadeh, Mohammad A.,Hosseini, Abolfazl
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p. 339 - 344
(2013/07/28)
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- High surface and magnetically recoverable mPANI/pFe3O 4 nanocomposites for C-S bond formation in water
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A high surface area mPANI/pFe3O4 nanocomposite from mesoporous polyaniline and porous magnetic Fe3O4 was used as a catalyst in the S-arylation of thiophenol with aryl chlorides and in the C-S bond formation between aryl iodides and thiourea in water. The mesoporosity of the polyaniline enhances the efficiency and stability of the porous magnetic Fe3O4 nanoparticles in both coupling reactions. The mPANI/pFe3O4 nanocomposite can be recovered with an external magnet and reused several times due to the superparamagnetic nature of the porous Fe3O4 nanoparticles.
- Damodara,Arundhathi,Likhar, Pravin R.
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p. 797 - 802
(2013/04/10)
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- Diversified synthesis of novel quinoline and dibenzo thiazepine derivatives using known active intermediates
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The novel drug development to control resisting infections in conventional drug therapy is a need of today. Few antiulcer relative derivatives developed by approaching convergent synthesis. The derivatives synthesized successfully are dibenzo thiazepine-pyridine (SLN11-SLN15) and benzimidazole-hydroquinoline based derivatives (SLN16-SLN20). It involved the coupling through microwave, sonication and conventional techniques at final step. The efficient technology identified as sonication technique basically time and yield. The reported compounds were structural characterized by elemental analysis and spectral studies such as 1H, 13C NMR and MS.
- Sharada,Satyanarayana Reddy,Sammaiah,Sumalatha
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p. 7959 - 7966
(2013/09/23)
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- Synthesis of substituted diphenyl sulfones and their structure-activity relationship with the antagonism of 5-HT6 receptors
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Substituted diphenyl sulfones (10a-n) were synthesised, and the structures were confirmed by NMR, LC-MS and X-ray crystallography. Their antagonistic activities towards 5-HT6 receptor were assessed in a cell-based functional assay. Diphenyl sulfone 10a, in spite of being the smallest and simplest known sulfonyl-containing 5-HT6R antagonist, showed a strong potency (Ki = 1.6 μM). Its derivative with a methylamine substituent, 10g (N-methyl-2-(phenylsulfonyl)aniline), was ~66-times as active as diphenyl sulfone (Ki = 24.3 nM). Addition of a piperazinyl moiety in the para-position relative to the sulfonyl group in compound 10m (N-methyl-2-(phenylsulfonyl)-5-piperazin-1-ylaniline) led to a further 150-fold increase in potency (Ki = 0.16 nM) to block the serotonin-induced response of HEK-293 cells that were stably transfected with the human recombinant 5-HT6 receptor.
- Ivachtchenko, Alexandre,Golovina, Elena,Kadieva, Madina,Mitkin, Oleg,Tkachenko, Sergei,Okun, Ilya
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p. 4614 - 4627
(2013/07/26)
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- Potassium tert-butoxide-mediated synthesis of unsymmetrical diaryl ethers, sulfides and selenides from aryl bromides
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Potassium tert-butoxide mediated carbon-chalcogen C-E (E=O, S and Se) coupling reaction has been studied from aryl bromide and phenol/aryl disulfide/diselenide substrates. A series of unsymmetrical diaryl chalcogenides were accessed from aryl bromide and diaryl dichalcogenide precursors by using 2.5 equiv of potassium tert-butoxide in DMSO at 80 C. Unsymmetrical diaryl ethers were also obtained by using phenol precursors at 40-45 C. Aryl bromides with methyl, trifluoromethyl, methoxy and nitro substituents showed compatibility in the carbon-chalcogen bond forming reaction. 4-Methoxy, methyl, trifluoromethyl substituted bromobenzene substrates gave two regioisomers: 3-substituted and 4-substituted diaryl chalcogenides when reacted with phenols/diaryl disulfides/diselenides. Formation of two regioisomeric diaryl chalcogenides in the reaction mixture suggests that potassium tert-butoxide reacts with bromobenzene to produce benzyne intermediate, which subsequently reacts with diaryl dichalcogenides and finally give a regioisomeric mixture of 4-substituted and 3-substituted diaryl chalcogenides.
- Kumar, Amit,Bhakuni, Bhagat Singh,Prasad, Ch. Durga,Kumar, Shailesh,Kumar, Sangit
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p. 5383 - 5392
(2013/07/04)
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- Exploration of the structure-activity relationship of the diaryl anilide class of ligands for translocator protein - Potential novel positron emitting tomography imaging agents
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A series of novel ligands based on the diaryl anilide (DAA) class of translocator protein (TSPO) ligands was synthesised and evaluated as potential positron emitting tomography (PET) ligands for imaging TPSO in vivo. Fluorine-18 labelling of the molecules was achieved using direct radiolabelling or synthon based labelling approaches. Several of the ligands prepared have promising profiles as potential TSPO PET imaging ligands and will be evaluated further as potential clinical imaging agents.
