- Efficient Pyrazolo[5,4-f]quinoxaline Functionalized Os(II) Based Emitter with an Electroluminescence Peak Maximum at 811 nm
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Upon fusing the pyrazinyl pyrazole entity in giving pyrazolo[3,4-f]quinoxaline chelate, the corresponding Os(II) based NIR emitter exhibited “invisible” and efficient electroluminescence with a peak maximum at 811 nm. A maximum external quantum efficiency
- Zhu, Ze-Lin,Wang, Sheng-Fu,Fu, Li-Wen,Tan, Ji-Hua,Cao, Chen,Yuan, Yi,Yiu, Shek-Man,Zhang, Ye-Xin,Chi, Yun,Lee, Chun-Sing
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- Enantiomerically Pure Quinoline-Based κ-Opioid Receptor Agonists: Chemoenzymatic Synthesis and Pharmacological Evaluation
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Racemic K-opioid receptor (KOR) agonist 2-(3,4-dichlorophenyl)-1-[(4aRS,8SR,8aSR)-8-(pyrrolidin-1-yl)-3,4,4a,5,6,7,8,8a-octahydroquinolin-1(2H)-yl]ethan-1-one ((±)-4) was prepared in a diastereoselective synthesis. The first key step of the synthesis was the diastereoselective hydrogenation of the silyl ether of 1,2,3,4-tetrahydroquinoin-8-ol ((±)-9) to afford cis,cis-configured perhydroquinoline derivative (±)-10. Removal of the TBDMS protecting group led to a β-aminoalcohol that reacted with SO2Cl2 to form an oxathiazolidine. Nucleophilic substitution with pyrrolidine resulted in the desired cis,trans-configured perhydroquinoline upon inversion of the configuration. In order to obtain enantiomerically pure KOR agonists 4 (99.8 % ee) and ent-4 (99.0 % ee), 1,2,3,4-tetrahydroquinolin-8-ols (R)-8 (99.1 % ee) and (S)-8 (98.4 % ee) were resolved by an enantioselective acetylation catalyzed by Amano lipase PS-IM. The absolute configuration was determined by CD spectroscopy. The 4aR,8S,8aS-configured enantiomer 4 showed sub-nanomolar KOR affinity (Ki=0.81 nM), which is more than 200 times higher than the KOR affinity of its enantiomer ent-4. In the cAMP assay and the Tango β-arrestin-2 recruitment assay, 4 behaved as a KOR agonist. Upon incubation of human macrophages, human dendritic cells, and mouse myeloid immune cells with 4, the number of cells expressing co-stimulatory receptor CD86 and proinflammatory cytokines interleukin 6 and tumor necrosis factor α was significantly reduced; this indicates the strong anti-inflammatory activity of 4. The anti-inflammatory effects correlated well with the KOR affinity: (4aR,8S,8aS)-4 was slightly more potent than the racemic mixture (±)-4, and the distomer ent-4 was almost inactive.
- Martin, Benedikt,Schepmann, Dirk,Bernal, Freddy A.,Schmidt, Thomas J.,Che, Tao,Loser, Karin,Wünsch, Bernhard
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supporting information
p. 1408 - 1420
(2020/07/06)
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- Asymmetric Hydroboration of Heteroaryl Ketones by Aluminum Catalysis
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A series of methyl aluminum complexes bearing chiral biphenol-type ligands were found to be highly active catalysts in the asymmetric reduction of heterocyclic ketones (S/C = 100-500, ee up to 99%). The protocol is suitable for a wide range of substrates and has a high tolerance to functional groups. The formed 2-heterocyclic-alcohols are valuable building blocks in drug discovery or can be used as ligands in asymmetric catalysis. Isolation and comprehensive characterization of the reaction intermediates support a catalysis cycle proposed by DFT calculations.
- Lebedev, Yury,Polishchuk, Iuliia,Maity, Bholanath,Dinis Veloso Guerreiro, Miguel,Cavallo, Luigi,Rueping, Magnus
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supporting information
p. 19415 - 19423
(2019/12/24)
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- Monofunctional PtII Complexes Based on 8-Aminoquinoline: Synthesis and Pharmacological Characterization
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Among the heterocyclic compounds, 8-aminoquinoline and its derivatives have become important candidates for the preparation of new antiproliferative metallo-drugs. Here, we reported the synthesis and cytotoxicity evaluation of a series of platinum complexes using 8-aminoquinoline and its chiral 5,6,7,8-tetrahydro-derivatives as chelating ligands. In the proposed complexes, a differently and opportunely alkylated imidazole was used to prepare the corresponding monofunctional platinum complexes. The preliminary cytotoxicity evaluation was carried out on the highly aggressive MDA-MB-231, invasive and poorly differentiated triple-negative breast cancer (TNBC) cell line, furnishing a significant IC50 10.9 ± 1.3 μM for Pt-IV. This series of complexes revealed an induction of p53, interfering with the progression of the G0/G1 phase of the cell cycle.
