- Structural and Reactivity Comparisons of JosiPhos CyPF-Cy and a Simplified Variant ("CyPBn-Cy") in Nickel-Catalyzed C(sp2)-N Cross-Couplings
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The synthesis and characterization of the new complexes (CyPBn-Cy)NiCl2 and (CyPBn-Cy)Ni(o-tol)Cl are reported (CyPBn-Cy = o-di(cyclohexyl)phosphino-benzyl-di(cyclohexyl)phosphine), along with a head-to-head structural and reactivity comparison of (L)Ni(o-tol)Cl precatalyst complexes (L = JosiPhos CyPF-Cy and CyPBn-Cy) in the Ni-catalyzed cross-couplings of (hetero)aryl chlorides or phenol-derived electrophiles with ammonia or furfurylamine. The structures of these precatalysts were found not to differ significantly (e.g., coordination geometry and % buried volume), and these similarities were, generally speaking, reflected in the observed catalytic behavior of these precatalysts, with notable exceptions including reactions involving the hindered electrophile 2-chloro-m-xylene, where (CyPBn-Cy)Ni(o-tol)Cl proved superior; the N-arylation of furfurylamine by use of 1-(N,N-diethylcarbamoyl)-naphthalene, where CyPF-Cy proved to be the preferred ligand; and monoarylation (CyPBn-Cy) versus diarylation (CyPF-Cy) selectivity in the cross-coupling of furfurylamine with 2-chloro-6-methoxypyridine. In studying the time-course of the cross-coupling of furfurylamine and 1-chloronaphthalene, significantly faster conversion to product and higher overall yield were noted when using CyPBn-Cy. These results confirm that CyPBn-Cy can be viewed as being competitive with, and complementary to, the well-established JosiPhos ligand CyPF-Cy in this class of Ni-catalyzed cross-couplings.
- Bodé, Nicholas E.,Ferguson, Michael J.,Stradiotto, Mark,Tassone, Joseph P.
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p. 2915 - 2922
(2021/08/27)
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- Preparation method of 2-methyl-4-aminoquinoline
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The invention relates to a preparation method of 2-methyl-4-aminoquinoline. The method comprises the following steps: (1) dissolving 2-methyl-4-chloroquinoline in a solvent, adding substituted benzylamine or benzylamine and an alkali, and carrying out an ammoniation reaction in order to obtain 2-methyl-4-aminoquinoline; and (2) carrying out a debenzylation reaction on the 2-methyl-4-aminoquinolineto obtain the 2-methyl-4-aminoquinoline. The preparation method of the 2-methyl-4-aminoquinoline takes the 2-methyl-4-chloroquinoline as a starting material, the substituted benzylamine or benzylamine is added, the ammoniation reaction is carried out under an alkaline condition, and the debenzylation reaction is carried out to obtain the target product. The method has characteristics of low preparation condition requirement, solving of the problem of high reaction difficulty in the synthesis of amino compounds from chlorides, high purity and high yield of the obtained product, production costreduction, and promotion values.
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Paragraph 0032; 0035; 0036; 0039
(2020/04/17)
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- Preparation method of dequalinium chloride
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The invention relates to a preparation method of dequalinium chloride. The method comprises the following steps: reacting 2-methyl-4-chloroquinoline, used as a starting material, with p-methoxybenzylamine to obtain an amination intermediate II, carrying out a debenzylation reaction on the intermediate to obtain 2-methyl-4-aminoquinaldine, then reacting the 2-methyl-4-aminoquinaldine with 1,10-diiododecane to obtain dequalinium iodide, continuously reacting the dequalinium iodide with hydrochloric acid to obtain dequalinium chloride, and finally recrystallizing with a mixed solvent to obtain refined dequalinium chloride. The preparation method of the dequalinium chloride does not adopt a highly toxic solvent nitrobenzene, and adopts a nontoxic or low-toxicity solvent, and the reaction temperature is reduced in the reaction process, so the method is environmentally friendly, and the reaction conditions are simple; and the refined dequalinium chloride product is prepared through recrystallization using the mixed solvent, so impurities in the dequalinium chloride process are controllable, the yield and purity of the prepared dequalinium chloride are high, the product quality is stable,and the method is suitable for industrial production.
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Paragraph 0040; 0043; 0047; 0050; 0054; 0057; 0061; 0064
(2020/05/01)
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- Synthesis method of 4-aminoquinaldine
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The invention relates to a synthesis method of 4-aminoquinaldine. The invention discloses the synthesis method of the 4-aminoquinaldine; the method comprises the following steps: enabling 2-methyl quinoline, taken as a starting raw material, to be subjected to a hydrogen peroxide oxidation reaction in acetic acid so as to generate 2-methylquinoline N-oxide; then, carrying out a nitration reactionto generate 2-methyl-4-nitroquinoline N-oxide; after that, illuminating for carrying out a reaction to generate 2-methyl-4-nitroquinoline; producing 2-methyl-4-aminoquinoline N-oxide by means of interaction of ferric trichloride hexahydrate and hydrazine hydrate in ethanol; finally, carrying out a reduction reaction by using iron powder under the action of acetic acid so as to generate the 4-aminoquinaldine. The synthesis method provided by the invention has the beneficial effects that the used raw materials and reagents are low in price and easy to obtain, the synthesis method is simple and feasible, the reaction conditions are mild, and a simple and convenient synthetic route is opened up to the synthesis of the 4-aminoquinaldine.
