- BODIPY-Based Photoacid Generators for Light-Induced Cationic Polymerization
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Photoacid generators (PAGs) are organic compounds that can generate protons (H+) upon irradiation with certain wavelengths of light. In this work, we designed and synthesized the first BODIPY-based PAGs with D-A and D-?-A conjugation structures and achieved green and red LED light-induced acid generation. By the use of red-light absorbance, red-LED-triggered cationic polymerization was demonstrated as a proof-of-concept application of these PAGs.
- Sambath, Karthik,Wan, Zhaoxiong,Wang, Qi,Chen, Hao,Zhang, Yuanwei
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Read Online
- Expedient Preparation of Aryllithium and Arylzinc Reagents from Aryl Chlorides Using Lithium 4,4′-Di- tert -Butylbiphenylide and Zinc(II) Chloride
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We report an efficient method for the preparation of aryllithium and zinc reagents from inexpensive and readily available aryl chlorides by using lithium 4,4′-di-tert-butylbiphenylide (LiDBB) as a lithiation reagent. The resulting organometallic reagents underwent subsequent reactions with a variety of electrophiles, such as an aldehydes, DMF, PhSSO2Ph, TsCN, an aryl halide, or an acid chloride (through Pd-catalyzed cross-coupling). Aryl chlorides bearing substituents, including methoxy, 3,4-methylenedioxy, fluoride, TMS, OTMS, NMe2, acetal, and ketal, were shown to be appropriate substrates. Interestingly, aryl chlorides containing a formyl group could also be used, provided that the formyl group was temporarily converted into an α-amino alkoxide by using the lithium amide of N,N,N′-trimethylethylenediamine (LiTMDA). The presence of a hydroxyl group was also tolerated when it was deprotonated with n-BuLi prior to the addition of LiDBB.
- Shen, Zhi-Liang,Sommer, Korbinian,Knochel, Paul
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Read Online
- Nucleophilic aromatic substitution reaction of nitroarenes with alkyl- or arylthio groups in dimethyl sulfoxide by means of cesium carbonate
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Treatment of nitroarenes having electron-withdrawing groups at the ortho or para position with alkanethiol in the presence of cesium carbonate in dimethyl sulfoxide at 25°C leads to nucleophilic displacement of the nitro group with the alkylthio group. Cesium carbonate is superior to other bases such as potassium carbonate, sodium carbonate, and triethylamine. The cesium-mediated nucleophilic aromatic substitution reaction provides a mild yet powerful and user-friendly protocol for the synthesis of aryl sulfides.
- Kondoh, Azusa,Yorimitsu, Hideki,Oshima, Koichiro
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Read Online
- A Visible-Light-Harvesting Covalent Organic Framework Bearing Single Nickel Sites as a Highly Efficient Sulfur–Carbon Cross-Coupling Dual Catalyst
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Covalent Organic Frameworks (COFs) have recently emerged as light-harvesting devices, as well as elegant heterogeneous catalysts. The combination of these two properties into a dual catalyst has not yet been explored. We report a new photosensitive triazine-based COF, decorated with single Ni sites to form a dual catalyst. This crystalline and highly porous catalyst shows excellent catalytic performance in the visible-light-driven catalytic sulfur–carbon cross-coupling reaction. Incorporation of single transition metal sites in a photosensitive COF scaffold with two-component synergistic catalyst in organic transformation is demonstrated for the first time.
- Chen, Hui,Liu, Wanlu,Laemont, Andreas,Krishnaraj, Chidharth,Feng, Xiao,Rohman, Fadli,Meledina, Maria,Zhang, Qiqi,Van Deun, Rik,Leus, Karen,Van Der Voort, Pascal
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supporting information
p. 10820 - 10827
(2021/04/09)
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- Synthesis and biological evaluation of new 1,2,4-triazolo[1,5-a] pyridine and 1,2,4-triazolo[1,5-a] isoquinolinederivatives bearing diphenyl sulfide moiety as antimicrobial agents
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Hydrazone derivative (3) was used as a precursor for the synthesis of novel [1,2,4]triazolo[1,5-a]pyridine derivatives via its reaction with some electrophilic reagents. Treatment of hydrazone derivative (3) with arylidenemalononitriles(4) in the presence of piperidine afforded the 1,2,4-triazolo[1,5-a]pyridine derivatives (7a-d). Ternary condensation of hydrazone (3), aliphatic aldehyde and malononitrile (1:1:1 molar ratio) in the presence of a basic catalyst furnished the novel 1,2,4-triazolo[1,5-a]pyridine derivatives (8a,b). Similarly, cyclization of hydrazone (3) with ethyl α-cyanocinnamates (9) (1:1 molar ratio) yields the corresponding 1,2,4-triazolo[1,5-a]pyridines (10a-c). The hydrazone (3) can be cyclized with appropriate arylazomalononitriles(11) to afford the corresponding 1,2,4-triazolo[1,5-a]pyridines (14a,b). The behavior of fused thiophene derivative (15) towards electron-poor olefins was investigated. It is has been found that, 1,2,4-triazolo[1,5-a]isoquinoline derivative (17) was obtained by treatment of thiophene derivative (15) with dimethyl acetylenedicarboxylate (DMAD). Condensation of compound (15) with N-phenylmalemide furnished pyrrolotriazoloisoquinoline derivative (18). Also, the triazoloisoquinoline derivative (19) was obtained by condensation of compound (15) with chalcone. All the newly synthesized compounds were characterized by analytical and spectral data and evaluated for their antibacterial and antifungal activities in vitro against two Gram-positive bacteria, two Gram negative bacteria as well as two fungi. In general, the newly synthesized compounds showed good antimicrobial activities.
