- 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 0144; 0145; 0147-0151
(2021/07/31)
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- OLIGOAZAFLUORENE MONOMER
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PROBLEM TO BE SOLVED: To provide an oligoazafluorene monomer that exhibits optical properties, heat resistance, thermal stability and good solubility. SOLUTION: The oligoazafluorene monomer is represented by the general formula (1) in the figure. SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0234-0235; 0237
(2020/09/05)
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- A nickel catalyzed acceptorless dehydrogenative approach to quinolines
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A general, efficient and environmentally benign, one-step synthesis of substituted quinoline derivatives was achieved by acceptorless dehydrogenative coupling of o-aminobenzylalcohols with ketones and secondary alcohols catalyzed by a cheap, earth abundant and easy to prepare nickel catalyst [Ni(MeTAA)], featuring a tetraaza macrocyclic ligand (tetramethyltetraaza[14]annulene (MeTAA)). A wide variety of substituted quinolines were synthesized in high yields starting from readily available o-aminobenzylalcohols and ketones or secondary alcohols. A few controlled reactions were carried out to establish the acceptorless dehydrogenative nature of the reactions.
- Parua, Seuli,Sikari, Rina,Sinha, Suman,Das, Siuli,Chakraborty, Gargi,Paul, Nanda D.
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p. 274 - 284
(2018/01/12)
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- Phosphine-Free NNN-Manganese Complex Catalyzed α-Alkylation of Ketones with Primary Alcohols and Friedl?nder Quinoline Synthesis
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Herein, we report a very simple and inexpensive catalytic system based on Earth's abundant transition metal manganese and on a bench-stable phosphine-free NNN-pincer ligand for an atom-efficient α-alkylations of ketones with primary alcohols via hydrogen-autotransfer C?C bond formation protocol. The precatalyst could be generated in situ and could be activated by using catalytic amount of base under milder conditions. A range of ketones were efficiently diversified with a broad range of primary alcohols in good to excellent isolated yields. Remarkably, this catalyst could also be employed for the synthesis of quinoline derivatives using 2-aminobenzyl alcohol as an alkylating agent. The later reaction is highly benign producing only hydrogen and water as byproducts. (Figure presented.).
- Barman, Milan K.,Jana, Akash,Maji, Biplab
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supporting information
p. 3233 - 3238
(2018/07/31)
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- Blue-light-promoted carbon-carbon double bond isomerization and its application in the syntheses of quinolines
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A blue-light-promoted carbon-carbon double bond isomerization in the absence of any photoredox catalyst is reported. It provides rapid access to a series of quinolines in good to excellent yields under simple aerobic conditions. The protocol is direct, catalyst-free and operationally convenient.
- Chen, Xinzheng,Qiu, Shuxian,Wang, Sasa,Wang, Huifei,Zhai, Hongbin
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supporting information
p. 6349 - 6352
(2017/08/10)
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- Efficient Synthesis of Quinolines via a Knoevenagel/Staudinger/aza-Wittig Sequence
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A simple and efficient method for the construction of quinoline derivatives from 2-azidobenzaldehyde and various carbonyl compounds was developed. The process involves a Knoevenagel condensation of 2-azidobenzaldehyde with carbonyl compound and subsequently an intramolecular normal Staudinger/aza-Wittig reaction to form the quinolone ring in satisfactory yields.