- Facchetti, Giorgio,Ferri, Nicola,Lupo, Maria Giovanna,Giorgio, Lucchini,Rimoldi, Isabella
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p. 3389 - 3395
(2019/08/01)
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- Thermo-enhanced ring-opening polymerization of ?-caprolactone: The synthesis, characterization, and catalytic behavior of aluminum hydroquinolin-8-olates
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A series of highly sensitive aluminum hydroquinolin-8-olates (C1-C8) was synthesized and characterized by 1H/13C NMR spectroscopy. The molecular structures of compounds C1, C3, C4, and C5 were confirmed by single crystal X-ray crystallography and demonstrated the binuclear form. In the presence of BnOH, all the aluminum complexes exhibited moderate to high activities towards the ring-opening polymerization of ?-CL at high temperatures, but quite low activities at ambient temperature. Microstructure analysis of the resultant polycaprolactones showed that the polymers were linear in nature with a BnO- end group. In addition, the mechanism was investigated by monitoring the 1H NMR and 27Al NMR of C1 and these results suggested that the complexes existed as dimeric species at low temperature and partly converted into active mononuclear species at higher temperatures, which was easily coordinated by BnOH to afford the active species for the ring-opening polymerization of ?-caprolactone.
- Zhang, Qiurui,Zhang, Wenjuan,Rajendran, Natesan Mannangatti,Liang, Tongling,Sun, Wen-Hua
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p. 7833 - 7843
(2017/07/11)
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- NaBH4-TMEDA and a palladium catalyst as efficient regio- and chemoselective system for the hydrodehalogenation of halogenated heterocycles
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The pair NaBH4-TMEDA as hydride source and a palladium catalyst in THF prove to be an efficient system for the hydrodehalogenation of halogenated heterocycles with one or more heteroatoms. In general, Pd(OAc) 2-PPh3 rapidly hydrodehalogenates reactive halo-heterocycles such as bromo-pyridines, -quinolines, -thiophenes, -indoles, -imidazoles, etc., at room temperature in very good yields, whereas in most cases PdCl2(dppf) reduces less reactive halides such as chloro-pyridines, -quinolines, -pyrimidines and bromo-indoles, -benzofurans, etc. Moreover, PdCl2(tbpf) shows to be even more active removing the 2- and 5-chlorine from both thiophene and thiazole rings. The reaction conditions tolerate various functional groups, allowing highly chemoselective reactions in the presence of halide, ester, alkyne, alkene and nitrile substituents. Moreover, with a proper selection of the catalyst it is also possible to obtain a good control in the regioselective hydrodehalogenation of a variety of polyhalogenated substrates.
- Chelucci, Giorgio,Figus, Susanna
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p. 191 - 209
(2014/07/21)
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- Hydrodehalogenation of halogenated pyridines and quinolines by sodium borohydride/N,N,N′,N′-tetramethylethylenediamine under palladium catalysis
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A protocol for the hydrodehalogenation of halogenated pyridines and quinolines by the sodium borohydride/N,N,N′,N′-tetramethylethylenediamine (NaBH4-TMEDA) system under palladium catalysts is reported. Catalytic amounts of [1,1′-bis(diphenylphosphino)ferrocene] dichloropalladium(II) in combination with NaBH4-TMEDA rapidly hydrodehalogenate chloro(bromo)-pyridines and -quinolines at room temperature in quantitative yields. Chemoselective reduction of 4,7-dichloroquinoline affords 7-chloroquinoline as the sole product in almost quantitative yield. Moreover, palladium(II) acetate-triphenylphosphine and NaBH4-TMEDA are able to reduce efficiently reactive bromo-pyridines and -quinolines.
- Chelucci, Giorgio
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experimental part
p. 1562 - 1565
(2010/06/14)
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- Kinetic resolution of diols and pyridyl alcohols by cu(II)(borabox)- catalyzed acylation
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Boron-bridged bisoxazoline (borabox) ligands have been used in the copper(II)-catalyzed benzoylation of pyridyl alcohols and 1,2-diols. Efficient kinetic resolution of 1,2-diols was achieved using both borabox and bisoxazoline (box) ligands. Borabox ligands induced high selectivities in the benzoylation of suitable pyridyl alcohols, where they outperformed bisoxazolines. In addition, highly enantioselective Cu(II)(borabox)-catalyzed benzoylation has been used for the synthesis of both enantiomers of a pyridyl alcohol.
- Mazet, Clement,Roseblade, Stephen,Koehler, Valentin,Pfaltz, Andreas
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p. 1879 - 1882
(2007/10/03)
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- Iridium catalysts with bicyclic pyridine-phosphinite ligands: Asymmetric hydrogenation of olefins and furan derivatives
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(Chemical Equation Presented) Superior bicyclics: Iridium catalysts as 1 derived from pyridine-phosphinite ligands considerably extend the scope of asymmetric hydrogenation. In addition to various unfunctionalized and functionalized olefins, furans, and benzofurans, for which no catalysts were known before, are also hydrogenated with high enantioselectivity (see scheme).