- El-Adasy, Abu-Bakr A.,El-Haleem Hussein, Abd M.,Ishak, Esam A.,Hafiz, Ibrahim S.A.,Gawish, Emad H.,Elapasery, Morsy A.,El-Gaby, Mohamed S.A.
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p. 913 - 921
(2021/02/12)
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- Modulation of photochemical oxidation of thioethers to sulfoxides or sulfones using an aromatic ketone as the photocatalyst
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We have developed an eco-friendly and chemo-selective photocatalytic synthesis of sulfoxides or sulfones via oxidation of sulfides (thioethers) at ambient temperature using air or O2 as the oxidant. An inexpensive thioxanthone was used as the photocatalyst. Our method offers excellent chemical yields and good functional group tolerance. The hydrogen bonding between hexafluoro-2-propanol (HFIP) and sulfoxides may play an important role in minimizing the over-oxidization of sulfoxides.
- Zhao, Bin,Hammond, Gerald B.,Xu, Bo
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supporting information
(2021/09/13)
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- Chan-Lam-Type C-S Coupling Reaction by Sodium Aryl Sulfinates and Organoboron Compounds
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A Chan-Lam-Type C-S coupling reaction using sodium aryl sulfinates has been developed to provide diaryl thioethers in up to 92% yields in the presence of a copper catalyst and potassium sulfite. Both electron-rich and electron-poor sodium aryl sulfinates and diverse organoboron compounds were tolerated for the synthesis of aryl and heteroaryl thioethers and dithioethers. The mechanistic study suggested that potassium sulfite was involved in the deoxygenation of sulfinate through a radical process.
- Lam, Long Yin,Ma, Cong
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supporting information
p. 6164 - 6168
(2021/08/16)
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- Design, synthesis, and biological evaluation of pyrimidine analogs as SecA inhibitors
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SecA, a key component of the bacterial Sec-dependent secretion pathway, is an attractive target for the development of new antimicrobial agents. We have previously reported pyrimidine analogs as SecA inhibitors. Herein, we report an extension of the earlier work in the synthesis and evaluation of a series of 15 5-cyanothiouracil derivatives as SecA inhibitors. All the compounds have been evaluated for their inhibition of SecA ATPase (EcSecAN68) and for their antimicrobial activity against Escherichia coli NR698 (a leaky mutant) and Bacillus anthracis Sterne. Twelve compounds showed IC50 of less than 6.3 μM when tested against EcSecAN68. In antimicrobial studies against E. coli NR698, six compounds showed MIC of 12.5 μM with three being less than 6.3 μM. Against B. anthracis Sterne, three compounds showed MIC of 6.3 μM.
- Bamba, Fante,Jin, Jinshan,Chaudhary, Arpana S.,Tai, Phang C.,Wang, Binghe
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p. 1334 - 1340
(2021/03/19)
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- Room temperature nickel-catalyzed cross-coupling of aryl-boronic acids with thiophenols: Synthesis of diarylsulfides
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A NiCl2/2,2′-bipyridine-catalyzed cross-coupling of thiophenols with arylboronic acids has been developed for the synthesis of symmetric and unsymmetric diarylsulfides at room temperature and in air. This methodology is reliable and offers a mild and easy to operate process for the synthesis of arylthioethers, which are essential compounds with applications in the pharmaceutical and agricultural industries. This method avoids the use of expensive transition metals, such as Pd, Ir or Rh, sophisticated ligands and elevated temperatures. It also has a wide substrate scope (55 examples) and provides products in good to excellent yields (72-93%).
- Bhowmik, Amit,Fernandes, Rodney A.,Yadav, Mahesh
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p. 2447 - 2458
(2020/04/15)
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- CoII immobilized on an aminated magnetic metal-organic framework catalyzed C-N and C-S bond forming reactions: A journey for the mild and efficient synthesis of arylamines and arylsulfides
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In this work, we report a simple and versatile method for the modification of a metal-organic framework (NH2-MIL53(Al)) in a step-wise manner. To characterize the synthesized nanostructured catalyst, a variety of spectroscopic and microscopic techniques including FT-IR, XRD, BET, TEM, FE-SEM, EDX, EDX-mapping, TGA, XPS, VSM, ICP-OES and CHN have been employed. Fe3O4@AMCA-MIL53(Al)-NH2-CoII NPs, which benefit from small nanocrystalline size (10-30 nm, according to the XRD and TEM data) in combination with the coexistence of magnetic nanoparticles, a metal-organic framework, and cobalt species, were found to be an excellent environment catalyst to promote the C-N and C-S cross coupling reactions. A wide range of functional substrates including electron-withdrawing and electron-donating aryl halides underwent the coupling reaction with aromatic/heteroaromatic/benzylic and aliphatic amines and sulfides. The results demonstrated that the yields of the target products were good to excellent and the catalyst can be recycled for at least seven recycling runs without a discernible decrease in its catalytic activity. Furthermore, the heterogeneity studies (such as hot filtration and poisoning tests) efficiently confirmed that the as-synthesized nanostructured catalyst is heterogeneous and completely stable under the reaction conditions. We hope that our study inspires more interest in designing novel catalysts based on using low-cost metal ions (such as cobalt) in the field of cross coupling reactions.