- Qu, Feng,He, Ping,Hu, Ruo-Fei,Cheng, Xiao-Hong,Wang, Song,Wu, Jing
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supporting information
p. 2802 - 2809
(2015/12/23)
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- An efficient synthesis of quinolines via copper-catalyzed C-N cleavage
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An efficient method to synthesize substituted quinolines from ketones and 2-amino benzylamines is described. Copper-catalyzed C-N cleavage of amines followed by condensation with ketones deliver quinolines in moderate to high yields. The broad scope of su
- Xi, Long-Yi,Zhang, Ruo-Yi,Zhang, Lei,Chen, Shan-Yong,Yu, Xiao-Qi
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p. 3924 - 3930
(2015/03/30)
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- Deproto-metallation using mixed lithium-zinc and lithium-copper bases and computed CH acidity of 2-substituted quinolines
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2-Substituted quinolines were synthesized, and their deproto-metallation using the bases prepared by mixing LiTMP with either ZnCl2TMEDA (1/3 equiv.) or CuCl (1/2 equiv.) was studied. With phenyl and 2-naphthyl substituents, the reaction occurred at the 8 position of the quinoline ring, affording the corresponding iodo derivatives or 2-chlorophenyl ketones using the lithium-zinc or the lithium-copper combination, respectively. With a 4-anisyl substituent, a dideprotonation at the 8 and 3′ position was noted using the lithium-zinc base. With 3-pyridyl, 2-furyl and 2-thienyl substituents, the reaction took place on the substituent, at a position adjacent to its heteroatom. 2-Chlorophenyl-2-phenyl-8-quinolyl ketone could be cyclized under palladium catalysis. The experimental results were analyzed with the help of the CH acidities of the substrates, determined in THF solution using the DFT B3LYP method.
- Marquise, Nada,Bretel, Guillaume,Lassagne, Frederic,Chevallier, Floris,Roisnel, Thierry,Dorcet, Vincent,Halauko, Yury S.,Ivashkevich, Oleg A.,Matulis, Vadim E.,Gros, Philippe C.,Mongin, Florence
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p. 19602 - 19612
(2014/05/20)
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- An N-heterocyclic carbene-catalyzed approach to the indirect Friedl?nder quinoline synthesis
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Quinolines have been obtained through the indirect Friendl?nder annulation starting from 2-aminobenzyl alcohol or derivatives from it and ketones catalyzed by N-heterocyclic carbene, and the synthesis of polysubstituted quinolines through a one-pot, two-step tandem reaction starting from readily available ketones and alcohols via alpha-alkylation and indirect Friedl?nder annulation under air also has been presented.
- Zhu, Yanfang,Cai, Chun
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p. 52911 - 52914
(2015/02/05)
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- One-pot friedlnder quinoline synthesis: Scope and limitations
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A highly effective one-pot Friedlnder quinoline synthesis from o-nitroarylcarbaldehydes and ketones or aldehydes was developed and the scope and limitations of the method were examined. The o-nitroarylcarbaldehydes were reduced to o-aminoarylcarbaldehydes with iron in the presence of a catalytic amount of aqueous hydrochloric acid; the amino compounds were then condensed in situ with ketones or aldehydes to form mono- or disubstituted quinolines, respectively, in good-to-excellent yields (58-100%). Georg Thieme Verlag Stuttgart - New York.
- Li, An-Hu,Beard, David J.,Coate, Heather,Honda, Ayako,Kadalbajoo, Mridula,Kleinberg, Andrew,Laufer, Radoslaw,Mulvihill, Kristen M.,Nigro, Anthony,Rastogi, Pawan,Sherman, Dan,Siu, Kam W.,Steinig, Arno G.,Wang, Ti,Werner, Doug,Crew, Andrew P.,Mulvihill, Mark J.