- Wadsworth, Harry,Jones, Paul A.,Chau, Wai-Fung,Durrant, Clare,Morisson-Iveson, Veronique,Passmore, Joanna,O'Shea, Dennis,Wynn, Duncan,Khan, Imtiaz,Black, Andrew,Avory, Michelle,Trigg, William
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p. 5795 - 5800,6
(2020/07/30)
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- 8-hydroxyquinolin-N-oxide-promoted copper-catalyzed C-S cross-coupling of thiols with aryl iodides
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8-Hydroxyquinolin-N-oxide was identified as a superior ligand for CuI-catalyzed C-S coupling reactions of aryl iodides with thiols to afford the corresponding thioethers in excellent yield. The method shows excellent chemoselectivity and high functional-group tolerance in both coupling partners. Copyright
- Su, Kun,Qiu, Yatao,Yao, Yiwu,Zhang, Dayong,Jiang, Sheng
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supporting information
p. 2853 - 2857
(2013/02/21)
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- Facile and mild displacement of nitrite ions in electron-deficient nitroarenes by alkyl or aryl thiols in the presence of magnesium methoxide as a solid base catalyst
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The nucleophilic aromatic substitution reaction (Sr) between nitroarenes (having electron-withdrawing groups in the ortho or para position), and alkyl- or arylthiols using magnesium methoxide as a solid base catalyst is described. This method leads to the creation of a series of valuable compounds from arylsulfides via nucleophilic displacement of the nitro group with the sulfanyl moiety. This facile method is a synthetically useful process, and it is significant that the nucleophile is promoted effectively by magnesium methoxide as a base in N,N-dimethylformamide. The displacement of then nitrite ion occurred in the presence of a variety of functional groups that caused an electron-deficient ring such as aldehyde, ketone, ester, cyano, and nitro groups. Georg Thieme Verlag Stuttgart ? New York.
- Naeimi, Hossein,Moradian, Mohsen
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p. 2223 - 2226
(2012/10/30)
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- Nano-CuFe2O4 as a magnetically separable and reusable catalyst for the synthesis of diaryl/aryl alkyl sulfides via cross-coupling process under ligand-free conditions
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An efficient protocol was developed for the CuFe2O4 nanopowder-catalyzed aryl-sulfur bond formation between aryl halide and thiol/disulfide. A variety of aryl sulfides were synthesized in impressive yields with good chemoselectivity and functional group tolerance in the presence of a catalytic amount of CuFe2O4, Cs2CO 3 as base, in nitrogen atmosphere, under ligand-free conditions, in DMSO as solvent at 100 °C. The catalyst is air-stable, inexpensive, magnetically separable and recyclable up to four cycles.
- Swapna, Kokkirala,Murthy, Sabbavarapu Narayana,Jyothi, Mocharla Tarani,Nageswar, Yadavalli Venkata Durga
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experimental part
p. 5989 - 5996
(2011/10/08)
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- Microwave-promoted TBAF-catalyzed SNAr reaction of aryl fluorides and ArSTMS: An efficient synthesis of unsymmetrical diaryl thioethers
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Microwave irradiation was found to promote tetrabutylammonium fluoride catalyzed nucleophilic aromatic substitution of aryl fluorides and arylthiotrimethylsilanes, affording high yields of unsymmetrical diaryl thioethers efficiently under mild, transition-metal- and base-free conditions. Microwave showed unusual improvement on the reaction in not only the conditions and reaction rate, but also in selectivity and substrate scope. Georg Thieme Verlag Stuttgart - New York.
- Liu, Chuanzhi,Zang, Xufeng,Yu, Baohua,Yu, Xiaochun,Xu, Qing
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supporting information; experimental part
p. 1143 - 1148
(2011/07/09)
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- Ring opening of pymisyl-protected aziridines with organocuprates
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The pyrimidine-2-sulfonyl (pymisyl) group is introduced as a new protecting group that can be used to activate aziridines towards ring opening. It is readily introduced and removed under mild conditions. Regioselective ring opening of pymisyl-protected 2-methyl-aziridine with organocuprates gives the corresponding sulfonamides in high yields, and the pymisyl group can subsequently be removed upon treatment with a thiolate. The versatility of this new nitrogen protecting group is illustrated with a new synthesis of Selegiline, a monoamine oxidase-B inhibitor marketed for the treatment of Parkinson's disease. Easy on'easy off: The pymisyl group is introduced as a new protecting group for the activation of aziridines towards ring opening with organocuprates (see scheme). It is readily removed under very mild conditions with thiolates. The versatility of the approach is illustrated in a new synthesis of Selegiline, a drug marketed for the treatment of Parkinson's disease.
- Bornholdt, Jan,Felding, Jakob,Clausen, Rasmus P.,Kristensen, Jesper L.
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supporting information; experimental part
p. 12474 - 12480
(2010/12/25)
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- Synthesis of azido arylselenides and azido aryldiselenides: a new class of selenium-nitrogen compounds
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We present here our results of the efficient synthesis of azido arylselenides and azido aryldiselenides under mild conditions. Starting from nitrogen-substituted benzenes, we incorporated selenium atom at aromatic ring and obtained amino arylselenides and diselenides in satisfactory yields. Treatment of these compounds with iso-pentyl nitrite (i-C5H11ONO) and azido trimethylsilane (Me3SiN3) in THF affords a variety of azido arylselenides and diselenides in good to excellent yields.