- Mohammadinezhad, Arezou,Akhlaghinia, Batool
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p. 15525 - 15538
(2019/10/19)
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- Design, synthesis and biological evaluation of “Multi-Site”-binding influenza virus neuraminidase inhibitors
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Encouraged by our earlier discovery of neuraminidase inhibitors targeting 150-cavity or 430-cavity, herein, to yield more potent inhibitors, we designed, synthesized, and biologically evaluated a series of novel oseltamivir derivatives via modification of C-1 and C5–NH2 of oseltamivir by exploiting 150-cavity and/or 430-cavity. Among the synthesized compounds, compound 15e, the most potent N1-selective inhibitor targeting 150-cavity, showed 1.5 and 1.8 times greater activity than oseltamivir carboxylate (OSC) against N1 (H5N1) and N1 (H5N1–H274Y). In cellular assays, 15e also exhibited greater potency than OSC against H5N1 with EC50 of 0.66 μM. In addition, 15e demonstrated low cytotoxicity in vitro and low acute toxicity in mice. Molecular docking studies provided insights into the high potency of 15e against N1 and N1–H274Y mutant NA. Overall, we envisioned that the significant breakthrough in the discovery of potent group-1-specific neuraminidase inhibitors may lead to further investigation of more potent anti-influenza agents.
- Jia, Ruifang,Zhang, Jian,Ai, Wei,Ding, Xiao,Desta, Samuel,Sun, Lin,Sun, Zhuosen,Ma, Xiuli,Li, Zhong,Wang, Defeng,Huang, Bing,Zhan, Peng,Liu, Xinyong
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- A semiconducting supramolecular Co(ii)-metallohydrogel: an efficient catalyst for single-pot aryl-S bond formation at room temperature
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A novel mechanically stable supramolecular Co(ii)-metallohydrogel has been synthesized. Cobalt(ii) nitrate hexahydrate and monoethanolamine, as a low molecular weight organic gelator, are used to get the gel. The mechanical stability of the supramolecular hydrogel was analyzed. The morphology of the supramolecular metallohydrogel was scrutinized. The semiconducting features of the metallohydrogel were studied. The conducting properties of the Co(ii)-metallohydrogel establish a Schottky barrier diode type nature. The catalytic nature of the Co(ii)-metallohydrogel based room temperature single pot aryl-S coupling reaction was explored. Most interestingly, the Co(ii)-metallohydrogel based catalytic aryl-S coupling reaction does not require any column-chromatographic purification protocol to get pure aryl-thioethers. Thus, through this work a semiconducting Schottky barrier diode application and catalytic role in the room temperature single pot aryl-S coupling reaction of a supramolecular Co(ii)-metallohydrogel have been explored.
- Dhibar, Subhendu,Dey, Amiya,Jana, Rajkumar,Chatterjee, Arpita,Das, Gourab Kanti,Ray, Partha Pratim,Dey, Biswajit
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supporting information
p. 17388 - 17394
(2019/12/02)
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- Merging Photoredox and Organometallic Catalysts in a Metal–Organic Framework Significantly Boosts Photocatalytic Activities
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Metal–organic frameworks (MOFs) have been extensively used for single-site catalysis and light harvesting, but their application in multicomponent photocatalysis is unexplored. We report here the successful incorporation of an IrIII photoredox catalyst and a NiII cross-coupling catalyst into a stable Zr12 MOF, Zr12-Ir-Ni, to efficiently catalyze C?S bond formation between various aryl iodides and thiols. The proximity of the IrIII and NiII catalytic components to each other (ca. 0.6 nm) in Zr12-Ir-Ni greatly facilitates electron and thiol radical transfers from Ir to Ni centers to reach a turnover number of 38 500, an order of magnitude higher than that of its homogeneous counterpart. This work highlights the opportunity in merging photoredox and organometallic catalysts in MOFs to effect challenging organic transformations.
- Zhu, Yuan-Yuan,Lan, Guangxu,Fan, Yingjie,Veroneau, Samuel S.,Song, Yang,Micheroni, Daniel,Lin, Wenbin
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supporting information
p. 14090 - 14094
(2018/10/15)
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- Structure-Based Optimization of N-Substituted Oseltamivir Derivatives as Potent Anti-Influenza A Virus Agents with Significantly Improved Potency against Oseltamivir-Resistant N1-H274Y Variant
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Due to the emergence of highly pathogenic and oseltamivir-resistant influenza viruses, there is an urgent need to develop new anti-influenza agents. Herein, five subseries of oseltamivir derivatives were designed and synthesized to improve their activity toward drug-resistant viral strains by further exploiting the 150-cavity in the neuraminidases (NAs). The bioassay results showed that compound 21h exhibited antiviral activities similar to or better than those of oseltamivir carboxylate (OSC) against H5N1, H5N2, H5N6, and H5N8. Besides, 21h was 5- to 86-fold more potent than OSC toward N1, N8, and N1-H274Y mutant NAs in the inhibitory assays. Computational studies provided a plausible rationale for the high potency of 21h against group-1 and N1-H274Y NAs. In addition, 21h demonstrated acceptable oral bioavailability, low acute toxicity, potent antiviral activity in vivo, and high metabolic stability. Overall, the above excellent profiles make 21h a promising drug candidate for the treatment of influenza virus infection.
- Zhang, Jian,Murugan, Natarajan Arul,Tian, Ye,Bertagnin, Chiara,Fang, Zengjun,Kang, Dongwei,Kong, Xiujie,Jia, Haiyong,Sun, Zhuosen,Jia, Ruifang,Gao, Ping,Poongavanam, Vasanthanathan,Loregian, Arianna,Xu, Wenfang,Ma, Xiuli,Ding, Xiao,Huang, Bing,Zhan, Peng,Liu, Xinyong
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p. 9976 - 9999
(2018/12/11)
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- Method for synthesizing fenticonazole nitrate
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The invention belongs to the technical field of chemical synthesis, and discloses a method for synthesizing fenticonazole nitrate. By the aid of a phase transfer catalytic method, condensation reaction is performed at the presence of sodium hydroxide. The method particularly includes the steps: 1) synthesizing 4-mercaptophenyl-benzaldehyde; 2) synthesizing 4-mercaptophenyl benzyl alcohol; 3) synthesizing 4-mercaptophenyl-benzyl chloride; 4) synthesizing fenticonazole nitrate crude products. Used reagents are low in cost and easy to obtain, synthesis cost is greatly reduced, operation is simpleand convenient, special requirements on equipment are omitted, and the method is more suitable for scale production.