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Paragraph 0057; 0081; 0082; 0083
(2018/09/08)
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- Nickel-Catalyzed Amination of Aryl Carbamates with Ammonia
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Aryl carbamates were employed in the nickel-catalyzed monoarylation of ammonia. The applied, well-defined single-component nickel(II) precatalyst contains a Josiphos ligand, is air-stable, and operates without any ancillary reductant. This catalyst system
- Schranck, Johannes,Furer, Patrick,Hartmann, Veronika,Tlili, Anis
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supporting information
p. 3496 - 3500
(2017/07/04)
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- Nickel-Catalyzed Cross-Coupling of Ammonia or Primary Alkylamines with (Hetero)aryl Sulfamates, Carbamates, or Pivalates
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A catalyst system capable of effecting the cross-coupling of ammonia or primary alkylamines with (hetero)aryl sulfamates, carbamates, or pivalates is reported for the first time. The air-stable nickel(II) pre-catalyst C1 tolerates a broad spectrum of heterocyclic functionality within both reaction partners, as well as ether, nitrile, pyrrole, trifluoromethyl, and boronate ester substituents. In the case of reactions involving primary alkylamines and (hetero)aryl sulfamates and carbamates, room-temperature cross-couplings were achieved.
- MacQueen, Preston M.,Stradiotto, Mark
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supporting information
p. 1652 - 1656
(2017/08/11)
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- Nickel-Catalyzed Synthesis of Primary Aryl and Heteroaryl Amines via C-O Bond Cleavage
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A nickel-catalyzed protocol for the conversion of aryl and heteroaryl alcohol derivatives to primary and secondary aromatic amines via C(sp2)-O bond cleavage is described. The new amination protocol can be applied to a range of substrates bearing diverse functional groups and uses readily available benzophenone imines as an effective nitrogen source.
- Yue, Huifeng,Guo, Lin,Liu, Xiangqian,Rueping, Magnus
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supporting information
p. 1788 - 1791
(2017/04/11)
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- Nickel-catalyzed monoarylation of ammonia
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Structurally diverse (hetero)aryl chloride, bromide, and tosylate electrophiles were employed in the Ni-catalyzed monoarylation of ammonia, including chemoselective transformations. The employed JosiPhos/[Ni(cod)2] catalyst system enables the use of commercially available stock solutions of ammonia, or the use of ammonia gas in these reactions, thereby demonstrating the versatility and potential scalability of the reported protocol. Proof-of-principle experiments established that air-stable [(JosiPhos)NiCl2] precatalysts can be employed successfully in such transformations. Lighten Up: The substrate scope of the title reaction includes (hetero)aryl chloride, bromide, and tosylate electrophiles. The versatility and potential scalability of the reported method is demonstrated by the use of either commercially available stock solutions of ammonia or ammonia gas.
- Borzenko, Andrey,Rotta-Loria, Nicolas L.,Macqueen, Preston M.,Lavoie, Christopher M.,McDonald, Robert,Stradiotto, Mark
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supporting information
p. 3773 - 3777
(2015/03/18)
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- Exploring the Catalytic Reactivity of Nickel Phosphine-Phosphite Complexes
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In this study, we present an investigation into various nickel phosphite and phosphite-phosphine complexes for use in the Mizoroki-Heck and Suzuki-Miyaura cross-coupling reactions and the ammonia arylation reaction. In these coupling reactions, it was discovered that the Ni[P(OEt)3]4, (dppf)Ni[P(OPh)3]2, and (binap)Ni[P(OPh)3]2 catalysts were the most effective. In addition, an optimisation process for these catalytic systems as well as functional group compatibility are discussed.
- Kampmann, Sven S.,Man, Nikki Y. T.,McKinley, Allan J.,Koutsantonis, George A.,Stewart, Scott G.
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p. 1842 - 1853
(2015/12/26)
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- In situ generation of ammonia for the copper-catalyzed synthesis of primary aminoquinolines
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The synthesis of primary aminoquinolines from iodoquinolines was carried out in the presence of copper(i) iodide and formamide as the solvent and source of ammonia generated in situ. The reaction proceeded under mild conditions within a few hours and was applicable to various iodoquinolines.
- Aillerie, Alexandre,Pellegrini, Sylvain,Bousquet, Till,Pélinski, Lydie
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p. 1389 - 1391
(2014/05/06)
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- The divergent transformations of aromatic o-aminonitrile with carbonyl compound
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A modified Friedlaender conversion of the cyclocondensation of aromatic o-aminonitriles with carbonyl compounds was discovered. Systematic studies reveal that both the new transformation and the classic Friedlaender annulation in the presence of ZnCl2 constitute a pair of divergent reaction, and thecontrolled PDF transformation of this divergent reaction was achieved in the present of bases.