- Kaiser, Stefan,Smidt, Sebastian P.,Pfaltz, Andreas
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p. 5194 - 5197
(2007/10/03)
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- Chemokine receptor binding heterocyclic compounds
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This invention relates to a novel class of heterocyclic compounds that bind chemokine receptors, inhibiting the binding of their natural ligands thereby. These compounds result in protective effects against infection by HIV through binding to chemokine receptors, including CXCR4 and CCR5, thus inhibiting the subsequent binding by these chemokines. The present invention provides a compound of Formula I wherein, W is a nitrogen atom and Y is absent or, W is a carbon atom and Y═H; R1to R7may be the same or different and are independently selected from hydrogen or straight, branched or cyclic C1-6alkyl; R8is a substituted heterocyclic group or a substituted aromatic group Ar is an aromatic or heteroaromatic ring each optionally substituted at single or multiple, non-linking positions with electron-donating or withdrawing groups; n and n′ are independently, 0-2; X is a group of the formula: Wherein, Ring A is an optionally substituted, saturated or unsaturated 5 or 6-membered ring, and P is an optionally substituted carbon atom, an optionally substituted nitrogen atom, sulfur or oxygen atom. Ring B is an optionally substituted 5 to 7-membered ring. Ring A and Ring B in the above formula can be connected to the group W from any position via the group V, wherein V is a chemical bond, a (CH2)n″group (where n″=0-2) or a C═O group. Z is, (1) a hydrogen atom, (2) an optionally substituted C1-6alkyl group, (3) a C0-6alkyl group substituted with an optionally substituted aromatic or heterocyclic group, (4) an optionally substituted C0-6alkylamino or C3-7cycloalkylamino group, (5) an optionally substituted carbonyl group or sulfonyl. These compounds further include any pharmaceutically acceptable acid addition salts and metal complexes thereof and any stereoisomeric forms and mixtures of stereoisomeric forms thereof.
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Page column 15
(2008/06/13)
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- NITROGENOUS COMPOUNDS AND ANTIVIRAL DRUGS CONTAINING THE SAME
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The present invention provides novel compounds having antiviral activities and antiviral drugs containing the compounds as the active ingredient. The compounds are shown by the following general formula (1), wherein typically A1 and A2 are each guanidine or a group of the general fomula (ia) ; A3 is a mono- or poly-cyclic heteroaromatic ring contining 1 or 2 heteroatoms ; B1 is a single bond or alkylene group; R1 is hydrogen or alkyl group; W is an alkylene having 2-3 carbons, a cycloalkylene having 5-10 carbons, aromatic ring having 6-10 carbons, or a heteroaromatic ring having 5-10 carbons; y is C(=O)-; x is -C(=O)-NH-; n1 is an integer of 1-2; n2 is an integer of 2-3; D is a substituent selected from among various groups.
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- Tetrahydrobenzindole derivatives
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Compounds containing tetrahydrobenzindole which bind to serotonin receptor and are useful in treatment or prevention of disease induced by abnormality of central peripheral serotonin controlling functions.
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- Synthesis of enantiomerically pure 8-substituted 5,6,7,8-tetrahydro quinolines
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Enantiomerically pure (S)-5,6,7,8-tetrahydroquinolin-8-ol [(S)-1] and (R)-8-acetoxy-5,6,7,8-tetrahydroquinoline [(R)-2] have been prepared by the lipase-catalyzed kinetic acetylation of racemic 5,6,7,8-tetrahydroquinolin-8-ol [(±)-1] in excellent chemical
- Uenishi, Junichi,Hamada, Masahiro
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p. 625 - 630
(2007/10/03)
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- Heterocyclic-fused lactams promote release of growth hormone
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There are disclosed certain novel compounds identified as heterocyclic-fused lactams which promote the release of growth hormone in humans and animals. This property can be utilized to promote the growth of food animals to render the production of edible
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- The Boekelheide reaction: Trifluoroacetic anhydride as a convenient acylating agent
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2-Alkyl substituted pyridine N-oxides react with trifluoroacetic anhydride at room temperature to give selectively and with high yields the corresponding 2-(α-hydroxyalkyl)-pyridines.
- Fontenas,Bejan,Haddou,Balavoine
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p. 629 - 633
(2007/10/02)
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- Selectivity in the Hydrogenation of 6- and 8-Substituted-quinolines
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Quinoline (1) and the 6- or 8-substituted-quinolines (2)-(14) (R = Me, Pri, But, Ph, OMe, OH, CF3, or F) were hydrogenated catalytically on platinum under either weakly basic (solvent MeOH) or strongly acidic (solvent CF3CO2H) conditions.In methanol the only product was the corresponding 1,2,3,4-tetrahydro-compound.In trifluoroacetic acid, compounds hydrogenated in the benzene ring were isolated as major products; both electron-withdrawing and electron-donating substituents at C-6 or C-8 cause (sometimes drastic) reduction in yield.The products were characterized by their 1H and 13C n.m.r. spectra.
- Hoenel, Michael,Vierhapper, Friedrich W.
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p. 1933 - 1939
(2007/10/02)
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