- 3-nitrile quinoline derivative and preparation method thereof
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The invention discloses a 3-nitrile quinoline derivative. The structural formula of the 3-nitrile quinoline derivative is shown as a formula I, wherein R1 is hydrogen, alkyl or aryl; R2-R5 are respectively and independently hydrogen, halogen, alkyl, alkoxy, trifluoromethyl, ester group, hydroxyl or amino; and R6 is hydrogen, alkyl, ester group, aryl or substituted aryl. According to the 3-nitrile quinoline derivative provided by the invention, R1-R6 sites can be connected with various substituent groups, and the 3-nitrile quinoline derivative is an organic synthesis intermediate with wide application and has important application value in the fields of medicines and organic synthesis. The invention further provides the preparation method of the 3-nitrile quinoline derivative, the preparation method can be carried out under the air condition, the reaction condition is mild and easy to control, the used raw materials are easy to obtain, toxic nitrile compounds are not needed to serve as nitrile groups sources, the substrate application range is wide, the reaction conversion rate is high, high selectivity and yield can be obtained within short time, and the method is simple in post-treatment, green, environment-friendly and suitable for large-scale industrial production.
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Paragraph 0025-0075
(2021/11/10)
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- Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
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We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
- Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
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supporting information
p. 3723 - 3728
(2021/04/07)
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- Revisiting the synthesis of aryl nitriles: a pivotal role of CAN
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Facilitated by the dual role of Ceric Ammonium Nitrate (CAN), herein we report a cost-effective approach for the cyanation of aryl iodides/bromides with CAN-DMF as an addition to the existing pool of combined cyanation sources. In addition to being an oxidant, CAN acts as a source of nitrogen in our protocol. The reaction is catalyzed by a readily available Cu(ii) salt and the ability of CAN to generate ammonia in the reaction medium is utilized to eliminate the additional requirement of a nitrogen source, ligand, additive or toxic reagents. The mechanistic study suggests an evolution of CN?leading to the synthesis of a variety of aryl nitriles in moderate to good yields. The proposed mechanism is supported by a series of control reactions and labeling experiments.
- Saikia, Rakhee,Park, Kwihwan,Masuda, Hayato,Itoh, Miki,Yamada, Tsuyoshi,Sajiki, Hironao,Mahanta, Sanjeev P.,Thakur, Ashim J.
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p. 1344 - 1351
(2021/02/27)
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- Decarbonylative Synthesis of Aryl Nitriles from Aromatic Esters and Organocyanides by a Nickel Catalyst
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A decarbonylative cyanation of aromatic esters with aminoacetonitriles in the presence of a nickel catalyst was developed. The key to this reaction was the use of a thiophene-based diphosphine ligand, dcypt, permitting the synthesis of aryl nitrile without the generation of stoichiometric metal- or halogen-containing chemical wastes. A wide range of aromatic esters, including hetarenes and pharmaceutical molecules, can be converted into aryl nitriles.
- Iizumi, Keiichiro,Kurosawa, Miki B.,Isshiki, Ryota,Muto, Kei,Yamaguchi, Junichiro
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supporting information
p. 1555 - 1559
(2020/11/10)
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- Highly chemoselective deoxygenation of N-heterocyclic: N -oxides under transition metal-free conditions
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Because their site-selective C-H functionalizations are now considered one of the most useful tools for synthesizing various N-heterocyclic compounds, the highly chemoselective deoxygenation of densely functionalized N-heterocyclic N-oxides has received much attention from the synthetic chemistry community. Here, we provide a protocol for the highly chemoselective deoxygenation of various functionalized N-oxides under visible light-mediated photoredox conditions with Na2-eosin Y as an organophotocatalyst. Mechanistic studies imply that the excited state of the organophotocatalyst is reductively quenched by Hantzsch esters. This operationally simple technique tolerates a wide range of functional groups and allows high-yield, multigram-scale deoxygenation. This journal is
- Kim, Se Hyun,An, Ju Hyeon,Lee, Jun Hee
-
supporting information
p. 3735 - 3742
(2021/05/04)
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- Highly Chemoselective Deoxygenation of N-Heterocyclic N-Oxides Using Hantzsch Esters as Mild Reducing Agents
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Herein, we disclose a highly chemoselective room-temperature deoxygenation method applicable to various functionalized N-heterocyclic N-oxides via visible light-mediated metallaphotoredox catalysis using Hantzsch esters as the sole stoichiometric reductant. Despite the feasibility of catalyst-free conditions, most of these deoxygenations can be completed within a few minutes using only a tiny amount of a catalyst. This technology also allows for multigram-scale reactions even with an extremely low catalyst loading of 0.01 mol %. The scope of this scalable and operationally convenient protocol encompasses a wide range of functional groups, such as amides, carbamates, esters, ketones, nitrile groups, nitro groups, and halogens, which provide access to the corresponding deoxygenated N-heterocycles in good to excellent yields (an average of an 86.8% yield for a total of 45 examples).
