- Probing the salt-metathesis route to bis(aryl)calcium compounds: Structure of an arylcalcate complex
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1,3-Diisopropoxybenzene can be selectively metalated by nBuLi or by the superbase mixtures nBuLi/NaOC(Me)2Et or nBuLi/KOC(Me)2Et to give 2,6-diisopropoxyphenyllithium (71 %), 2,6-diisopropoxyphenylsodium (61 %), or 2,6-diisopropoxyph
- Harder, Sjoerd,Ruspic, Christian
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Read Online
- HISTONE DEMETHYLASE 5 INHIBITORS AND USES THEREOF
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Provided herein are compounds of Formulae (I) and (II), and pharmaceutically acceptable salts, solvates, hydrates, polymorphs, co-crystals, tautomers, stereoisomers, isotopically labeled derivatives, prodrugs, and compositions thereof. Also provided are methods and kits involving the compounds or compositions disclosed herein for treating and/or preventing proliferative diseases, cancers, carcinoma lung cancer, breast cancer, liver cancer, pancreatic cancer, gastric cancer, ovarian cancer, colon cancer, colorectal cancer, leukemia, sarcoma and/or cardiovascular diseases in a subject in need thereof. In certain embodiments, the sarcoma is Ewing's sarcoma. Provided are methods of inhibiting a histone demethylase in a subject and/or in a cell, tissue, or biological sample. In certain embodiments, the histone demethylase is a KDM. In certain embodiments, the KDM is KDM5. In certain embodiments, the biological sample is a cell. In certain embodiments, the biological sample is a tissue.
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Paragraph 00355
(2020/03/02)
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- Barbier–Negishi Coupling of Secondary Alkyl Bromides with Aryl and Alkenyl Triflates and Nonaflates
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A mild and practical Barbier–Negishi coupling of secondary alkyl bromides with aryl and alkenyl triflates and nonaflates has been developed. This challenging reaction was enabled by the use of a very bulky imidazole-based phosphine ligand, which resulted in good yields as well as good chemo- and site selectivities for a broad range of substrates at room temperature and under non-aqueous conditions. This reaction was extended to primary alkyl bromides by using an analogous pyrazole-based ligand.
- Zhang, Ke-Feng,Christoffel, Fadri,Baudoin, Olivier
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supporting information
p. 1982 - 1986
(2018/02/06)
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- Imine compound, novel catalyst for olefin polymerization, and method for producing olefin polymer
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Disclosed is a compound represented by the following general formula (1). In the formula, X represents a nitrogen atom, Y represents a nitrogen atom or a phosphorous atom, R5 and R6 independently represent C1-30 hydrocarbon groups which may contain a hydrogen atom or a hetero atom, and at least one of R5 and R6 is a hydrocarbon group having two or more hetero atom-containing groups, and R1 to R4 independently represent a hydrogen atom, a halogen atom or a C1-20 hydrocarbon group which may contain a hetero atom. A plurality of groups selected from the R1 to the R4 may be connected with one another to form aliphatic rings, aromatic rings or heterocycles containing hetero atoms selected from oxygen, nitrogen and sulfur. At the time, the number of ring members is 5-8, and the ring may have a substituent.
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Paragraph 0198; 0200
(2016/10/09)
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- Remarkable Ability of the Benzylidene Ligand To Control Initiation of Hoveyda–Grubbs Metathesis Catalysts
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The structure of the chelating benzylidene ligand offers the unique ability to control the initiation of Hoveyda–Grubbs metathesis catalysts. Apart from steric and electronic effects acting on the step involving opening of the chelate ring, changes related to the following ligand-exchange process may also play a critical role. Our mechanistic model reveals that ligands substituted at the 6-position of the benzylidene ring enter the metathesis cycle in a nonoptimal chelating conformation, and thus the coordination number of the ruthenium center transiently increases to six (associative mechanism). In effect, the synthesis and initiation of the catalysts becomes difficult, and the energy barrier of the ligand-exchange process is controlled by the structure of the coordinating OR group. Moreover, we explain how isomeric naphthalene ligands affect the catalytic performance by an indivisible combination of steric and π-electron delocalization effects.
- Basak, Tymoteusz,Grudzień, Krzysztof,Barbasiewicz, Micha?