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Paragraph 0020; 0021
(2018/03/26)
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- Refining process, detection standard and application of fenticonazole nitrate
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The invention belongs to the technical field of chemical synthesis and discloses a refining process of fenticonazole nitrate. The refining process comprises the following steps: 1) synthesizing an intermediate I, namely 4-benzene sulfydryl benzaldehyde; 2) synthesizing an intermediate II, namely 4-benzene sulfydryl phenylcarbinol; 3) synthesizing an intermediate III, namely 4-benzene sulfydryl benzyl chloride; 4) synthesizing a crude product of fenticonazole nitrate; and 5) refining fenticonazole nitrate. The invention further discloses a detection method of an intermediate of the fenticonazole nitrate and an application of the fenticonazole nitrate in medicines.
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Paragraph 0014; 0022
(2018/03/01)
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- Synthesis process of fenticonazole nitrate
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The invention belongs to the technical field of chemical synthesis, and discloses a synthesis process of fenticonazole nitrate. The synthesis process comprises the following steps: 1) synthesis of intermediate I:4-phenylthio-benzaldehyde; 2) synthesis of intermediate II:4-phenylthio benzyl alcohol; 3) synthesis of intermediate III:4-phenylthio benzyl chloride; 4) synthesis of crude fenticonazole nitrate; 5) refining of the fenticonazole nitrate; 6) preparation of suppository. The synthetic process is simple and feasible and suitable for popularization and use, and has broad market applicationprospects.
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Paragraph 0036; 0040; 0041; 0042
(2019/01/14)
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- Room-Temperature Arylation of Thiols: Breakthrough with Aryl Chlorides
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The formation of aryl C?S bonds is an important chemical transformation because aryl sulfides are valuable building blocks for the synthesis of biologically and pharmaceutically active molecules and organic materials. Aryl sulfides have traditionally been synthesized through the transition-metal-catalyzed cross-coupling of aryl halides with thiols. However, the aryl halides used are usually bromides and iodides; readily available, low-cost aryl chlorides often not reactive enough. Furthermore, the deactivation of transition-metal catalysts by thiols has forced chemists to use high catalyst loadings, specially designed ligands, high temperatures, and/or strong bases, thus leading to high costs and the incompatibility of some functional groups. Herein, we describe a simple and efficient visible-light photoredox arylation of thiols with aryl halides at room temperature. More importantly, various aryl chlorides are also effective arylation reagents under the present conditions.
- Jiang, Min,Li, Haifang,Yang, Haijun,Fu, Hua
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supporting information
p. 874 - 879
(2017/01/14)
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- A oseltamivir derivative and its preparation method and application (by machine translation)
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The invention discloses a oseltamivir derivative and its preparation method and application. The derivatives of general formula I has the structure shown, the invention also discloses a method for the preparation of oseltamivir derivatives, can be for influenza virus neuraminidase inhibitors, and containing one or more of composition in the preparation of anti-influenza virus drugs in the application. (by machine translation)
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Paragraph 0163; 0164; 0165; 0166
(2017/09/02)
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- Nature of the copper-oxide-mediated C-S cross-coupling reaction: Leaching of catalytically active species from the metal oxide surface
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Copper-oxide-catalyzed cross-coupling reaction is a well-known strategy in heterogeneous catalysis. A large number of applications have been developed, and catalytic cycles have been proposed based on the involvement of the copper oxide surface. In the present work, we have demonstrated that copper(I) and copper(II) oxides served as precursors in the coupling reaction between thiols and aryl halides, while catalytically active species were formed upon unusual leaching from the oxide surface. A powerful cryo-SEM technique has been utilized to characterize the solution-state catalytic system by electron microscopy. A series of different experimental methods were used to reveal the key role of copper thiolate intermediates in the studied catalytic reaction. The present study shows an example of leaching from a metal oxide surface, where the leaching process involved the formation of a metal thiolate and the release of water. A new synthetic approach was developed, and many functionalized sulfides were synthesized with yields of up to 96%, using the copper thiolate catalyst. The study suggests that metal oxides may not act as an innocent material under reaction conditions; rather, they may represent a source of reactive species for solution-state homogeneous catalysis.
- Panova, Yulia S.,Kashin, Alexey S.,Vorobev, Maxim G.,Degtyareva, Evgeniya S.,Ananikov, Valentine P.
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p. 3637 - 3643
(2016/07/06)
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- OXACAZONE COMPOUNDS TO TREAT CLOSTRIDIUM DIFFICILE
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Compounds, compositions, and methods for treating C. difficile are provided.
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Page/Page column 86
(2016/04/04)
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- Pd-PVP-Fe (palladium-poly(N-vinylpyrrolidone)-iron) catalyzed S-arylation of thiols with aryl halides in aqueous media
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Pd-PVP-Fe (palladium-poly(N-vinylpyrrolidone)-iron) nano catalyst catalyzes selective C–S cross-coupling (S-arylation) reactions of thiols with aryl halides and avoids the formation of S–S (disulfide) homocoupling byproducts. The reactions were carried out in aqueous media using only 0.23?mol% palladium with high selectivity and short reaction time. The effects of the Pd0and Fe0moieties on the C–S cross-coupling reaction mechanism, yield, and selectivity were investigated. The yield and selectivity can be controlled by adjusting the order of adding the reactants and catalyst into the reaction medium. The X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), electron backscatter diffraction (EBSD) microscopy, energy dispersive X-ray (EDX) spectroscopy, and thermal gravimetric analysis (TGA) tools were used to characterize the catalyst. The C–S cross-coupling reaction process could be repeated up to six times without losing effectiveness. The metals leaching of Pd-PVP-Fe nanocatalyst after reusing cycles were investigated by atomic absorption spectroscopic (AAS) and EDX spectroscopy. The nature of Pd metal after the first run of the C–S cross-coupling reaction was studied by UV–vis spectrophotometry. The morphology of bimetallic nanocatalyst after the first run of the C–S cross-coupling reaction was investigated by SEM, EBSD, and EDX microscopy.
