- Utilization of renewable formic acid from lignocellulosic biomass for the selective hydrogenation and/or N-methylation
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Lignocellulosic biomass is one of the most abundant renewable sources in nature. Herein, we have developed the utilization of renewable formic acid from lignocellulosic biomass as a hydrogen source and a carbon source for the selective hydrogenation and further N-methylation of various quinolines and the derivatives, various indoles under mild conditions in high efficiencies. N-methylation of various anilines is also developed. Mechanistic studies indicate that the hydrogenation occurs via a transfer hydrogenation pathway.
- Zhou, Chao-Zheng,Zhao, Yu-Rou,Tan, Fang-Fang,Guo, Yan-Jun,Li, Yang
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p. 4724 - 4728
(2021/09/06)
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- Design and development of Tetrahydro-Quinoline derivatives as dual mTOR-C1/C2 inhibitors for the treatment of lung cancer
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Lung cancer is one of the most prevailed cancer worldwide. Many genes get mutated in lung cancer but the involvement of EGFR, KRAS, PTEN and PIK3CA are more common. Unavailability of potent drugs and resistance to the available drugs are major concern in
- Chaube, Udit J.,Rawal, Rakesh,Jha, Abhishek B.,Variya, Bhavesh,Bhatt, Hardik G.
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- Method for selective catalytic hydrogenation of aromatic heterocyclic compounds in non-hydrogen participation manner
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The invention discloses a method for selective catalytic hydrogenation of aromatic heterocyclic compounds in a non-hydrogen participation manner. The method comprises the following steps: by taking 1, 5-cyclooctadiene iridium chloride dimer as a catalyst and phenylsilane as a hydrogen source, carrying out stirring reaction under mild conditions without adding a ligand, namely catalytically hydrogenating the aromatic heterocyclic compounds to obtain hydrogenated products of the aromatic heterocyclic compounds. The method has the advantages of low cost, mild reaction conditions, high selectivity and the like, and special equipment such as a high-pressure kettle and the like and high-temperature conditions which are required when hydrogen is used are avoided.
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Paragraph 0025-0029; 0168-0172
(2021/08/19)
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- Boric acid catalyzed chemoselective reduction of quinolines
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Boric acid promoted transfer hydrogenation of substituted quinolines to synthetically versatile 1,2,3,4-tetrahydroquinolines (1,2,3,4-THQs) was described under mild reaction conditions using a Hantzsch ester as a mild organic hydrogen source. This methodology is practical and efficient, where isolated yields are excellent and reducible functional groups are well tolerated in the N-heteroarene moiety. The reaction parameters and tentative mechanistic pathways are demonstrated by various control experiments and NMR studies. The present work can also be scaled up to obtain gram quantities and the utility of the developed process is illustrated by the transformation of 1,2,3,4-THQs into a series of biologically important molecules including the antiarrhythmic drug nicainoprol.
- Adhikari, Priyanka,Bhattacharyya, Dipanjan,Das, Animesh,Konwar, Monuranjan,Nandi, Sekhar,Sarmah, Bikash Kumar
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supporting information
p. 1214 - 1220
(2020/02/22)
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- Activation of Quinolines by Cationic Chalcogen Bond Donors
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The application of already established as well as novel selenium- and sulfur-based cationic chalcogen bond donors in the catalytic activation of quinoline derivatives is presented. In the presence of selected catalysts, rate accelerations of up to 2300 compared to virtually inactive reference compounds are observed. The catalyst loading can be reduced to 1 molpercent while still achieving nearly full conversion for electron-poor and electron-rich quinolines. Contrary to expectations, preorganized catalysts were less active than the more flexible variants.
- Huber, S. M.,Steinke, T.,Wonner, P.
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supporting information
p. 1673 - 1678
(2019/08/26)
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- Iodine catalyzed reduction of quinolines under mild reaction conditions
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A reduction of quinolines to synthetically versatile tetrahydroquinoline molecules with I2 and HBpin is described. In the presence of iodine (20 mol%) as a catalyst, reduction of quinolines and other N-heteroarenes proceeded readily with hydroboranes as the reducing reagents. The broad functional-group tolerance, good yields and mild reaction conditions imply high practical utility.