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supporting information
p. 3513 - 3523
(2016/07/29)
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- Α-olefin complexes and using the same, and (meth) acrylic acid ester copolymer
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PROBLEM TO BE SOLVED: To provide a catalyst component for producing polymer having high molecular weight, and a method of producing α-olefin (meth)acrylic ester copolymer using the same.SOLUTION: There are provided the metal complex represented by general
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Paragraph 0085; 0086; 0087
(2017/01/05)
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- Synthesis of 2,6-disubstituted benzylamine derivatives as reversible selective inhibitors of copper amine oxidases
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In order to obtain substrate-like inhibitors of copper amine oxidases (CAOs), a class of enzymes involved in important cellular processes as well as in crosslinking of elastin and collagen and removal of biogenic primary amines, we synthesized a set of benzylamine derivatives properly substituted at positions 2 and 6 and studied their biological activity towards some members of CAOs. With benzylamines 6, 7, 8 containing linear alkoxy groups we obtained reversible inhibitors of benzylamine oxidase (BAO), very active and selective toward diamine oxidase (DAO), lysyl oxidase (LO) and monoamine oxidase B (MAO B) characterized by a certain toxicity consequent to the crossing of the brain barrier. Poorly toxic, up to very active, reversible inhibitors of BAO, very selective toward DAO, LO and MAO B, were obtained with benzylamines 10, 11, 12 containing hydrophilic ω-hydroxyalkoxy groups. With benzylamines 13, 14, 15, containing linear alkyl groups endowed with steric, but not conjugative effects for the absence of properly positioned oxygen atoms, we synthesized moderately active inhibitors of BAO reversible and selective toward DAO, LO and MAO B. The cross examination of the entire biological data brought us to the conclusion that the bioactive synthesized compounds most likely exert their physiological role of reversible inhibitors in consequence of the formation of a plurality of hydrogen bonds or hydrophobic non-covalent interactions with proper sites in the protein. Accordingly, the reported inhibitors may be considered as a set of research tools for general biological studies and the formation of enzyme complexes useful for X-ray structure determinations aimed at the design of more sophisticated inhibitors to always better modulate the protein activity without important side effects.
- Lucchesini, Francesco,Pocci, Marco,Alfei, Silvana,Bertini, Vincenzo,Buffoni, Franca
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p. 1558 - 1567
(2014/03/21)
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- The AZARYPHOS family of ligands for ambifunctional catalysis: Syntheses and use in ruthenium-catalyzed anti-markovnikov hydration of terminal alkynes
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The family of AZARYPHOS (aza-aryl-phosphane) phosphane ligands, containing a phosphine unit and sterically shielded nitrogen lone pairs in the ligand periphery, is introduced as a tool for developing ambifunctional catalysis by the metal center and nitrogen lone pairs in the ligand sphere. General synthetic strategies have been developed to synthesize over 25 examples of structurally diverse (6-aryl-2pyridyl)phosphanes (ARPYPHOS), (6alkyl-2-pyridyl)phosphanes (ALPY-PHOS), 4,6-disubsituted l,3-diazin-2ylphosphanes or l,3,5-triazin-2- ylphosphanes, quinazolinylphosphanes, quinolinylphosphanes, and others. The scalable syntheses proceed in a few steps. The incorporation of AZARYPHOS ligands (L) into complexes [RuCp(L)2(MeCN)][PF6] (Cp = cyclopentadieny1)gives catalysts for the anti-Markovnikov hydration of terminal alkynes of the highest known activities. Electronic and steric ligand effects modulate the reaction kinetics over a range of two orders of magnitude. These results highlight the importance of using structurally diverse ligand families in the process of developing cooperative ambifunctional catalysis by a metal and its ligand.
- Hintermann, Lukas,Dang, Tuan Thanh,Labonne, Aurelie.,Kribber, Thomas,Xiao, Li,Naumov, Pance
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supporting information; experimental part
p. 7167 - 7179
(2010/02/28)
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- NOVEL BENSOPHENONE DERIVATIVES OR SALTS THEREOF
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A benzophenone derivative represented by the following formula: whereinR1 represents, for example, an optionally substituted heterocyclic group, or a substituted phenyl group; Z represents, for example, an alkylene group; R2 represents, for example, a carboxyl group optionally protected with alkyl;R3 represents, for example, an optionally protected hydroxyl group; R4 represents, for example, an optionally substituted cycloalkyloxy group; and R5 represents, for example, a hydrogen atom, ???or a salt thereof has anti-arthritic activity, inhibits bone destruction caused by arthritis, and provides high safety and excellent pharmacokinetics and thus is useful as therapeutic agent for arthritis. These compounds have inhibitory effect on AP-1 activity and are useful as preventive or therapeutic agent for diseases in which excessive expression of AP-1 is involved.