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experimental part
p. 1678 - 1686
(2010/06/22)
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- A ruthenium-catalyzed approach to the friedlaender quinoline synthesis
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In a modification of the Friedlaender reaction, 2-aminobenzyl alcohol is oxidatively cyclized with a variety of ketones to yield substituted quinolines. Of all the ruthenium catalysts that were tested for this reaction, the second-generation Grubbs' catalyst gives the highest quinoline yield, in combination with KOtBu as a base. The presence of a hydrogen acceptor is required to regenerate the catalyst. Also the reaction mechanism is discussed, and the results show that there are possibly two different pathways towards quinolines. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Mierde, Hans Vander,Van Der Voort, Pascal,De Vos, Dirk,Verpoort, Francis
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experimental part
p. 1625 - 1631
(2009/04/11)
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- Synthesis and evaluation of isosteres of N-methyl indolo[3,2-b]-quinoline (cryptolepine) as new antiinfective agents
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Isosteres of cryptolepine (1) were synthesized and evaluated for their antiinfective activities. Overall, the sulfur isostere, 5-methyl benzothieno[3,2-b]quinolinium salt (5b), was equipotent to 1 and has shown no cytotoxicity at 23.8 μg/mL. Compound 5b was also found to have a broad spectrum of activity. Both the carbon and oxygen isosteres were less potent than cryptolepine. A limited library of 2-substituted analogs of 5b has been synthesized and evaluated in antifungal screens but did not show increase in potency compared to the unsubstituted 5b. Similarly, evaluation of tricyclic benzothieno[3,2-b]pyridines while showing promise in individual screens did not produce an overall increase in potency. Overall, the evaluation of the activities of 5b compared with standard antifungal/anti-protozoal agents suggests that the benzothienoquinoline scaffold could serve as a lead for optimization.
- Zhu, Xue Y.,Mardenborough, Leroy G.,Li, Shouming,Khan, Abdul,Zhang, Wang,Fan, Pincheng,Jacob, Melissa,Khan, Shabana,Walker, Larry,Ablordeppey, Seth Y.
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p. 686 - 695
(2007/10/03)
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- Improved ruthenium catalysts for the modified Friedlaender quinoline synthesis
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Herein we describe an improved ruthenium catalyst for the oxidative cyclization of 2-aminobenzylalcohol with ketones, leading to quinolines via a modified Friedlaender synthesis. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique.
- Vander Mierde, Hans,Ledoux, Nele,Allaert, Bart,Van Der Voort, Pascal,Drozdzak, Renata,De Vos, Dirk,Verpoort, Francis
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p. 1572 - 1574
(2008/03/13)
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- Biradicals/zwitterions from enallene-isonitriles. Formal [4 + 1] cycloadditions leading to 11H-indeno[1,2-b]quinoline and related compounds
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1,3-Prototropic rearrangement of the benzannulated enyne-isonitriles to the corresponding enallene-isonitriles followed by cycloaromatization generated the putative quinoline biradicals/zwitterions. A subsequent intramolecular radical-radical coupling or electrophilic aromatic substitution then gave the formal [4 + 1] cycloaddition adducts leading to 11H-indeno[1,2-b]quinoline and related compounds.
- Lu, Xiaoling,Petersen, Jeffrey L.,Wang, Kung K.
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p. 3277 - 3280
(2007/10/03)
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- Ruthenium-catalysed oxidative cyclisation of 2-aminobenzyl alcohol with ketones: modified Friedlaender quinoline synthesis
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2-Aminobenzyl alcohol is oxidatively cyclised with an array of ketones in dioxane at 80 deg C in the presence of a catalytic amount of a ruthenium catalyst and KOH to afford the corresponding quinolines in high yields.
- Cho, Chan Sik,Kim, Bok Tae,Kim, Tae-Jeong,Shim, Sang Chul
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p. 2576 - 2577
(2007/10/03)
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- Diels-Alder reaction of 1,2,3-benzotriazine with enamine: Application to the synthesis of alkaloids, 2-propylquinoline and 2-pentylquinoline
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The Diels-Alder reaction of 1,2,3-benzotriazine with several pyrrolidine enamines of carbonyl compounds was carried out in chloroform in the presence of zinc bromide to afford 2- or 3-mono-, or 2,3-disubstituted quinolines. This method was applied to the synthesis of the alkaloids, 2-propylquinoline and 2-pentylquinoline.
- Koyama, Junko,Toyokuni, Izumi,Tagahara, Kiyoshi
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p. 332 - 334
(2007/10/03)
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- Tandem radical reactions of isonitriles with 2-pyridonyl and other aryl radicals: Scope and limitations, and a first generation synthesis of (±)-camptothecin
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Photolysis of N-propargyl-6-halo-2-pyridones and related aromatic halides in the presence of aryl isonitriles provides tetra- and penta-cyclic products in a single step by a sequence of radical addition to the isonitrile followed by two cyclizations. The scope and limitations of the process are described along with a first generation synthesis of racemic camptothecin.
