- Direct synthesis of ring-fused quinolines and pyridines catalyzed byNNHY-ligated manganese complexes (Y = NR2or SR)
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Four cationic manganese(i) complexes, [(fac-NNHN)Mn(CO)3]Br (Mn-1-Mn-3) and [(fac-NNHS)Mn(CO)3]Br (Mn-4) (whereNNHis a 5,6,7,8-tetrahydro-8-quinolinamine moiety), have been synthesized and evaluated as catalysts for the direct synthesis of quinolines and pyridines by the reaction of a γ-amino alcohol with a ketone or secondary alcohol;NNHS-ligatedMn-4proved the most effective of the four catalysts. The reactions proceeded well in the presence of catalyst loadings in the range 0.5-5.0 mol% and tolerated diverse functional groups such as alkyl, cycloalkyl, alkoxy, chloride and hetero-aryl. A mechanism involving acceptorless dehydrogenation coupling (ADC) has been proposed on the basis of DFT calculations and experimental evidence. Significantly, this manganese-based catalytic protocol provides a promising green and environmentally friendly route to a wide range of synthetically important substituted monocyclic, bicyclic as well as tricyclicN-heterocycles (including 50 quinoline and 26 pyridine examples) with isolated yields of up to 93%.
- Han, Mingyang,Lin, Qing,Liu, Qingbin,Liu, Song,Ma, Ning,Solan, Gregory A.,Sun, Wen-Hua,Wang, Zheng,Yan, Xiuli
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p. 8026 - 8036
(2021/12/27)
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- Pincerlike manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application
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The invention discloses a pincerlike manganese complex, a preparation method thereof, a ligand for preparation, a preparation method of the ligand, a catalyst composition taking the complex as an active component and application of the catalyst composition. According to the pincerlike manganese complex, a cycloalkyl ring is introduced into a ligand framework, and by regulating and controlling the cyclic tension, flexibility and steric hindrance of the cycloalkyl ring, the reactivity and stability of the manganese metal center can be effectively adjusted, and the catalytic activity and substrate applicability of a manganese metal system are remarkably improved. The catalyst composition taking the pincerlike manganese complex as an active component has the advantages of high catalyst activity, wide substrate application range, mild reaction conditions and the like in the process of preparing quinoline or pyridine derivatives by catalyzing dehydrogenation coupling reaction of o-amino aromatic alcohol or gamma-amino alcohol, ketone or secondary alcohol; and the synthesis advantages of low cost and stable performance are embodied, the operation is simple, and the yield is high.
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Paragraph 0159-0165
(2021/07/31)
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- Cu-Catalyzed Pyridine Synthesis via Oxidative Annulation of Cyclic Ketones with Propargylamine
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A Cu-catalyzed, easily scalable one-pot synthesis of fused pyridines by the reaction of cyclic ketones with propargylamine is described. The protocol was optimized based on the results of more than 30 experiments. The highest product yields were achieved in i-PrOH as a solvent in the presence of 5.0 mol % CuCl2 in air. In contrast to the well-known Au-catalyzed protocol, our procedure is "laboratory friendly", cost-effective, and suitable for preparing dozens of grams of fused pyridine-based building blocks and does not require a high-pressure autoclave technique. Decreasing the catalyst amount in the reaction to 1.25 mol % CuCl2 provided a yield comparable to that achieved with 5 mol % catalyst, though a longer reaction time was required. A plausible reaction mechanism was proposed. The scope and limitation of the reaction were studied using 24 different cyclic ketones as starting materials. The fused pyridine yield decreased among cyclic ketones in the following order: six-membered ? eight-membered > five-membered ～seven-membered. The elaborated reaction conditions demonstrated tolerance to a number of protective functional groups in ketone such as ester, tert-butoxycarbonyl (Boc)-protected amine, and acetal moieties.
- Sotnik, Svitlana O.,Subota, Andrii I.,Kliuchynskyi, Anton Y.,Yehorov, Dmytro V.,Lytvynenko, Anton S.,Rozhenko, Alexander B.,Kolotilov, Sergey V.,Ryabukhin, Sergey V.,Volochnyuk, Dmitriy M.
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p. 7315 - 7325
(2021/05/29)
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- Synthesis of Pyridines, Quinolines, and Pyrimidines via Acceptorless Dehydrogenative Coupling Catalyzed by a Simple Bidentate P^ N Ligand Supported Ru Complex
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A ruthenium hydrido chloride complex (1) supported by a simple, heteroleptic bidentate P^N ligand (L1) containing a diarylphosphine and a benzannulated phenanthridine donor arm is reported. In the presence of base, complex 1 catalyzes multicomponent reactions using alcohol precursors to produce structurally diverse molecules including pyridines, quinolines, and pyrimidines via acceptorless dehydrogenative coupling pathways. Notably, L1 does not bear readily (de)protonated Br?nsted acidic or basic groups common to transition metal catalysts capable of these sorts of transformations, suggesting metal-ligand cooperativity does not play a significant role in the catalytic reactivity of 1. A rare example of an η2-aldehyde adduct of ruthenium was isolated and structurally characterized, and its role in acceptorless dehydrogenative coupling reactions is discussed.