- An, Ju Hyeon,Kim, Kyu Dong,Lee, Jun Hee
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supporting information
p. 2876 - 2894
(2021/02/01)
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- Nickel-Catalyzed Cyanation of Aryl Thioethers
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A nickel-catalyzed cyanation of aryl thioethers using Zn(CN)2 as a cyanide source has been developed to access functionalized aryl nitriles. The ligand dcype (1,2-bis(dicyclohexylphosphino)ethane) in combination with the base KOAc (potassium acetate) is essential for achieving this transformation efficiently. This reaction involves both a C-S bond activation and a C-C bond formation. The scalability, low catalyst and reagents loadings, and high functional group tolerance have enabled both late-stage derivatization and polymer recycling, demonstrating the reaction's utility across organic chemistry.
- Delcaillau, Tristan,Woenckhaus-Alvarez, Adrian,Morandi, Bill
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supporting information
p. 7018 - 7022
(2021/09/13)
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- Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
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Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
- Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
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supporting information
p. 19257 - 19262
(2019/12/02)
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- Visible-Light Photocatalyzed Deoxygenation of N-Heterocyclic N-Oxides
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A scalable and operationally simple method is described that allows for the chemoselective deoxygenation of a wide range of N-heterocyclic N-oxides (a total of 36 examples). This visible-light-induced protocol features the use of only commercially available reagents, room-temperature conditions, and unprecedented chemoselective removal of the oxygen atom in a quinoline N-oxide in the presence of a pyridine N-oxide in the same molecule through the judicious selection of a photocatalyst.
- Kim, Kyu Dong,Lee, Jun Hee
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supporting information
p. 7712 - 7716
(2019/01/03)
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- Cyanation of aromatic/vinylic boronic acids with α-cyanoacetates
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A friendly protocol is reported to achieve cyanation of aromatic and vinylic boronic acids using nontoxic and readily available α-cyanoacetates as a cyano source under aerobic conditions. Many aryl/vinyl boronic acids (as well as some iodides and bromides) are amenable substrates to give aryl nitriles and acrylonitriles. This cyanation method provides a safe and operationally convenient alternative to traditional ones requiring toxic cyanide salts.
- Wang, Xian-Jin,Zhang, Song-Lin
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supporting information
p. 14826 - 14830
(2017/12/15)
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- Ex situ generation of stoichiometric HCN and its application in the Pd-catalysed cyanation of aryl bromides: Evidence for a transmetallation step between two oxidative addition Pd-complexes
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A protocol for the Pd-catalysed cyanation of aryl bromides using near stoichiometric and gaseous hydrogen cyanide is reported for the first time. A two-chamber reactor was adopted for the safe liberation of ex situ generated HCN in a closed environment, which proved highly efficient in the Ni-catalysed hydrocyanation as the test reaction. Subsequently, this setup was exploited for converting a range of aryl and heteroaryl bromides (28 examples) directly into the corresponding benzonitriles in high yields, without the need for cyanide salts. Cyanation was achieved employing the Pd(0) precatalyst, P(tBu)3-Pd-G3 and a weak base, potassium acetate, in a dioxane-water solvent mixture. The methodology was also suitable for the synthesis of 13C-labelled benzonitriles with ex situ generated 13C-hydrogen cyanide. Stoichiometric studies with the metal complexes were undertaken to delineate the mechanism for this catalytic transformation. Treatment of Pd(P(tBu)3)2 with H13CN in THF provided two Pd-hydride complexes, (P(tBu)3)2Pd(H)(13CN), and [(P(tBu)3)Pd(H)]2Pd(13CN)4, both of which were isolated and characterised by NMR spectroscopy and X-ray crystal structure analysis. When the same reaction was performed in a THF : water mixture in the presence of KOAc, only (P(tBu)3)2Pd(H)(13CN) was formed. Subjection of this cyano hydride metal complex with the oxidative addition complex (P(tBu)3)Pd(Ph)(Br) in a 1 : 1 ratio in THF led to a transmetallation step with the formation of (P(tBu)3)2Pd(H)(Br) and 13C-benzonitrile from a reductive elimination step. These experiments suggest the possibility of a catalytic cycle involving initially the formation of two Pd(ii)-species from the oxidative addition of LnPd(0) into HCN and an aryl bromide followed by a transmetallation step to LnPd(Ar)(CN) and LnPd(H)(Br), which both reductively eliminate, the latter in the presence of KOAc, to generate the benzonitrile and LnPd(0).