- Tang, Jianhong,Li, Jiarong,Zhang, Lijun,Ma, Shuling,Shi, Daxin,Zhang, Qi,Yang, Liupan,Wang, Xiuzhen,Liu, Xuan,Liu, Change
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experimental part
p. 533 - 542
(2012/08/27)
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- Recyclable catalysts for palladium-catalyzed aminations of aryl halides
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Aminated and recycled: Palladium/imidazolium phosphane catalysts enable efficient and general aminations of aryl halides, including direct amination with ammonia. Subsequent recycling is possible without any additional heterogenization (see scheme).
- Dumrath, Andreas,Luebbe, Christa,Neumann, Helfried,Jackstell, Ralf,Beller, Matthias
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experimental part
p. 9599 - 9604
(2011/10/04)
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- Recyclable catalysts for palladium-catalyzed C - O coupling reactions, Buchwald-Hartwig aminations, and Sonogashira reactions
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Simply reuse: Homogeneous palladium catalysts are effective and attractive tools for advanced organic synthesis (see example). Compound 1 belongs to a new class of ligands that enable recycling of the precious-metal catalyst directly from the reaction without any heterogenization.
- Dumrath, Andreas,Wu, Xiao-Feng,Neumann, Helfried,Spannenberg, Anke,Jackstell, Ralf,Beller, Matthias
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supporting information; experimental part
p. 8988 - 8992
(2011/02/23)
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- Efficient copper-catalyzed coupling of aryl chlorides, bromides and iodides with aqueous ammonia
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The copper(i)-catalyzed synthesis of a range of primary anilines from electron-rich and electron-deficient aryl halides including aryl chlorides has been achieved with aqueous ammonia, avoiding the need for inert atmosphere, expensive catalysts and ligands, anhydrous solvents, and additional base or other additives. The Royal Society of Chemistry 2009.
- Xu, Hanhui,Wolf, Christian
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supporting information; experimental part
p. 3035 - 3037
(2009/12/01)
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- A general palladium-catalyzed animation of aryl halides with ammonia
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A study was conducted to demonstrate palladium(Pd)-catalyzed amination of aryl halides with ammonia. The active catalyst was formed in situ from Pd(OAc)2, along with air- and moisture stable phosphines as pre-catalysts. It was found that the productivity of the catalyst system was similar to that of competitive Pd and phosphine systems. It was demonstrated that the novel electron-rich sterically demanding phosphine ligand was unable to be displaced from the palladium by ammonia to a significant extent, which prevented the deactivation of the catalyst by the ligand. It was also demonstrated that the Pd-catalyzed animation worked at ambient pressure. It was observed that the optimized system showed an excellent substrate scope including deactivated, electron-neutral, and activated halides, o-, m- p-substituted substrates, aryl chlorides, and heterocycles.
- Schulz, Thomas,Torborg, Christian,Enthaler, Stephan,Schaeffner, Benjamin,Dumrath, Andreas,Spannenberg, Anke,Neumann, Helfried,Boerner, Armin,Beller, Matthias
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experimental part
p. 4528 - 4533
(2009/12/24)
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- An unusual de-nitro reduction of 2-substituted-4-nitroquinolines
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The treatment of a variety of 2-substituted-4-nitroquinolines with Sn in the presence of concentrated hydrochloric acid in ethanol at 70 °C for 2-4 h afforded unusual de-nitro products 2-substituted-quinolines in good yields.
- Zhou, Yu,Li, Jian,Liu, Hong,Zhao, Linxiang,Jiang, Hualiang
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p. 8511 - 8514
(2007/10/03)
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- Selective removal of the N-(tert-butoxycarbonyl) protecting group using H-β zeolite
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A simple and efficient protocol for the selective removal of Boc group from nitrogen atom in conjugation with an aromatic system employing H-β zeolite is described.
- Tillu, Vasudha H.,Wakharkar, Radhika D.,Pandey, Rajesh K.,Kumar, Pradeep
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p. 1004 - 1007
(2007/10/03)
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- Substituted aminoquinolines as modulators of chemokine receptor activity
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The present invention is directed to aminoquinolines of Formula I: STR1 (wherein R 1, R 2, R 3, and R 4 are defined herein) which are useful as modulators of chemokine receptor activity. In particular, these compounds are useful as modulators of the chemokine receptors CCR-1, CCR-2, CCR-2A, CCR-2B, CCR-3, CCR-4, CCR-5, CXCR-3, and/or CXCR-4.
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- A simple strategy for the preparation of 4-aminoquinolines from β-functionalized enamines
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An easy and efficient synthesis of 4-aminoquinolines substituted with a phosphine oxide group in the 3-position 1, is described. The key step is a heterocyclization of cyano-aryl β-enamino phosphine oxides 4. The treatment of β-enamines derived from phosphonium salts 7, with a base afforded phosphazenes 8 and the hydrolysis of these phosphazenes led to the formation of substituted 4-aminoquinolines 9.
- Palacios, Francisco,Aparicio, Domitila,Garcia, Jesus
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p. 1647 - 1656
(2007/10/03)
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