- Synthesis and studies on gem-fluorinated 2-azabicyclo[n.1.0]alkanes
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Three novel amines all possessing gem-difluorocyclopropane, secondary amino group and a fused aliphatic cycle were synthesized by difluorocyclopropanation of N-Boc protected enamides. The compounds were stable when amino group was blocked by protonation o
- Kubyshkin, Vladimir,Kheylik, Yurii,Mykhailiuk, Pavel K.
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- Electrochemical Amide Bond Formation from Benzaldehydes and Amines: Oxidation by Cathodic-Generated Hydrogen Peroxide
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Although amide bond formation from aldehydes and amines is a popular synthetic tool, most of the previously reported reactions depend on transition-metal catalysts or expensive oxidants. We considered that a more environmentally benign and safer approach could be achieved by electrochemistry. Nineteen benzamide derivatives were obtained with this reaction. NMR studies, cyclic voltammetry (CV) investigations, and control experiments showed that the corresponding intermediate, a hemiaminal, was transformed into the amide by oxidation with hydrogen peroxide generated in situ by cathodic reduction of molecular oxygen.
- Kurose, Yuma,Imada, Yasushi,Okada, Yohei,Chiba, Kazuhiro
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supporting information
p. 3844 - 3846
(2020/06/23)
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- Palladium-Catalyzed Desulfurative Amide Formation from Thioureas and Arylboronic Acids
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The development of the reactivity on carbene complexes would lead to the creation of novel synthetic strategies. We discovered herein the Pd-catalyzed desulfurative amide formation involved Suzuki-Miyaura coupling reaction, notably the Pd complex was generated in situ from thioureas, Ag salt and Pd catalyst. Silver salt was essential for the construction of this type of carbenes from available and stable thioureas and well participated in the catalytic cycle. We report a method for the synthesis of arylamides from arylboronic acids, which greatly enriched the application of thiourea chemistry and expanded the application of the Suzuki-Miyaura coupling.
- Su, Jianke,Li, Wendong,Li, Xin,Xu, Jian,Song, Qiuling
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p. 5664 - 5668
(2020/10/02)
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- Cobalt-catalyzed aminocarbonylation of (hetero)aryl halides promoted by visible light
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The catalytic aminocarbonylation of (hetero)aryl halides is widely applied in the synthesis of amides but relies heavily on the use of precious metal catalysis. Herein, we report an aminocarbonylation of (hetero)aryl halides using a simple cobalt catalyst under visible light irradiation. The reaction extends to the use of (hetero)aryl chlorides and is successful with a broad range of amine nucleophiles. Mechanistic investigations are consistent with a reaction proceeding via intermolecular charge transfer involving a donor-acceptor complex of the substrate and cobaltate catalyst.
- Alexanian, Erik J.,Veatch, Alexander M.
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p. 7210 - 7213
(2020/07/23)
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- Cross-Dehydrogenating Coupling of Aldehydes with Amines/R-OTBS Ethers by Visible-Light Photoredox Catalysis: Synthesis of Amides, Esters, and Ureas
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A straightforward synthesis of amides, ureas, and esters is reported by visible-light cross-dehydrogenating coupling (CDC) of aldehydes (or amine carbaldehydes) and amines/R-OTBS ethers by photoredox catalysis. The reaction is found to be general and high yielding. A plausible mechanistic pathway has been proposed for these transformations and is supported by appropriate controlled experiments.
- Pandey, Ganesh,Koley, Suvajit,Talukdar, Ranadeep,Sahani, Pramod Kumar
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supporting information
p. 5861 - 5865
(2018/09/21)
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- Visible-Light-Mediated Efficient Metal-Free Catalyst for α-Oxygenation of Tertiary Amines to Amides
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A metal-free system has been discovered for the efficient α-oxygenation of tertiary amines to the corresponding amides using oxygen as an oxidant. This visible-light-mediated oxygenation reaction exhibited excellent substrates scope under mild reaction conditions and generated water as the only byproduct. The synthetic utility of this approach has been demonstrated by applying onto drug molecules. At the end, detailed mechanistic reactions clearly showed the role of oxygen and the photocatalyst.
- Zhang, Yu,Riemer, Daniel,Schilling, Waldemar,Kollmann, Jiri,Das, Shoubhik
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p. 6659 - 6664
(2018/06/25)
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- Copper-Catalyzed Carbonylative Cross-Coupling of Arylboronic Acids with N-Chloroamines for the Synthesis of Aryl Amides
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A novel copper-catalyzed carbonylative cross-coupling between N-chloroamines and arylboronics acids has been developed. With copper(I) oxide as the catalyst, various desired amide compounds were produced in moderate to good yields. Functional groups such as iodide and alkene are tolerated. Notably, this is the first example of a copper-catalyzed aminocarbonylation with N-chloroamines.