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- An extremely active catalyst for the Negishi cross-coupling reaction
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A new catalyst system for the Pd-catalyzed cross-coupling of organozinc reagents with aryl halides (Negishi coupling) has been developed. This system permits efficient preparation of hindered biaryls (triand tetra-ortho- substituted), functions effectively at low levels of catalyst, and tolerates a wide range of functional groups and heterocyclic substrates. A systematic study of ligand structure was performed and was correlated with catalyst activity.
- Milne, Jacqueline E.,Buchwald, Stephen L.
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p. 13028 - 13032
(2007/10/03)
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- Kwakhurin, a unique isoflavone with rejuvenating activity from "kwao keur": Further characterization by 2D-NMR spectrometry and synthesis of triisopropylkwakhurin
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Kwakhurin (5), a characteristic isoflavone component of Pueraria mirifica which has been used in folk medicine as "kwao keur" for rejuvenating purpose, was structurally approached by 2D-NMR experiments. Furthermore, the synthesis of kwakhurin (5) was attempted starting from the methyl ketone (12). Thus, deoxybenzoin derivative (22) was prepared by Friedel-Crafts acylation after protection of the phenolic function with a triisopropyl group. Modification of the substituents, O-prenylation, prenyl 1,3-rearrangement, and O-methylation afforded kwakhurin triisopropyl ether (38).
- Iwasaki, Misako,Watanabe, Toshiko,Ishikawa, Tsutomu,Chansakaow, Sunee,Higuchi, Yoshihiro,Tahara, Satoshi
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p. 1375 - 1392
(2007/10/03)
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- Synthesis of 2,6-dialkoxylphenyllanthanoid complexes and their polymerization catalysis
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The 1:1-2:1 reaction of [2,6-(iPrO)2C6H3]Li with anhydrous SmCl3 in THF gave [2,6-(iPrO)2C6H3]3 Sm 1 exclusively, while the 3:1 reaction gave [2,6-(iPrO)2C6H3]4SmLi 2 as major product, which crystallizes in the monoclinic space group C2/c(No. 15) with a=47.52(1) A, b=11.680(9) A, c=18.862(9) A, β=112.19(3)°, V=9694(8) A3, Z=8, R=0.077 and Rw=0.074. In a similar manner, [2,6-(iPrO)2C6H3]3La was obtained by reacting with LaCl3(THF)2. The 2:1 reaction of [2,6-(iPrO)2C6H3]Li with YbCl3 gave [2,6-(iPrO)2C6H3]2YbCl, which produces [2,6-(iPrO)2C6H3] 2Yb[CH(SiMe3)2]2Li 4 by reaction with (SiMe3)2CHLi. Polymerizations of ε-caprolactone and alkyl isocyanates were examined using the resulting complexes.
- Ihara, Eiji,Adachi, Yoshifumi,Yasuda, Hajime,Hashimoto, Hiroshi,Kanehisa, Nobuko,Kai, Yasushi
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p. 147 - 157
(2007/10/03)
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- PHASE-TRANSFER NUCLEOPHILIC AROMATIC SUBSTITUTION OF Cr(CO)3-COMPLEXED DICHLOROBENZENES WITH ALCOHOLS
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Cr(CO)-complexed ortho- and para-dichlorobenzenes react with primary and secondary alcohols, in the presence of KOH, under phase-transfer conditions to give monosubstitution products only.The meta isomer affords disubstitution products also.The same reaction, carried out in DMSO with alcohols in excess, leads in all cases to dialkoxy derivatives.Factors potentially influencing the reactivity of Cr(CO)3-complexed ortho-, meta-, and para-dichlorobenzenes are discussed.
- Alemagna, Andreina,Baldoli, Clara,Del Buttero, Paola,Licandro, Emanuela,Maiorana, Stefano
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p. 555 - 560
(2007/10/02)
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