- Kristensen, Steffan K.,Eikeland, Espen Z.,Taarning, Esben,Lindhardt, Anders T.,Skrydstrup, Troels
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p. 8094 - 8105
(2017/11/27)
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- Synthesis of nitriles from aldehydes with trimethylphenylammonium tribromide and ammonium acetate
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Various aromatic and heterocyclic aldehydes were easily converted to respective nitriles with the combination of trimethylphenylammonium tribromide and ammonium acetate in good yields at room temperature.
- Sayama, Shinsei
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p. 1796 - 1802
(2016/11/06)
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- Rearrangements of 4-Quinolylcarbene, 3-Quinolylcarbene, and 2-Quinolylcarbene to 1-Naphthylnitrene and Cyanoindenes by Falling Solid Flash Vacuum Pyrolysis
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The relationship between 4-quinolylcarbene 17, 3-quinolylcarbene 21, 2-quinolylcarbene 25, and 1-naphthylnitrene 35 has been explored experimentally and computationally. The diazomethylquinolines generated from (5-tetrazolyl)quinolines or 1,2,3-triazolo[1,5-a]quinoline by conventional flash vacuum pyrolysis (FVP) were observed by IR spectroscopy. The carbenes were generated by falling solid flash vacuum pyrolysis (FS-FVP). 4-Quinolylcarbene 17 was found to rearrange to 3-quinolylcarbene 21 and then to 2-quinolylcarbene 25, and finally via 1-naphthylnitrene 35 to 1-cyanoindene 36, which then isomerizes to 3- and 2-cyanoindenes 12 and 13. The thermal rearrangement of 2-quinolylcarbene to 1-naphthylnitrene was verified by ESR spectroscopy. The reaction mechanism has been elucidated with the help of calculations of the structures and energies of the quinolylcarbenes and 1-naphthylnitrene and the intervening aza-benzobicyclo[4.1.0]heptatrienes, aza-benzocycloheptatetraenes, and aza-benzocycloheptatrienylidenes and the transition states connecting them at the B3LYP/6-31G? level. The nonobserved 1,2-hydrogen shifts in aza-benzocycloheptatetraenes/aza-benzocycloheptatrienylidenes are found to have very high activation barriers.
- Aylward, Nigel,Kvaskoff, David,Becker, Jürgen,Wentrup, Curt
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p. 4609 - 4615
(2016/07/06)
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- A Homogeneous Method for the Conveniently Scalable Palladium- and Nickel-Catalyzed Cyanation of Aryl Halides
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Homogeneous conditions for the palladium-catalyzed cyanation of aryl halides were developed. This new system features a broad scope of aryl chlorides and bromides, uses 2-propanol or 1-butanol as solvent, and is readily scalable. The same conditions can also provide simple benzonitriles using the recently developed (TMEDA)NiCl(o-tolyl) precatalyst in conjunction with 1,1′-bis(diphenylphosphino)ferrocene (dppf) as a ligand.