- Deobald, Anna Maria,Simon de Camargo, Leandro R.,Tabarelli, Greice,H?rner, Manfredo,Rodrigues, Oscar E.D.,Alves, Diego,Braga, Ant?nio L.
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experimental part
p. 3364 - 3367
(2010/08/19)
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- The [Cu]-catalyzed SNAR reactions: Direct amination of electron deficient aryl halides with sodium azide and the synthesis of arylthioethers under Cu(II) - Ascorbate redox system
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A one pot [Cu]-promoted SNAr reaction of electron-deficient halobenzenes with sodium azide and the reduction of the intermediate aryl azides under the same Cu(II)-ascorbate redox conditions leading to anilines has been documented. Control experiments revealed that both ascorbate and proline play important role in the reaction path way. Further, the use of this catalytic Cu(II)-ascorbate redox system has been explored for the synthesis of arylthioethers.
- Goriya, Yogesh,Ramana
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experimental part
p. 7642 - 7650
(2010/12/19)
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- Dimethyl sulfoxide/potassium hydroxide: A superbase for the transition metal-free preparation of cross-coupling products
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Potassium hydroxide (KOH) in dimethyl sulfoxide (DMSO) forms a superbasic medium that allows one to access cross-coupling products from reactions between aryl halides with various sulfur-, oxygen- and nitrogen-based nucleophiles under transition metal-free conditions. Copyright
- Yuan, Yu,Thome, Isabelle,Kim, Seok Hwan,Chen, Duanteng,Beyer, Astrid,Bonnamour, Julien,Zuidema, Erik,Chang, Sukbok,Bolm, Carsten
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experimental part
p. 2892 - 2898
(2011/01/05)
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- TBAF-catalysed facile synthesis of unsymmetrical diaryl thioethers via mild SNAr reactions
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By using tetrabutylammonium fluoride as the catalyst, the synthesis of unsymmetrical diaryl thioethers could be easily achieved in high yields via a mild nucleopilic aromatic substitution reaction of aryl fluorides and phenylthiotrimethylsilane.
- Yu, Baohua,Zang, Xufeng,Yu, Xiaochun,Xu, Qing
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experimental part
p. 351 - 353
(2010/10/04)
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- Indium-catalyzed C-S cross-coupling of aryl halides with thiols
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Indium-catalyzed C-S cross-coupling of aromatic and alkane thiols with aryl halides proceeds smoothly in the presence of In(OTf)3 (10 mol %), TMEDA (20 mol %), and KOH as a base in DMSO at 135 °C. When this protocol was utilized, a variety of thiols could be cross-coupled with aryl halides to afford the corresponding aryl sulfides in good to excellent yields.
- Reddy, V. Prakash,Swapna,Kumar, A. Vijay,Rao, K. Rama
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supporting information; experimental part
p. 3189 - 3191
(2009/08/08)
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- Lanthanum(III) oxide as a recyclable catalyst for the synthesis of diaryl sulfides and diaryl selenides
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La2O3 as a new and efficient recyclable catalyst in coupling various aryl halides with aromatic/alkyl thiols and diphenyl diselenide in combination with KOH as a base and DMEDA as a ligand in DMSO at 110 °C is reported.
- Murthy, Sabbavarapu Narayana,Madhav, Bandaru,Reddy, Vutukuri Prakash,Nageswar, Yadavalli Venkata Durga
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supporting information; experimental part
p. 5902 - 5905
(2010/03/02)
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- Discovery of orally active, pyrrolidinone-based progesterone receptor partial agonists
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We have designed and synthesized a novel series of pyrrolidinones as progesterone receptor partial agonists. Compounds from this series had improved AR selectivity, rat pharmacokinetic properties, and in vivo potency compared to the lead compound. In addi
- Washburn, David G.,Hoang, Tram H.,Frazee, James S.,Johnson, Latisha,Hammond, Marlys,Manns, Sharada,Madauss, Kevin P.,Williams, Shawn P.,Duraiswami, Chaya,Tran, Thuy B.,Stewart, Eugene L.,Grygielko, Eugene T.,Glace, Lindsay E.,Trizna, Walter,Nagilla, Rakesh,Bray, Jeffrey D.,Thompson, Scott K.
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supporting information; experimental part
p. 4664 - 4668
(2010/04/28)
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- Synthesis of aryl sulfides by decarboxylative C-S cross-couplings
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A study was conducted to demonstrate the transition-metal-catalyzed synthesis of aryl sulfides by decarboxylative C-S cross-couplings. Coupling reaction of 2-nitrobenzoic acid with 1-octanethiol were carried in the presence of different combinations of tr
- Duan, Zhongyu,Ranjit, Sadananda,Zhang, Pengfei,Liu, Xiaogang
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supporting information; experimental part
p. 3666 - 3669
(2009/12/07)
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