- Ghaderi-Shekhi Abadi, Parvaneh,Rafiee, Ezzat,Joshaghani, Mohammad
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p. 162 - 170
(2016/07/25)
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- Polystyrene resin-supported CuI-cryptand 22 complex: a highly efficient and reusable catalyst for the formation of aryl–sulfur bonds in aqueous media
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The air and moisture stable polystyrene resin-supported copper(I) iodide-cryptand-22 complex (PS-C22-CuI) behaves as an efficient and robust heterogeneous catalyst in the cross-coupling reaction of aryl halides and thiols in aqueous media. Moreover, the heterogeneous catalyst can be easily recovered by filtration and reused for five cycles without significant loss in activity.
- Rezaei, Nasrin,Movassagh, Barahman
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supporting information
p. 1625 - 1628
(2018/03/29)
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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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- An efficient heterogeneous Cu-grafted mesoporous organosilicas nanocatalyst for two and three component C-S coupling reactions
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Furfural-imine functionalized mesoporous organosilica material has been synthesized by postsynthesis surface functionalization of 2D-hexagnoal mesoporous SBA-15 with organosilane precursor 3-aminopropyltriethoxy-silane (APTES) followed by Schiff-base condensation with furfural. On the other hand, furfural-imine functionalized MCM-41 has been synthesized by Schiff-base condensation of furfural and 3-aminopropyltriethoxy-silane (APTES) followed by its hydrothermal co-condensation with tetraethylorthosilicate (TEOS) in the presence of a cationic surfactant CTAB. Subsequent reaction of the imine-functionalized mesoporous organosilicas with Cu(OAc)2 in absolute ethanol produced Cu(II)-grafted mesoporous nanocatalysts 1 and 2, respectively. Powder XRD, HR TEM, FE SEM, N2 sorption and EPR experimental tolls are employed to characterize these Cu-grafted furfural-imine functionalized nanocatalysts. Cu-grafted MCM-41 (1) showed very good catalytic efficiency for the coupling of aryl bromides and thiophenol under aerobic conditions to produce different thioethers. On the other hand, Cu-anchored mesoporous SBA-15 nanocatalyst (2) exhibited high catalytic activity for one-pot three component coupling of different aryl halides with thiourea and benzyl bromide in aqueous medium to produce different aryl alkyl thioethers in very good yields. Both Cu-grafted mesoporous nanocatalysts can be efficiently reused for several reaction cycles. Copyright
- Mondal, John,Salam, Noor,Bhaumik, Asim
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p. 4883 - 4895
(2013/08/23)
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- Room temperature Ullmann type C-O and C-S cross coupling of aryl halides with phenol/thiophenol catalyzed by CuO nanoparticles
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C-O/C-S cross coupling of aryl halides with phenol or thiophenol was studied under ligand-free condition at room temperature over CuO nanocatalyst. The scope of the reaction was extended to various aryl halides and substituted phenols under optimized condition. In general, efficient, selective, and reusable heterogeneous nano CuO catalytic system has been developed for room temperature C-O and C-S Ullmann type cross coupling reactions.
- Babu, S. Ganesh,Karvembu
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p. 1677 - 1680
(2013/03/28)
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- Palladium-catalyzed C-S bond formation by using N-amido imidazolium salts as ligands
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N-Amido imidazolium salt was employed as a ligand in the palladium-catalyzed cross-coupling reaction of aryl halides and thiols, and showed good activity in the formation of thioether. The best combination for the coupling with aryl bromides was N-amido imidazolium salt 2 and NaHMDS, and that for the coupling with aryl iodides was N-amido imidazolium salt 1 and KO tBu. The coupling reactions were conducted in the presence of Pd(OAc)2 (1 mol %) in DMSO at 80 C for 12 h.
- Byeun, Aleum,Baek, Kyungkyu,Han, Min Su,Lee, Sunwoo
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p. 6712 - 6715
(2013/11/19)
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- Efficient synthesis of unsymmetrical diaryl thioethers via TBAF-mediated denitrative substitution of nitroarenes with PhSTMS under mild and neutral conditions
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Tetrabutylammonium fluoride (TBAF) effectively facilitated a denitrative substitution reaction of electron-deficient nitroarenes with phenylthiotrimethylsilane (PhSTMS) under mild and base-free neutral conditions at room temperature, providing a practical and efficient synthesis of useful unsymmetrical diaryl thioethers. Nitroarenes bearing ortho- and para-positioned electron-withdrawing groups are the most reactive substrates, indicating that this reaction most possibly proceeded via the nucleophilic aromatic substitution (SNAr) mechanism.
- Yu, Xiao-Chun,Li, Bo,Yu, Bao-Hua,Xu, Qing
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p. 605 - 608
(2013/07/27)
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- Synthesis and antimicrobial evaluation of new 5-(2-hydroxyphenyl)-3-(4- (phenylthio)phenyl)-1 H -pyrazole-2(5 H)-carbothioamide analogues of 2-(4-(phenylthio)phenyl)-4 H -chromen-4-One
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A series of novel 5-(2-hydroxyphenyl)-3-(4-(phenylthio)phenyl)-1H-pyrazole- 2(5H)-carbothioamide derivatives have been synthesized via the ring opening of 2-(4-(phenylthio)phenyl)-4H-chromen-4-one with semicarbazide in ethanol and KOH under ultrasonic irradiation. The synthesized compounds were screened for antibacterial and antifungal activity against bacteria Staphylococcus aureus (MRSA E710) and Escherichia coli (25922) and fungi Candida albicans and Aspergillus fumigates, respectively. Some of the tested compounds showed significant antimicrobial activity. IR, 1H NMR, mass spectral data, and elemental analysis elucidated the structures of all the newly synthesized compounds. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Biological Assay.
