28712-60-9Relevant articles and documents
The chemistry of novel C2 diazabiaryl ligands: Cycloocta[2,1-b:3,4 -b′]dipyridine, cycloocta[2,1 -b:3,4-b′]diquinoline and their related compounds
Wang, Xiu Chun,Wong, Henry N. C.
, p. 6941 - 6960 (1995)
Three novel cyclooctadiazabiaryl ligands, namely cycloocta[2,1-b:3,4-b′]dipyridine (3), cycloocta[2,1 -b:3,4-b′]diquinoline (4) and cycloocta[2,1-b:3,4-b′]di[1,8]naphthyridine (5) have been synthesized and a number of metal complexes have been prepared for these novel ligands. The energy barrier to ring inversion of these compounds have also been studied.
Direct synthesis of ring-fused quinolines and pyridines catalyzed byNNHY-ligated manganese complexes (Y = NR2or SR)
Han, Mingyang,Lin, Qing,Liu, Qingbin,Liu, Song,Ma, Ning,Solan, Gregory A.,Sun, Wen-Hua,Wang, Zheng,Yan, Xiuli
, p. 8026 - 8036 (2021/12/27)
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%.
Cu-Catalyzed Pyridine Synthesis via Oxidative Annulation of Cyclic Ketones with Propargylamine
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.
, p. 7315 - 7325 (2021/05/29)
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.
Pincerlike manganese complex and preparation method thereof, related ligand and preparation method thereof, catalyst composition and application
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Paragraph 0159-0165, (2021/07/31)
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.
Synthesis of Pyridines, Quinolines, and Pyrimidines via Acceptorless Dehydrogenative Coupling Catalyzed by a Simple Bidentate P^ N Ligand Supported Ru Complex
Mondal, Rajarshi,Herbert, David E.
supporting information, p. 1310 - 1317 (2020/04/15)
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.
Au-complex containing phosphino and imidazolyl moieties as a bi-functional catalyst for one-pot synthesis of pyridine derivatives
Yang, Da,Liu, Huan,Wang, Dong-Liang,Lu, Yong,Zhao, Xiao-Li,Liu, Ye
, p. 323 - 330 (2016/09/23)
The complex of Au-L1 containing imidazolyl ring and the phosphine-ligated-Au moiety was synthesized and applied as the efficient bi-functional catalyst for the one-pot sequential condensation/annulation reaction for the synthesis of pyridine derivatives. It was found that, as for Au-L1, the involved imidazolyl group acted as a Lewis base to catalyze the condensation of carbonyl compounds with propargylamine to form the imino intermediate, and the involved Au+-complex species with alkynophilicity corresponded to the subsequent activation of imino-tailed alkynyl to afford dehydropyridine intermediate. The latter proceeded auto-oxidation reaction to afford the pyridine derivatives. The observed sequential catalysis over Au-L1 proved more efficient than that over the mechanical mixtures of the Au-complex (Au-L2) and N-methylimidazole, because the free N-methylimidazole as an N-containing donor competed with the alkyne substrate to coordinate to Au-center. Moreover, Au-L1 exhibited good generality to a wide range of the substrates for the synthesis of 2,3-fused pyridine derivatives and 2-aryl(heteroaryl)-substituted pyridines.
A Ruthenium Catalyst with Unprecedented Effectiveness for the Coupling Cyclization of - Amino Alcohols and Secondary Alcohols
Pan, Bing,Liu, Bo,Yue, Erlin,Liu, Qingbin,Yang, Xinzheng,Wang, Zheng,Sun, Wen-Hua
, p. 1247 - 1253 (2016/02/18)
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.
Sequential amination/annulation/aromatization reaction of carbonyl compounds and propargylamine: A new one-pot approach to functionalized pyridines
Abbiati, Giorgio,Arcadi, Antonio,Bianchi, Gabriele,Di Giuseppe, Sabrina,Marinelli, Fabio,Rossi, Elisabetta
, p. 6959 - 6966 (2007/10/03)
A general one-pot synthesis of pyridines 4a-t from the reaction of dialkyl acyclic/cyclic ketones 1a-i, methyl, aryl/heteroaryl ketones 1m-r, and aldehydes bearing α-hydrogens 1s,t with propargylamine 2 is described. Gold and copper salts are efficient catalysts for the reaction of ketones with 2. The formation of the pyridines 4 is suggested to proceed through the sequential amination of carbonyl compounds followed by regioselective 6-endo-dig cyclization of the N-propargylenamine (N-propargyldienamine) intermediate 3(5) and aromatization reaction. Whereas the preparation of linear polycyclic pyridine 4i can be carried out by reacting cholestan-3-one 1i with 2, the angular polycyclic pyridine 4j has been obtained starting from cholest-5-en-3-one 1j. Selectivity of the reaction of polycyclic dicarbonyls 1k,1 with 2 has also been investigated.
Synthesis, Metal Complex Formation, and Resolution of a New C2 Diazabiaryl Ligand: Cyclo-octadipyridine
Wang, Xiu Chun,Cui, Yu Xin,Mak, Thomas C. W.,Wong, Henry N. C.
, p. 167 - 169 (2007/10/02)
A new C2 diazabiaryl ligand cyclo-octadipyridine (1) has been prepared, and an X-ray crystallographic analysis of the tetracarbonyl molybdenum complex of (1) showed that the torsional angle between the alkenic bonds is 51 deg; attempted resolution of (1) with a chiral palladium complex apparently afforded a single diastereoisomer, whose stereochemical configuration was substantiated by one-dimensional and two-dimensional proton NMR studies.
SYNTHESIS OF 2,3-POLYMETHYLENEPYRIDINES FROM 3-AMINOACROLEIN AND CYCLIC KETONES
Matveeva, E. D.,Tungusova, E. E.,Bundel',Yu. G.,Sagitullin, R. S.
, p. 1334 - 1336 (2007/10/02)
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.