- Burg, Finn,Egger, Julian,Deutsch, Johannes,Guimond, Nicolas
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p. 1540 - 1545
(2016/08/30)
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- Chemistry informer libraries: A chemoinformatics enabled approach to evaluate and advance synthetic methods
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Major new advances in synthetic chemistry methods are typically reported using simple, non-standardized reaction substrates, and reaction failures are rarely documented. This makes the evaluation and choice of a synthetic method difficult. We report a standardized complex molecule diagnostic approach using collections of relevant drug-like molecules which we call chemistry informer libraries. With this approach, all chemistry results, successes and failures, can be documented to compare and evolve synthetic methods. To aid in the visualization of chemistry results in drug-like physicochemical space we have used an informatics methodology termed principal component analysis. We have validated this method using palladium- and copper-catalyzed reactions, including Suzuki-Miyaura, cyanation and Buchwald-Hartwig amination.
- Kutchukian, Peter S.,Dropinski, James F.,Dykstra, Kevin D.,Li, Bing,Dirocco, Daniel A.,Streckfuss, Eric C.,Campeau, Louis-Charles,Cernak, Tim,Vachal, Petr,Davies, Ian W.,Krska, Shane W.,Dreher, Spencer D.
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p. 2604 - 2613
(2016/04/05)
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- Aryl Nitriles from Alkynes Using tert -Butyl Nitrite: Metal-Free Approach to C≡C Bond Cleavage
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Alkyne C≡C bond breaking, outside of alkyne metathesis, remains an underdeveloped area in reaction discovery. Recently, nitrogenation has been reported to allow nitrile formation from alkynes. A new protocol for the metal-free C≡C bond cleavage of terminal alkynes to produce nitriles is reported. This method provides an opportunity to synthesize a vast range of nitriles containing aryl, heteroaryl, and natural product derivatives (38 examples). In addition, the potential of tBuONO to act as a powerful nitrogenating agent for terminal aryl alkynes is demonstrated. (Figure Presented).
- Dutta, Uttam,Lupton, David W.,Maiti, Debabrata
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supporting information
p. 860 - 863
(2016/03/01)
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- Copper-free Sandmeyer cyanation of arenediazonium o-benzenedisulfonimides
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Arene and heteroarenediazonium o-benzenedisulfonimides can be used as efficient reagents in Sandmeyer cyanation. This work reports such reactions carried out by us under very mild conditions using tetrabutyl ammonium cyanide as a safe cyanide source and, interestingly, without the need for a Cu catalyst. The reactions have given rise to aryl nitriles in good yields (25 examples, average yield 75%). A good amount of o-benzenedisulfonimide was recovered from each reaction and then reused to prepare other salts. Mechanistic insights have allowed us to highlight the fundamental role of the o-benzenedisulfonimide anion as an electron transfer agent.
- Barbero, Margherita,Cadamuro, Silvano,Dughera, Stefano
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p. 1437 - 1441
(2016/02/03)
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- Cu-Catalyzed Cyanation of Arylboronic Acids with Acetonitrile: A Dual Role of TEMPO
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The cyanation of arylboronic acids by using acetonitrile as the "CN" source has been achieved under a Cu(cat.)/TEMPO system (TEMPO=2,2,6,6-tetramethylpiperidine N-oxide). The broad substrate scope includes a variety of electron-rich and electron-poor arylboronic acids, which react well to give the cyanated products in high to excellent yields. Mechanistic studies reveal that TEMPO-CH2CN, generated in situ, is an active cyanating reagent, and shows high reactivity for the formation of the CN- moiety. Moreover, TEMPO acts as a cheap oxidant to enable the reaction to be catalytic in copper. The cyanation of arylboronic acids by using acetonitrile as the "CN" source has been achieved under a Cu(cat.)/TEMPO system. Electron-rich and electron-poor arylboronic acids react well to give the cyanated products in high to excellent yields. Mechanistic studies reveal that TEMPO-CH2CN, generated in situ, is an active cyanating reagent. Moreover, TEMPO, a cheap oxidant, enables the reaction to be catalytic in copper (see scheme; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide).