- Mondal, Rajarshi,Herbert, David E.
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supporting information
p. 1310 - 1317
(2020/04/15)
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- Palladium acetate-catalyzed one-pot synthesis of mono- And disubstitued pyridines
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A Pd-catalyzed one-pot synthesis of mono- and disubstituted pyridines was developed. The substituted pyridines were obtained from ketones or an aldehyde and 1,3-diaminopropane using a combination of catalytic Pd(OAc)2 and Cu(OAc)2. High-concentration reaction conditions enabled this catalytic reaction to be acid-free.
- Mikami, Shunya,Toyota, Masahiro
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p. 1315 - 1321
(2019/08/01)
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- COMPOUNDS AND METHODS FOR TREATING CANCER
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Substituted hydrazone compounds, methods of making such compounds and metal complexes thereof, pharmaceutical compositions and medicaments comprising such compounds, and methods of using such compounds and metal complexes to treat, prevent or ameliorate cancer are provided.
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Paragraph 0234
(2018/05/24)
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- 2 - (b benzene phosphine base ethyl) - (5, 6, 7, 8 - tetrahydro quinolyl) amine ruthenium complex preparation method and application thereof
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The invention discloses a preparation method and application of 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine ruthenium complexes. A ligand 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine is firstly prepared, and then reacted with RuHCl(CO)(PPh3)3 and RuCl2(PPh3)3 for preparing a complex 1 and a complex 2 which are different in structure, and then the 2-(diphenylphosphineethyl)-(5,6,7,8-tetrahydroquinolinyl)amine ruthenium complex 1 or complex 2 is used to catalyze a condensation reaction of an amino alcohol and a secondary alcohol or a ketone, so that pyridine and quinoline derivatives are synthesized. The preparation method is simple, good in stability, and the catalyst is high in catalytic activity and has the usage amount only being 0.025% by molar of a substrate. The preparation method is applied to production of pyridine and quinoline derivatives, the method is simple, environmental pollution is small, the yield is high and the cost is low.
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Paragraph 0055; 0056; 0057; 0058; 0059
(2017/06/19)
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- A Versatile Ru(II)-NNP Complex Catalyst for the Synthesis of Multisubstituted Pyrroles and Pyridines
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A pincer-type Ru(II)-NNP complex bearing a pyrazolyl-(NH-PtBu2)-pyridine ligand was synthesized and structurally characterized by NMR, IR, elemental analysis, and X-ray single-crystal crystallographic determinations, which efficiently catalyzed the synthesis of multisubstituted pyrroles and pyridines by means of the reactions of secondary alcohols and β- or γ-amino alcohols through deoxygenation and selective C-N and C-C bond formation. The coupling reactions took place with 0.3 mol % catalyst loading and tolerated diverse functional groups. The present work provides an alternative method to construct highly active transition-metal complex catalysts from readily available ligands.
- Chai, Huining,Wang, Liandi,Liu, Tingting,Yu, Zhengkun
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supporting information
p. 4936 - 4942
(2018/02/07)
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- A Ruthenium Catalyst with Unprecedented Effectiveness for the Coupling Cyclization of - Amino Alcohols and Secondary Alcohols
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The ruthenium complex (8-(2-diphenylphosphinoethyl)aminotrihydroquinolinyl)(carbonyl)(hydrido)ruthenium chloride exhibited extremely high efficiency toward the coupling cyclization of -amino alcohols with secondary alcohols. The corresponding products, pyridine or quinoline derivatives, are obtained in good to high isolated yields. On comparison with literature catalysts whose noble-metal loading with respect to -amino alcohols reached 0.5-1.0 mol % for Ru and a record lowest of 0.04 mol % for Ir, the current catalyst achieves the same efficiency with a loading of 0.025 mol % for Ru. The mechanism of acceptorless dehydrogenative condensation (ADC) was proposed on the basis of DFT calculations; in addition, the reactive intermediates were determined by GC-MS, NMR, and single-crystal X-ray diffraction. The catalytic process is potentially suitable for industrial applications.
- Pan, Bing,Liu, Bo,Yue, Erlin,Liu, Qingbin,Yang, Xinzheng,Wang, Zheng,Sun, Wen-Hua
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p. 1247 - 1253
(2016/02/18)
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- Aerobic C-N bond activation: A simple strategy to construct pyridines and quinolines
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Inspired by the autoxidation processes, a dioxygen induced C-N bond activation of primary alkyl amines was demonstrated toward the synthesis of pyridines and quinolines. The transition-metal free conditions with O2 as the sole oxidant make this transformation very attractive. Notably, the substrate applicability of different kinds of ketones is greatly broadened for this transformation.