- Chate, Asha V.,Joshi, Ratnadeep S.,Mandhane, Priyanka G.,Mohekar, Shweta R.,Gill, Charansingh H.
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scheme or table
p. 327 - 335
(2012/04/04)
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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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- New CRTH2 Antagonists
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The present invention relates to a compound of formula (I), to the process for preparing such compounds and to their use in the treatment of a pathological condition or disease susceptible to amelioration by CRTh2 antagonist activity.
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Page/Page column 40
(2012/12/13)
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- Copper-free sonogashira coupling reaction using a trans-spanning 1,2-Bis(2-thienylethynyl)benzene ligand
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Novel copper-free Sonogashira coupling reaction of aryl halides with terminal acetylenes proceeded in the presence of 1,2-bis(2-thienylethynyl) benzene (1) as a trans-bidentatable ligand.
- Atobe, Shingo,Sonoda, Motohiro,Suzuki, Yuki,Shinohara, Hiroyuki,Yamamoto, Takuya,Ogawa, Akiya
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supporting information; experimental part
p. 980 - 982
(2012/02/01)
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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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- One-pot synthesis of symmetrical and unsymmetrical aryl sulfides by Pd-catalyzed couplings of aryl halides and thioacetates
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Aryl sulfides were obtained from the coupling reaction of S-aryl (or S-alkyl) thioacetates and aryl bromides in the presence of palladium catalyst. This reaction method enables the one-pot synthesis of symmetrical and unsymmetrical diaryl sulfides by employing potassium thioacetate with aryl iodides and aryl bromides.
- Park, Namjin,Park, Kyungho,Jang, Mihee,Lee, Sunwoo
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experimental part
p. 4371 - 4378
(2011/07/06)
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- Efficient copper(I)-catalyzed C-S cross-coupling of thiols with aryl halides in an aqueous two-phase system
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A mild and convenient C-S bond formation reaction catalyzed by CuI/L-proline in an aqueous two-phase system was achieved, providing a simple method for the synthesis of aryl sulfides in good yields.
- Zhang, Xin-Yan,Zhang, Xiao-Yan,Guo, Sheng-Rong
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experimental part
p. 23 - 35
(2011/12/05)
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- DIHYDROOROTATE DEHYDROGENASE INHIBITORS
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The invention relates to compounds of formula (I) wherein R1, R2, X1, X2, Y, Ra, Rb, Q have the meanings given in claim 1. The compounds are useful e.g. in the treatment of autoimmune disorders, such as multiple sclerosis and also in the treatment of cancer disorders.
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Page/Page column 108
(2010/11/03)
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- Non-basic ligands for aminergic GPCRs: The discovery and development diaryl sulfones as selective, orally bioavailable 5-HT2A receptor antagonists for the treatment of sleep disorders
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Scaffold hopping from a non-basic series of 5-HT2A receptor antagonists developed in-house that possessed reduced activity in vivo enabled the discovery of a novel series of diaryl sulfones that gave excellent occupancy on oral dosing. Not only does this work further demonstrate that oral bioavailability of a given series can be enhanced by improving physicochemical parameters such as log P, but it corroborates the growing evidence that a protonated amine is not essential for affinity at aminergic GPCRs.
- Ladduwahetty, Tammy,Gilligan, Myra,Humphries, Alexander,Merchant, Kevin J.,Fish, Rebecca,McAlister, George,Ivarsson, Magnus,Dominguez, Maria,O'Connor, Desmond,MacLeod, Angus M.
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scheme or table
p. 3708 - 3712
(2010/09/18)
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- Facile preparation of aryl sulfides using palladium catalysis under mild conditions
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A convenient method for C-S cross-coupling of aryl bromides with various thiols has been developed that involves the use of a 1,1′- bis(diphenylphosphino)ferrocene (DPPF)-ligated palladium complex with N,N-diisopropylethylamine (DIPEA) as the base. This coupling is tolerant of a wide range of functional groups, including hydroxy, amino, cyano, nitro, formyl, and carboxyl groups. Georg Thieme Verlag Stuttgart - New York.
- Okauchi, Tatsuo,Kuramoto, Kouji,Kitamura, Mitsuru
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supporting information; experimental part
p. 2891 - 2894
(2011/02/28)
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- Synthesis and serotonin transporter activity of sulphur-substituted α-alkyl phenethylamines as a new class of anticancer agents
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The discovery that some serotonin reuptake transporter (SERT) ligands have the potential to act as pro-apoptotic agents in the treatment of cancer adds greatly to their diverse pharmacological application. 4-Methylthioamphetamine (MTA) is a selective ligand for SERT over other monoamine transporters. In this study, a novel library of structurally diverse 4-MTA analogues were synthesised with or without N-alkyl and/or C-α methyl or ethyl groups so that their potential SERT-dependent antiproliferative activity could be assessed. Many of the compounds displayed SERT-binding activity as well as cytotoxic activity. While there was no direct correlation between these two effects, a number of derivatives displayed anti-tumour effects in lymphoma, leukaemia and breast cancer cell lines, showing further potential to be developed as possible chemotherapeutic agents.
- Cloonan, Suzanne M.,Keating, John J.,Butler, Stephen G.,Knox, Andrew J.S.,Jorgensen, Anne M.,Peters, Guenther H.,Rai, Dilip,Corrigan, Desmond,Lloyd, David G.,Williams, D. Clive,Meegan, Mary J.