- Zhu, Yamin,Li, Linyi,Shen, Zengming
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supporting information
p. 13246 - 13252
(2015/09/15)
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- Copper-catalyzed oxygen atom transfer of N-oxides leading to a facile deoxygenation procedure applicable to both heterocyclic and amine N-oxides
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Deoxygenation of various types of N-oxides including both heterocyclic and alkyl(aryl)amine derivatives has successfully been developed by the copper-catalyzed oxygen atom transfer using diazo compounds as the oxygen acceptor. The reaction proceeds smoothly over a broad range of substrates with excellent functional group tolerance under mild conditions. This journal is
- Jeong, Jisu,Lee, Donggun,Chang, Sukbok
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supporting information
p. 7035 - 7038
(2015/04/22)
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- N-bromosuccinimide-mediated radical cyclization of 3-arylallyl azides: Synthesis of 3-substituted quinolines
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Visible light irradiation of N-bromosuccinimide serves as an effective means to convert methyl 2-(azidomethyl)-3-arylpropenoates and 2-(azidomethyl)-3-arylacrylonitriles to the corresponding iminyl radicals via ?±-hydrogen abstraction and subsequent extrusion of dinitrogen. Thus formed iminyl radicals then undergo intramolecular ortho attack on the aryl ring, affording methyl quin-oline-3-carboxylates and quinoline-3-carbonitriles respectively.
- Wang, Wei-Xia,Zhang, Qing-Zhao,Zhang, Tian-Qi,Li, Zhan-Shan,Zhang, Wei,Yu, Wei
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p. 221 - 226
(2015/02/19)
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- Rh(III)-catalyzed synthesis of (dihydro)quinolines via the annulation of N-sulfonyl 2-aminobenzaldehydes with olefins
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We developed a new synthetic method for the production of 1,2-dihydroquinolines and quinolines via the Rh(III)-catalyzed annulation of N-sulfonyl 2-aminobenzaldehydes with olefins. Various functionalities were found to be compatible under the operationally simple conditions. This study provides the first example of a Rh(III)-catalyzed synthesis of 1,2-dihydroquinolines.
- Zhang, Yimeng,Zhang, Tao,Zhan, Haoqiang,Li, Xingwei
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p. 1840 - 1845
(2015/09/28)
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- ZnO-supported Pd nanoparticle-catalyzed ligand- and additive-free cyanation of unactivated aryl halides using K4[Fe(CN)6]
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The use of a new ZnO-supported palladium(0) nanoparticle catalyst for the cyanation of aryl halides using a relatively benign cyanide source, K 4[Fe(CN)6], is described. This catalyst has been applied for the efficient cyanation of a variety of functionalized aryl bromides and activated aryl chlorides. This process circumvents the need for an additive and a ligand for the reaction and offers the advantages of high product yields, low catalyst loading (0.2 mol % Pd), and recyclability of the catalyst.
- Chatterjee, Tanmay,Dey, Raju,Ranu, Brindaban C.
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p. 5875 - 5879
(2014/07/08)
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- Ultrasounds in melted poly(ethylene glycol) promote copper-catalyzed cyanation of aryl halides with K4[Fe(CN)6]
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Melted poly(ethylene glycols) (PEGs) were used for the first time as solvent for the sonochemically promoted cyanation of aryl halides employing inexpensive and safe K4[Fe(CN)6] and a relatively low amount of Cu-based catalyst. The Mw (weight-average polymer molecular weight) of PEG proved to notably influence the substrate conversion, which is indicative of a strong dependence of the sonication efficacy on solvent properties. Gel permeation chromatography (GPC), X-ray photoelectron spectroscopy (XPS) and transmission electron microscopy (TEM) contributed to the characterization of the polymer and the elucidation of the catalytic system. Off the PEG: Melted poly(ethylene glycol)s (PEG)s were used for the first time as solvent for the sonochemical cyanation of aryl halides using K 4[Fe(CN)6] and a relatively low amount of Cu catalyst (5 %). The weight-average molecular weight of PEG was proven to exert a notable influence on conversion, and CuI proved to be the most efficient catalyst, affording good results within short reaction times with the use of aryl iodides and activated aryl bromides as substrates.