- Yang, Chun-Hua,Chen, Xixi,Li, Huimin,Wei, Wenbo,Yang, Zhantao,Chang, Junbiao
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supporting information
p. 8622 - 8625
(2018/08/06)
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- Recyclable Silica-Supported Iridium Catalysts for Selective Reductive Transformation of Quinolines with Formic Acid in Water
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Mesoporous silica (SBA-15)-supported iridium catalysts are prepared by grafting of the newly developed cyclometalated iridium 2-aryl benzoxazole complexes with 3-(triethoxysilyl)-propyl-isocyanate (TEPIC) as a linker. The supported catalysts are characterized by solid-state NMR spectroscopy, small-angle X-ray scattering (SAXS), nitrogen physisorption, FTIR spectroscopy, and electron microscopy analysis, which indicate that the coordination environment of the iridium center as well as the two-dimensional hexagonal pore structure of SBA-15 is maintained after the immobilization. These supported catalysts have been successfully applied to the selective transfer hydrogenation of quinoline derivatives to 1,2,3,4-tetrahydroquinolines (THQs) with formic acid in pure water. Moreover, by simply adapting the amount of formic acid used, N-formyltetrahydroquinolines (FTHQs) could be selectively synthesized from quinolines in two-step, one-pot transfer hydrogenation/N-formylation reactions with these supported catalysts. Notably, these supported catalysts showed better catalytic reactivity than their homogeneous analogs, and they can be easily reused 12 times in the transformation of quinoline to N-formyltetrahydroquinoline (FTHQ) without significant loss of activity.
- Zhang, Jing-Fan,Zhong, Rui,Zhou, Quan,Hong, Xi,Huang, Shuang,Cui, He-Zhen,Hou, Xiu-Feng
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p. 2496 - 2505
(2017/07/13)
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- High efficient iron-catalyzed transfer hydrogenation of quinolines with Hantzsch ester as hydrogen source under mild conditions
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A highly efficient transfer hydrogenation of quinolines with Hantzsch ester as hydrogen source in the presence of 1 mol% Fe(OTf)2 under mild conditions has been developed. A series of substituted 1,2,3,4-tetrahydroquinoline derivatives were afforded in excellent yields with good functional group tolerance.
- He, Renke,Cui, Peng,Pi, Danwei,Sun, Yan,Zhou, Haifeng
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supporting information
p. 3571 - 3573
(2017/10/05)
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- Catalysis with chalcogen bonds: Neutral benzodiselenazole scaffolds with high-precision selenium donors of variable strength
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The benzodiselenazoles (BDS) introduced in this report fulfill, for the first time, all the prerequisites for non-covalent high-precision chalcogen-bonding catalysis in the focal point of conformationally immobilized σ holes on strong selenium donors in a neutral scaffold. Rational bite-angle adjustment to the long Se-C bonds was the key for BDS design. For the unprecedented BDS motif, synthesis of 12 analogs from o-xylene, crystal structure, σ hole variation strategies, optoelectronic properties, theoretical and experimental anion binding as well as catalytic activity are reported. Chloride binding increases with the depth of the σ holes down to KD = 11 μM in THF. Catalytic activities follow the same trend and culminate in rate enhancements for transfer hydrogenation of quinolines beyond 100000.
- Benz, Sebastian,Mareda, Jiri,Besnard, Céline,Sakai, Naomi,Matile, Stefan
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p. 8164 - 8169
(2017/11/27)
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- A COMPOUND AND PHARMACEUTICAL COMPOUND FOR TREATMENT OF INFLAMMATORY DISEASES
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The present invention relates to a pharmaceutical composition for treating inflammatory diseases, comprising: a compound represented by chemical formula I, a pharmaceutically acceptable salt thereof; a hydrate thereof; or a compound as a solvate thereof,
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- Aminoluciferins extend firefly luciferase bioluminescence into the near-infrared and can be preferred substrates over d-luciferin
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Firefly luciferase adenylates and oxidizes D-luciferin to chemically generate visible light and is widely used for biological assays and imaging. Here we show that both luciferase and luciferin can be reengineered to extend the scope of this light-emitting reaction. D-Luciferin can be replaced by synthetic luciferin analogues that increase near-infrared photon flux >10-fold over that of D-luciferin in live luciferase-expressing cells. Firefly luciferase can be mutated to accept and utilize rigid aminoluciferins with high activity in both live and lysed cells yet exhibit 10 000-fold selectivity over the natural luciferase substrate. These new luciferin analogues thus pave the way to an extended family of bioluminescent reporters.