- Wu, Kun,Huang, Zhiliang,Liu, Chao,Zhang, Heng,Lei, Aiwen
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supporting information
p. 2286 - 2289
(2015/02/05)
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- Copper-catalyzed aerobic synthesis of 2-arylpyridines from acetophenones and 1,3-diaminopropane
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A copper-catalyzed reaction providing direct access to 2-arylpyridines from acetophenones and 1,3-diaminopropane is described. A range of electronically diverse acetophenones undergo this transformation, affording 2-arylpyridines in good yields. (Chemical Equation Presented).
- Xi, Long-Yi,Zhang, Ruo-Yi,Liang, Shuai,Chen, Shan-Yong,Yu, Xiao-Qi
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supporting information
p. 5269 - 5271
(2015/01/09)
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- Regioselectively functionalized pyridines from sustainable resources
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Make the most of it! An Ir-catalyzed dehydrogenative condensation of alcohols and 1,3-amino alcohol was used to construct pyridine derivatives regioselectively. This method provides access to unsymmetrically substituted pyridines and tolerates a wide variety of functional groups. Three equivalents of H2 are generated per pyridine unit formed and the alcohol substrates become completely deoxygenated. Copyright
- Michlik, Stefan,Kempe, Rhett
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supporting information
p. 6326 - 6329
(2013/07/05)
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- Direct synthesis of pyridines and quinolines by coupling of γ-amino-alcohols with secondary alcohols liberating H2 catalyzed by ruthenium pincer complexes
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A novel, one-step synthesis of substituted pyridine- and quinoline-derivatives was achieved by acceptorless dehydrogenative coupling of γ-aminoalcohols with secondary alcohols. The reaction involves consecutive C-N and C-C bond formation, catalyzed by a bipyridyl-based ruthenium pincer complex with a base.
- Srimani, Dipankar,Ben-David, Yehoshoa,Milstein, David
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supporting information
p. 6632 - 6634
(2013/07/26)
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- Mild and efficient deoxygenation of amine-N-oxides with BiCl3/Indium system
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The BiCl3/indium system was found to be a new reagent for deoxygenation of various amine-N-oxides to the corresponding amines in good to excellent yields under mild conditions.
- Yoo, Byung Woo,Choi, Jin Woo
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experimental part
p. 3550 - 3554
(2009/12/03)
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- Facile deoxygenation of amine-N-oxides with CoCl2·6H 2O-indium system
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CoCl2·6H2O/In system was found to be a new reagent for deoxygenation of various amine-N-oxides to the corresponding amines in good to excellent yields under sonication. Copyright Taylor & Francis Group, LLC.
- Jung, Hwa Han,Kyung, Il Choi,Joong, Hyup Kim,Cheol, Min Yoon,Byung, Woo Yoo
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p. 415 - 419
(2007/10/03)
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- Mild and Efficient Deoxygenation of Amine-N-oxides with Titanium Tetrachloride-Indium System
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TiCl4/In system was found to be a new reagent for deoxygenation of various amine-N-oxides to the corresponding amines in good to excellent yields under mild conditions.
- Yoo, Byung Woo,Choi, Kwang Hyun,Choi, Kyung Il,Kim, Joong Hyup
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p. 4185 - 4189
(2007/10/03)
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- SYNTHESIS OF 2,3-POLYMETHYLENEPYRIDINES FROM 3-AMINOACROLEIN AND CYCLIC KETONES
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It is shown that the reaction of 3-aminoacrolein with cyclic ketones of medium size can be used to synthesize inaccessible 2,3-polymethylenepyridines with polymethylene chains of 5, 6, 10, and 12 carbon atoms.
- Matveeva, E. D.,Tungusova, E. E.,Bundel',Yu. G.,Sagitullin, R. S.
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p. 1334 - 1336
(2007/10/02)
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- Thermolysis of Oxime O-Allyl Ethers: A New Method for Pyridine Synthesis
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Thermolysis of cycloalkanone oxime O-allyl ethers in air gave the corresponding cycloalkenopyridines, providing a new method for the synthesis of cycloalkenopyridine derivatives.Keywords - cycloalkanone oxime O-allyl ether; cycloalkenopyridine; thermolysis; O-allylhydroxylamine; cyclohexanone; tetrahydroquinoline
- Koyama, Junko,Sugita, Teruyo,Suzuta, Yukio,Irie, Hiroshi
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p. 2601 - 2606
(2007/10/02)
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- Intramolecular Alkylations of Aromatic Compounds, IX: Synthesis of N-Methyl-8-(3-methoxybenzyl)-1,2,3,5,6,7,8,8a-octahydroquinoline and N-Methyl-9-(3-methoxybenzyl)-1,2,3,6,7,8,9,9a-octahydro-5H-cycloheptenopyridine
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The benzylidene compounds 8a and 8b, obtained by condensation of the 2,3-cycloalkenopyridines 7a and 7b with 3-methoxybenzaldehyde, are converted by catalytic hydrogenation to their benzyl derivatives 9a and 9b.Reduction of the corresponding methoiodides 10a and 10b with sodium borohydride leads to the title compounds 11a and 11b.
- Dammertz, Wolf,Reimann, Eberhard
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p. 826 - 832
(2007/10/02)
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