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scheme or table
p. 4862 - 4888
(2010/01/16)
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- A highly efficient and widely functional-group-tolerant catalyst system for copper(I)-catalyzed S-arylation of thiols with aryl halides
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A mild, general, and efficient copper-catalyzed system for C-S bond formation with high chemoselectivity and wide functional group tolerance is developed. With CuBr as catalyst and 1,2,3,4-tetrahydro-8-hydroxy-quinoline as ligand, the S-arylation of thiols with aryl halides performed well, the activated aryl iodides could take place even at room temperature, and the activated aryl bromides and chlorides give the corresponding products with good to excellent yields as well.
- Feng, Yang,Wang, Huifeng,Sun, Fangfang,Li, Yaming,Fu, Xinmei,Jin, Kun
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supporting information; experimental part
p. 9737 - 9741
(2010/02/27)
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- TETRACYCLIC INHIBITORS OF FATTY ACID AMIDE HYDROLASE
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Certain tetracyclic compounds are described, which may be used in pharmaceutical compositions and methods for treating disease states, disorders, and conditions mediated by fatty acid amide hydrolase (FAAH) activity. Thus, the compounds may be administered to treat, e.g., anxiety, pain, inflammation, sleep disorders, eating disorders, or movement disorders (such as multiple sclerosis).
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Page/Page column 36
(2009/01/20)
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- Convenient synthesis of unsymmetrical organochalcogenides using organoboronic acids with dichalcogenides via cleavage of the S-S, Se-Se, or Te-Te bond by a copper catalyst
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(Chemical Equation Presented) This article describes the methodology for a copper-catalyzed preparation of numerous monochalcogenides from dichalcogenides with organoboronic acids. Unsymmetrical diorgano-monosulfides, selenides, and tellurides can be synthesized by the coupling of dichalcogenides with aryl- or alkylboronic acids using a copper catalyst in air. The present reaction can take advantage of both organochalcogenide groups on dichalcogenide.
- Taniguchi, Nobukazu
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p. 1241 - 1245
(2007/10/03)
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- Structure-activity relationships of α-ketooxazole inhibitors of fatty acid amide hydrolase
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A systematic study of the structure-activity relationships of 2b (OL-135), a potent inhibitor of fatty acid amide hydrolase (FAAH), is detailed targeting the C2 acyl side chain. A series of aryl replacements or substituents for the terminal phenyl group provided effective inhibitors (e.g., 5c, aryl = 1-napthyl, K, - 2.6 nM), with 5hh (aryl -3-ClPh, Ki = 900 pM) being 5-fold more potent than 2b. Conformationally restricted C2 side chains were examined, and many provided exceptionally potent inhibitors, of which 11j (ethylbiphenyl side chain) was established to be a 750 pM inhibitor. A systematic series of heteroatoms (O, NMe, S), electron-withdrawing groups (SO, SO2), and amides positioned within and hydroxyl substitutions on the linking side chain were investigated, which typically led to a loss in potency. The most tolerant positions provided effective inhibitors (12p, 6-position S, Ki = 3 nM, or 13d, 2-position OH, Ki = 8 nM) comparable in potency to 2b. Proteome-wide screening of selected inhibitors from the systematic series of >100 candidates prepared revealed that they are selective for FAAH over all other mammalian serine proteases.
- Hardouin, Christophe,Kelso, Michael J.,Romero, F. Anthony,Rayl, Thomas J.,Leung, Donmienne,Hwang, Inkyu,Cravatt, Benjamin F.,Boger, Dale L.
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p. 3359 - 3368
(2008/02/13)
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- Aryl- or alkylation of diaryl disulfides using organoboronic acids and a copper catalyst
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A variety of unsymmetrical monosulfides can be synthesized in good yields by copper-catalyzed coupling of disulfides with organoboronic acids in air. Furthermore, this method can result in the successful aryl- or alkylation of both organosulfide groups in a disulfide. Georg Thieme Verlag Stuttgart.
- Taniguchi, Nobukazu
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p. 1351 - 1354
(2007/10/03)
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- Cobalt-catalyzed aryl-sulfur bond formation
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A new cobalt-catalyzed coupling of aryl halides with thiophenols and alkanethiols is reported. A variety of aryl sulfides can be prepared in excellent yields under mild reaction conditions using 1-2 mol % of Col2(dppe) and Zn. This new cobalt-catalyzed coupling represents an interesting addition to previously known methods to synthesize thioethers.
- Wong, Ying-Chieh,Jayanth, Thiruvellore Thatai,Cheng, Chien-Hong
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p. 5613 - 5616
(2007/10/03)
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- Alkyl- and arylthiolation of aryl halides catalyzed by fluorinated bis-imino-nickel NNN pincer complexes [NiCl2{C5H 3N-2,6-(CHNArf)2}]
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The synthesis of bis-imino nickel(II) NNN pincer complexes of the type [NiCl2{C5H3N-2,6-(CHNArf) 2}]; Arf= C6H3-2,3-F2 (1), C6H3-2,5-F2 (2), C6H 3-3,4-F2 (3), C6H3-3,5-F2 (4), C6H2-2,3,4-F3 (5), C6H 2-2,3,6-F3 (6), C6H2-2,4,5-F 3 (7), C6H2-2,4,6-F3 (8), has been achieved and their reactivity in alkyl- and arylthiolation reactions of halobenzenes examined. The use of fluorinated substituents Arf on the imines has allowed the tuning of the electronics in these complexes and the influence of these substituents and those of the disulfides in the thiolation reactions have been analyzed.