- Mofford, David M.,Reddy, Gadarla Randheer,Miller, Stephen C.
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p. 13277 - 13282
(2015/03/30)
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- Selective anti-markovnikov cyclization and hydrofluorination reaction in superacid HF/SbF5: A tool in the design of nitrogen-containing (fluorinated) polycyclic systems
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The selective synthesis of tetrahydroquinolines and fluorinated arylamines was performed in superacid HF/SbF5 through a superelectrophilic ammonium-carbenium activation process. This anti-Markovnikov oriented reaction was applied to the straightforward synthesis of highly valued (fluorinated) nitrogen-containing heterocyclic compounds.
- Compain, Guillaume,Bonneau, Celine,Martin-Mingot, Agnes,Thibaudeau, Sebastien
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p. 4463 - 4472
(2013/06/05)
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- ROR MODULATORS AND THEIR USES
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The invention relates to ROR modulators; compositions comprising an effective amount of a ROR modulator; and methods for treating or preventing diseases associated with ROR. The invention is based in part on the discovery of ROR modulators which interact with RORa and/or RORy and thereby inhibit or induce RORa and/or RORy-activity, and RORa- and/or RORy-regulated target gene and protein expression.
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- Anti-Markovnikov additions to N-allylic derivatives involving ammonium-carbenium superelectrophiles
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Anti-Markovnikov additions to non-conjugated unsaturated amines in superacid are reported. In situ NMR studies, DFT calculations and labelled substrates reactions support the involvement of new ammonium-carbenium superelectrophiles in this original proces
- Compain, Guillaume,Martin-Mingot, Agnes,Frapper, Gilles,Bachmann, Christian,Jouannetaud, Marie-Paule,Thibaudeau, Sebastien
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supporting information; experimental part
p. 5877 - 5879
(2012/08/14)
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- Synthesis of 6-nitro-1,2,3,4-tetrahydroquinoline: An experimental and theoretical study of regioselective nitration
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A revision of the literature on the nitration of tetrahydroquinolines yielded a number of inconsistencies. Thus, we have carried out a thorough study on the nitration of tetrahydroquinoline and several of its N-protected derivatives both experimentally and at theoretical level. Usually, nitration is carried out in acidic conditions and, thus, tetrahydroquinoline would be N-protonated; however, if the amino group is protected, the neutral system will be the one undergoing nitration. Different protecting groups have been explored varying, not only electronic and steric effects, but also deprotection conditions. Additionally, different reagents and reaction conditions have been investigated. From this study we have been able to achieve total regioselectivity for nitration at the 6-position. A very detailed NMR study has been carried out to unequivocally characterise the four nitro isomers. In parallel, a computational study has been performed that is in agreement with the experimental results obtained. With this purpose, all the σ complexes of the four nitro isomers neutral and N-protonated have been optimized both in gas and water condensed phases by using the B3LYP/6-31++G* level of computation. The selective nitration of tetrahydroquinoline was studied. N-Protecting groups presence or absence directs nitration at different positions. Regioselective nitration at 6-position was achieved. A DFT computational study of all nitro σ complexes was performed in gas and water phases, the results are consistent with the experiments. Copyright
- Cordeiro, Alessandra,Shaw, Julian,O'Brien, John,Blanco, Fernando,Rozas, Isabel
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p. 1504 - 1513
(2011/04/25)
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- Regio- and chemoselective transfer hydrogenation of quinolines catalyzed by a Cp*Ir complex
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An efficient method for the transfer hydrogenation of quinolines catalyzed by a Cp*Ir complex was developed. A variety of 1,2,3,4-tetrahydroquinolines were obtained by regio- and chemoselective transfer hydrogenation of quinolines using 2-propanol as a hydrogen source.
- Fujita, Ken-Ichi,Kitatsuji, Chihiro,Furukawa, Shigetoyo,Yamaguchi, Ryohei
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p. 3215 - 3217
(2007/10/03)
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