- Curran, Dennis P.,Liu, Hui,Josien, Hubert,Ko, Sung-Bo
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p. 11385 - 11404
(2007/10/03)
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- Pyrolysis of quinoline-3,4-dicarboxylic anhydrides bearing 2-phenyl, 2-benzyl and 2-o-tolyl substituents: Formation of products of carbene insertion and addition
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Flash vacuum pyrolysis of 2-phenylquinoline-3,4-dicarboxylic anhydride at 800°/0.06 mm gave indeno[1,2-b]indole (30-40%), which readily added nucleophiles Y- at C-10 to give 5,10-dihydro derivatives (Y=H, Me, Ph, NEt2, OMe, CH(COOMe)2 and CMe2NO2). Similar pyrolysis of the 2-benzylquinoline anhydride gave a 1:2 mixture of the (expected) linear 5H-benzo[b]carbazole and the (unexpected) angular 7H-benzo[c]carbazole. The isomeric 2-o-tolylquinoline anhydride on similar pyrolysis gave mainly 11H-benzo[a]carbazole (85%), isomeric benzocarbazoles (4%) and 11H-indeno[1,2-b]quinoline (2.6%). Most of these products are probably derived from exocyclic carbenes formed by aryne-carbene equilibration, but the last compound may be formed by direct aryne-methyl interaction.
- Brown,Coulston,Eastwood,Moffat
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p. 7763 - 7774
(2007/10/02)
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- A Simple Synthesis of Indeno-quinolines
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A three-step synthesis of indeno quinolines (3) from indanone by treatment with POCl3/DMF followed by conversion of the resultant aldehyde (1) into anil hydrochlorides (2) and their thermal cyclization is described.
- Karmakar, A., C.,Sharma, S.,Chatterjee, B. G.,Kray, J. K.
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p. 364 - 365
(2007/10/02)
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- Annelated Derivatives of Phenylquinoline, 2-(2'-Pyridyl)quinoline and 2-Phenyl-1,8-naphthyridine
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Annelated derivatives of 2-phenylquinoline, 2-(2'-pyridyl)quinoline, and 2-phenyl-1,8-naphthyridine have been prepared where the bridging unit contains from one to four methylene units.The conformational properties of these molecules have been analyzed by 1H nmr and uv spectroscopy as well as by pKa determinations.
- Thummel, Randolph P.,Decloitre, Yves,Lefoulon, Francois
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p. 689 - 693
(2007/10/02)
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- SYNTHESIS OF METHYL-SUBSTITUTED INDENOQUINOLINES, INDENOQUINOXALINES, AND THEIR KETO DERIVATIVES AND INVESTIGATION OF THEIR STRUCTURES
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A series of difficultly obtainable and previously unknown methyl homologs of 11H-indenoquinoline, 11H-indenoquinoxaline, and the corresponding 11-keto derivatives were synthesized by new convenient methods, and their structures were investigated.By PMR with lanthanide shift reagents Eu(dpm)3, Pr(dpm)3 and Yb(dpm)3 it was established that the indenoquinolines and ketoindenoquinoxalines do not coordinate with any of the indicated reagents, while the 11-keto derivatives of the indenoquinolines, like those of the indenoquinoxalines, only enter coordination with Yb(dpm)3 at the oxygen atom in the case of the ketoindenoqui nolines and at the N10 nitrogen atom in the case of the indenoquinoxalines.The results from quantum-chemical calculations on the keto derivatives of the indenoquinoline and indenoquinoxaline series are given, and the reasons for the various directions of coordination of Yb(dpm)3 with this type of compound are discussed.
- Prostakov, N. S.,Pleshakov, V. G.,Abedin, Md. Zainul,Kordova, I. R.,Zakharov, V. F.,Zvolinskii, V. P.
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p. 556 - 566
(2007/10/02)
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