- Giachi, Guido,Frediani, Marco,Oberhauser, Werner,Lamaty, Frederic,Martinez, Jean,Colacino, Evelina
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p. 919 - 924
(2014/03/21)
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- Palladium(II)-catalyzed direct conversion of methyl arenes into aromatic nitriles
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From methyl to nitrile: A mild ammoxidation method, which directly converts methyl arenes into aromatic nitriles, has been developed by using Pd(OAc) 2 and N-hydroxyphthalimide (NHPI) as the catalysts, and tert-butyl nitrite as the nitrogen source and oxidant. Copyright
- Shu, Zhibin,Ye, Yuxuan,Deng, Yifan,Zhang, Yan,Wang, Jianbo
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supporting information
p. 10573 - 10576
(2013/10/21)
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- A general, practical palladium-catalyzed cyanation of (hetero)aryl chlorides and bromides
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Playing it safe: The nontoxic cyanide source K4[Fe(CN) 6]×3 H2O can be used for the cyanation of (hetero)aryl halides. The application of palladacycle catalysts prevents poisoning during catalyst formation, thereby allowing for low catalyst loadings, fast reaction times, and wide heterocyclic substrate scope.
- Senecal, Todd D.,Shu, Wei,Buchwald, Stephen L.
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supporting information
p. 10035 - 10039
(2013/10/01)
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- Cyanation of aryl bromides with K4[Fe(CN)6] catalyzed by dichloro[bis{1-(dicyclohexylphosphanyl)piperidine}]palladium, a molecular source of nanoparticles, and the reactions involved in the catalyst-deactivation processes
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Dichloro[bis{1-(dicyclohexylphosphanyl)piperidine}]palladium [(P{(NC 5H10)(C6H11)2}) 2PdCl2] (1) is a highly active and generally applicable C-C cross-coupling catalyst. Apart from its high catalytic activity in Suzuki, Heck, and Negishi reactions, compound 1 also efficiently converted various electronically activated, nonactivated, and deactivated aryl bromides, which may contain fluoride atoms, trifluoromethane groups, nitriles, acetals, ketones, aldehydes, ethers, esters, amides, as well as heterocyclic aryl bromides, such as pyridines and their derivatives, or thiophenes into their respective aromatic nitriles with K4[Fe(CN)6] as a cyanating agent within 24 h in NMP at 140 °C in the presence of only 0.05 mol % catalyst. Catalyst-deactivation processes showed that excess cyanide efficiently affected the molecular mechanisms as well as inhibited the catalysis when nanoparticles were involved, owing to the formation of inactive cyanide complexes, such as [Pd(CN)4]2-, [(CN)3Pd(H)]2-, and [(CN)3Pd(Ar)]2-. Thus, the choice of cyanating agent is crucial for the success of the reaction because there is a sharp balance between the rate of cyanide production, efficient product formation, and catalyst poisoning. For example, whereas no product formation was obtained when cyanation reactions were examined with Zn(CN)2 as the cyanating agent, aromatic nitriles were smoothly formed when hexacyanoferrate(II) was used instead. The reason for this striking difference in reactivity was due to the higher stability of hexacyanoferrate(II), which led to a lower rate of cyanide production, and hence, prevented catalyst-deactivation processes. This pathway was confirmed by the colorimetric detection of cyanides: whereas the conversion of β-solvato-α-cyanocobyrinic acid heptamethyl ester into dicyanocobyrinic acid heptamethyl ester indicated that the cyanide production of Zn(CN)2 proceeded at 25 °C in NMP, reaction temperatures of >100 °C were required for cyanide production with K4[Fe(CN) 6]. Mechanistic investigations demonstrate that palladium nanoparticles were the catalytically active form of compound 1. A balancing act: Compound 1 (see scheme) is a highly active cyanation catalyst. Furthermore, a sharp balance between the rates of cyanide generation, efficient product formation, and catalyst deactivation owing to excess cyanide was observed in deactivation processes. Copyright
- Gerber, Roman,Oberholzer, Miriam,Frech, Christian M.
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supporting information; experimental part
p. 2978 - 2986
(2012/04/04)
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- PTERIDINONES AS INHIBITORS OF POLO - LIKE KINASE
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The present invention provides compounds having a structure according to Formula (I) or a salt or solvate thereof, wherein ring A, X, R1, R2, R3, R4, R5 and R6, are defined herein. The invention further provides pharmaceutical compositions including the compounds of the invention and methods of making and using the compounds and compositions of the invention, e.g., in the treatment and prevention of various disorders, such as Parkinson's disease.