- Baldovino-Pantaleon, Oscar,Hernandez-Ortega, Simon,Morales-Morales, David
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p. 236 - 242
(2007/10/03)
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- Oxime ester photoinitiators
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Compounds of the formulae I, II, III, IV and V wherein R1 i.a. is C4-C9cycloalkanoyl, C1-C12alkanoyl, C4-C6alkenoyl, or benzoyl; R2 is for example phenyl, C1-C20alkyl, C3-C8cycloalkyl, C2-C20alkanoyl, or benzoyl; Ar1 is R4S-phenyl or NR5R6-phenyl, each of which optionally is substituted; or Ar1 i.a. is optionally substituted; or Ar1 is naphthyl or anthracyl each of which is unsubstituted or substituted; or Ar1 is benzoyl, naphthalenecarbonyl, phenanthrenecarbonyl, anthracenecarbonyl or pyrenecarbonyl, each of which is unsubstituted or substituted, or Ar1 is 3,4,5-trimethoxyphenyl, phenoxyphenyl or biphenyl; Ar2 i.a. is optionally substituted, or naphthyl or anthracyl, each of which is unsubstituted or substituted, x is 2 or 3; M1 when x is 2, for example is phenylene, naphthalene, anthracylene, each of which optionally is substituted; M1, when x is 3, is a trivalent radical; M2 for example is M3 is for example C1-C12alkylene, cyclohexylene, or phenylene; n is 1-20; R3 is for example hydrogen or C1-C12alkyl; R3′ i.a. is C1-C12alkyl; substituted or —O-interrupted C2-C6alkyl; R4 is for example hydrogen, or C1-C12alkyl; and R5 and R6 independently of each other i.a. are hydrogen, C1-C12alkyl, or phenyl; are suitable as photoinitiators in particular in resist applications.
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Page/Page column 56
(2010/02/14)
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- Diphenyl sulfoxides as selective antagonists of the muscarinic M2 receptor
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Structure-activity studies on [4-(phenylsulfonyl)phenyl]methylpiperazine led to the discovery of 4-cyclohexyl-α-[4-[[4-methoxyphenyl](S)-sulfinyl]phenyl]-1-piperazineacetoni trile, 1, an M2 selective muscarinic antagonist. Affinity at the cloned human M2 receptor was 2.7 nM; the M1/M2 selectivity is 40-fold. (C) 2000 Elsevier Science Ltd.
- Kozlowski, Joseph A,Lowe, Derek B.,Guzik, Henry S.,Zhou, Guowei,Ruperto, Vilma B.,Duffy, Ruth A.,McQuade, Robert,Crosby Jr., Gordon,Taylor, Lisa A.,Billard, William,Binch III, Herbert,Lachowicz, Jean E.
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p. 2255 - 2257
(2007/10/03)
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- Inhibitors of acyl-CoA:cholesterol O-acetyltransferase (ACAT). Part 1: Identification and structure-activity relationships of a novel series of substituted N-alkyl-N-biphenylmethyl-N'-arylureas
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A series of N-alkyl-N-biphenylylmethyl-N'-arylurea and related derivatives represented by 1 have been prepared and evaluated for their ability to inhibit acyl-CoA:cholesterol O-acyltransferase in vitro and to lower plasma cholesterol levels in cholesterol-fed rats in vivo. Linking of two phenyl groups via oxygen and introduction of fluorine at appropriate positions on the biphenyl moiety improved in vitro and in vivo activity. From this series of analogs, compound 40 (FR179254), which had potent in vitro potency (rabbit intestinal microsomes IC50 = 25 nM), showed excellent plasma cholesterol-lowering activity when administered via the diet (ED50 = 0.045 mg/kg). However, the hypocholesterolemic effect of this compound was moderate when dosed by oral gavage in PEG400 as a vehicle (ED50 = 5.3 mg/kg). Modification of the N'-aryl moiety led to the identification of compound 50 (FR182980) which was efficacious in both dosing models (ED50 = 0.034 mg/kg and 0.11 mg/kg, respectively).
- Tanaka, Akira,Terasawa, Takeshi,Hagihara, Hiroyuki,Sakuma, Yuri,Ishibe, Noriko,Sawada, Masae,Takasugi, Hisashi,Tanaka, Hirokazu
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-
- (Aryloxy)aryl semicarbazones and related compounds: A novel class of anticonvulsant agents possessing high activity in the maximal electroshock screen
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A number of (aryloxy)aryl semicarbazones and related compounds were synthesized and evaluated far anticonvulsant activities. After intraperitoneal injection to mice, the semicarbazones were examined in the maximal electroshock (MES), subcutaneous pentylenetetrazole (scPTZ), and neurotoxicity (NT) screens. The results indicated that greater protection was obtained in the MES test than the scPTZ screen. Quantitation of approximately one-third of the compounds revealed an average protection index (PI, i.e. TD50/ED50) of approximately 9. After oral administration to rats, a number of compounds displayed significant potencies in the MES screen (ED50 of 1-5 mg/kg) accompanied by very high protection indices. In fact over half the compounds had PI figures of greater than 100, and two were in excess of 300. The compounds were essentially inactive in the scPTZ and NT screens after oral administration to rats. Various compounds displayed greater potencies and PI figures in the mouse intraperitoneal and rat oral screens than three reference clinically used drugs. The data generated supported a binding site hypothesis. Quantitative structure-activity relationships indicated a number of physicochemical parameters which contributed to activity in the MES screen. X-ray crystallography of five compounds suggested the importance of certain interatomic distances and bond angles for activity in the mouse and rat MES screens.
- Dimmock, Jonathan R.,Puthucode, Ramanan N.,Smith, Jennifer M.,Hetherington, Mark,Quail, J. Wilson,Pugazhenthi, Uma,Lechler, Terry,Stables, James P.
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p. 3984 - 3997
(2007/10/03)
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