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Page/Page column 109
(2011/07/09)
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- Development of Pd/C-catalyzed cyanation of Aryl halides
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A practical method for palladium-catalyzed cyanation of aryl halides using Pd/C is described. The new method can be applied to a variety of aryl bromide and active aryl chloride substrates to effect efficient conversions. The process features many advantages over existing cyanation conditions and the practical utility of the process has been demonstrated on scale.
- Yu, Hannah,Richey, Rachel N.,Miller, William D.,Xu, Jiansheng,May, Scott A.
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supporting information; experimental part
p. 665 - 668
(2011/03/19)
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- Open air palladium catalyzed cyanation-the use of PMHS to protect from oxygen
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PMHS (polymethylhydrosiloxane) used in catalytic amounts has a remarkable ability to prevent catalyst poisoning by oxygen contamination during palladium catalyzed cyanation reactions. The procedure is applicable to a wide range of substrates and is so effective that it allows the reactions to be run fully open to the atmosphere.
- Martin, Michael T.,Liu, Bing,Cooley Jr., Bobby E.,Eaddy, John F.
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p. 2555 - 2557
(2007/10/03)
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- An environmentally benign procedure for the synthesis of aryl and arylvinyl nitriles assisted by microwave in ionic liquid
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Aryl and arylvinyl nitriles have been prepared in good yields from the corresponding bromides with potassium hexacyanoferrate (II) using palladium-catalyzed reactions in ionic liquid under microwave irradiation. Georg Thieme Verlag Stuttgart.
- Li, Lian-Hua,Pan, Zhen-Liang,Duan, Xin-Hua,Liang, Yong-Min
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p. 2094 - 2098
(2008/02/05)
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- COPPER-CATALYZED FORMATION OF CARBON-HETEROATOM AND CARBON-CARBON BONDS
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One aspect of the present invention relates to copper-catalyzed carbon-heteroatom and carbon-carbon bond-forming methods. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-sulfur bond between the sulfur atom of a thiol moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper(II)-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of an amide and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In certain embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-carbon bond between the carbon atom of cyanide ion and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In another embodiment, the present invention relates to a copper-catalyzed method of transforming and aryl, heteroaryl, or vinyl iodide. Yet another embodiment of the present invention relates to a tandem method, which may be practiced in a single reaction vessel, wherein the first step of the method involves the copper-catalyzed formation of an aryl, heteroaryl, or vinyl iodide from the corresponding aryl, heteroaryl, or vinyl chloride or bromide; and the second step of the method involves the copper-catalyzed formation of an aryl, heteroaryl, or vinyl nitrile, amide or sulfide from the aryl, heteroaryl, or vinyl iodide formed in the first step.
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- Palladium-catalyzed cyanation of aryl bromides promoted by low-level organotin compounds
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(Equation Presented) A novel method for palladium-catalyzed cyanation of aryl bromides promoted by low-level tri-n-butyltin chloride or cyanide is described. The method features low catalyst loading and mild reaction conditions. KCN is used as the cyanide source. Only trace levels of the tri-n-butyltin compound are required to achieve high conversion and yield in the cyanation of aryl bromides, iodides, and triflates.
- Yang, Chunhua,Williams, J. Michael
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p. 2837 - 2840
(2007/10/03)
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- Synthesis of 3-substituted quinolines via transition-metal-catalyzed reductive cyclization of o-nitro baylis-hillman acetates
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Reductive cyclization of o-nitro-substituted Baylis-Hillman acetates by carbon monoxide, catalyzed by [Cp*Fe(CO)2]2, gives moderate to good yields of 3-substituted quinolines.
- O'Dell, David K.,Nicholas, Kenneth M.
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p. 6427 - 6430
(2007/10/03)
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- Copper-catalyzed domino halide exchange-cyanation of aryl bromides
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An efficient copper-catalyzed domino halogen exchange-cyanation procedure for aryl bromides was developed utilizing 10 mol % CuI, 20 mol % KI, 1.0 equiv of the inexpensive N,N′-dimethylethylenediamine as ligand, and 1.2 equiv of NaCN in toluene at 110 °C. The new method represents a significant improvement over the traditional Rosenmund-von Braun reaction: the reaction conditions are much milder, and the use of stoichiometric amounts of copper(I) cyanide and polar solvents is avoided; therefore the isolation and purification of the aromatic nitrile products is greatly simplified. In addition, the new method exhibits excellent functional group compatibility comparable to that of the analogous Pd-catalyzed cyanation methodology. Copyright
- Zanon, Jacopo,Klapars, Artis,Buchwald, Stephen L.
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p. 2890 - 2891
(2007/10/03)
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- Palladium-catalyzed cyanation of aryl and heteroaryl iodides with copper(i) cyanide
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The palladium-catalyzed cyanation of aryl and heteroaryl iodides or bromides using copper(i) cyanide as a cyano group source afforded the corresponding aryl and heteroaryl cyanides in good yields.
- Sakamoto, Takao,Ohsawa, Kazutoshi
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p. 2323 - 2326
(2007/10/03)
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- The Cyanation of Aromatic Halides Catalyzed by Nickel(0) Complexes Generated in Situ. II. The Cyanation of Heteroaromatic Halides
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The cyanation of 3-bromopyridine catalyzed by in situ generated Ni(PPh3)n was examined with various MCN (M = K, Na)-dipolar aprotic solvent systems by four procedures.Under certain reaction conditions, 3-bromopyridine and several heteroaromatic halides were cyanated to give the corresponding nitriles in fair to good yields.Noticeable differences in reactivity among 3-bromopyridine, 3-bromofuran, 3-bromothiophene, and bromobenzene were observed.
- Sakakibara, Yasumasa,Ido, Yoshinori,Sasaki, Ken,Sakai, Mutsuji,Uchino, Norito
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p. 2776 - 2778
(2007/10/02)
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- Photochemical Reaction of Ethoxycarbonyl-Substituted Quinolines
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The photochemical reactions of the quinoline derivatives substituted by an ethoxycarbonyl group at the 2-, 3-, and 4-positions of a quinoline nucleus have been investigated in several alcohols and cyclohexane.Irradiation of ethyl 4-quinolinecarboxylate (1) yielded ethyl 2-hydroxyalkyl-4-quinolinecarboxylates (4a-c) in alcohols and ethyl 2-cyclohexyl-4-quinolinecarboxylate (4d) in cyclohexane in a good yield, respectively.The photochemical reactions of ethyl 3-quinolinecarboxylate (2) showed remarkable solvent dependency.Irradiation in methanol and cyclohexane afforded a solvent-additive product, ethyl 4-hydroxymethyl-1,4-dihydro-3-quinolinecarboxylate (5a) and ethyl 4-cyclohexyl-1,4-dihydro-3-quinolinecarboxylate (5b), while such photoaddition of the solvent did not proceed in ethanol and 2-propanol but instead ethyl 1,4-dihydro-3-quinolinecarboxylate (6) and dimeric compounds were formed, both of which were unstable and finally reverted to 2 at room temperature in air.In the case of ethyl 2-quinolinecarboxylate two types of the products, ethyl 4-hydroxyalkyl-1,4-dihydro-2-quinolinecarboxylate (7) and ethyl 1,4-dihydro-2-quinolinecarboxylate (8) were obtained in ethanol and 2-propanol but the yields of those products were poor.On the basis of triplet quenching experiments, the photochemical reactions of those ethyl quinolinecarboxylates are suggested to occur through hydrogen abstraction from the solvents by the ring nitrogen in the S1 state.
- Ono, Isao,Hata, Norisuke
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p. 2891 - 2898
(2007/10/02)
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- Novel Pyrethroid Insecticides. II. Synthesis of α-Cyano Substituted 3-Quinolylmethyl Esters
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A new type of pyrethroid insecticides containing quinoline system has been synthesized from the corresponding cyclopropanecarboxylic acid chlorides and α-cyano-3-quinolylmethanol.
- Balicki, Roman,Kozlowska, Margarita,Sobotka, Wieslaw
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p. 281 - 287
(2007/10/02)
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