- Yin, Zhiping,Wang, Zechao,Li, Wanfang,Wu, Xiao-Feng
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p. 1769 - 1772
(2017/04/13)
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- Palladium-Catalyzed Carbonylative Synthesis of Amides from Aryltriazenes under Additive-Free Conditions
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An interesting palladium-catalyzed carbonylative synthesis of amides from aryltriazenes was developed. By using Pd(MeCN2)Cl2 as the catalyst precursor under CO pressure through a N2 extrusion/CO insertion sequence, a broad range of aryltriazenes were transformed into the corresponding amides in good yields with excellent functional group tolerance. Remarkably, no additives such as acids or phosphine ligands were required.
- Yin, Zhiping,Wang, Zechao,Wu, Xiao-Feng
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supporting information
p. 3992 - 3995
(2017/07/28)
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- Copper-Catalyzed Aerobic Oxidative Amidation of Benzyl Alcohols
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A Cu-catalyzed synthesis of amides from alcohols and secondary amines using the oxygen in air as the terminal oxidant has been developed. The methodology is operationally simple requiring no high pressure equipment or handling of pure oxygen. The commercially available, nonprecious metal catalyst, Cu(phen)Cl2, in conjunction with di-tert-butyl hydrazine dicarboxylate and an inorganic base provides a variety of benzamides in moderate to excellent yields. The pKa of amine conjugate acid and electronics of alcohol were shown to impact the selection of base for optimal reactivity. A mechanism consistent with the observed reactivity trends, KIE, and Hammett study is proposed.
- Krabbe, Scott W.,Chan, Vincent S.,Franczyk, Thaddeus S.,Shekhar, Shashank,Napolitano, José G.,Presto, Carmina A.,Simanis, Justin A.
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p. 10688 - 10697
(2016/11/29)
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- Iron-catalyzed direct synthesis of amides from methylarenes
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An efficient, green and first catalytic process has been developed for the direct synthesis of amides from readily available petroleum by-products (methylarenes) and amines using an iron catalyst. In this new catalytic reaction, the methyl group of the me
- Srinivas Kotha, Surya,Badigenchala, Sindhura,Sekar, Govindasamy
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p. 1437 - 1445
(2015/05/19)
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- Anionic phenoxy-amido rare-earth complexes as efficient catalysts for amidation of aldehydes with amines
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A series of anionic organo-rare-earth amido complexes stabilized by dianionic phenoxy-amido ligands were prepared and their catalytic behavior for amidation reactions of aldehydes with amines was elucidated. Amine elimination reaction of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with an equimolar of lithium aminophenoxy {[HNO]1Li(THF)}2, which was prepared by the reaction of [HNOH]1 {[HNOH]1 = N-p-fluoro-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine} with one equivalent of n-BuLi in tetrahydrofuran (THF) in situ, gave the anionic phenoxy-amido rare earth amido complexes [NO]12Ln[N(SiMe3)2][Li(THF)]2 [Ln = Y (1), Yb (2), Sm (3), Nd (4)] in high isolated yields. Similar reactions of Ln[N(SiMe3)2]3(μ-Cl)Li(THF)3 with {[HNO]2Li(THF)}2, and {[HNO]3Li(THF)}2 in THF gave the anionic rare-earth amides [NO]22Ln[N(SiMe3)2][Li(THF)]2 [Ln = Sm (5), Nd (6)] and [NO]32Ln[N(SiMe3)2][Li(THF)]2 [Ln = Sm (7), Nd (8)] {[HNOH]2 = N-p-chloro-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine; [HNOH]3 = N-p-bromo-phenyl(2-hydroxy-3,5-di-tert-butyl)benzylamine}, respectively. All of these complexes were fully characterized. X-ray structural determination revealed that these complexes are isostructural, and have solvated monomeric structures. Each of the rare-earth ions is coordinated by two phenoxy-amido ligands and one N(SiMe3)2 group, and the coordination geometry can be described as a distorted trigonal bipyramid. Each of the lithium atoms is surrounded by one aryloxo group, one amido group and one THF molecule, and the coordination geometry can be described as a trigonal plane. The catalytic behavior of these rare-earth amides for the amidation reaction of aldehyde with amine was elucidated. It was found that these complexes are efficient catalysts for this transformation to produce amides in good to excellent yields under mild reaction conditions, and in some cases, diacylamide compounds can be prepared conveniently.
- Wang, Chao,Huang, Lingling,Lu, Min,Zhao, Bei,Wang, Yaorong,Zhang, Yong,Shen, Qi,Yao, Yingming
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p. 94768 - 94775
(2015/11/24)
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- N2 extrusion and co insertion: A novel palladium-catalyzed carbonylative transformation of aryltriazenes
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A novel procedure for the replacement of N2 with CO of aryltriazenes has been developed. Aryltriazenes were converted to the corresponding arylamides catalyzed by 1 mol % of PdCl2/P(o-Tol)3 under CO pressure. In this process, aryldiazonium salts were generated in the presence of 40 mol % of MeSO3H. Nitrogen was released from the substrates and CO formally inserted. Aryl bromides, iodides, alkynes, and free hydroxyl groups can be tolerated in this transformation.
- Li, Wanfang,Wu, Xiao-Feng
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p. 1910 - 1913
(2015/04/27)
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- Mild and selective Et2Zn-catalyzed reduction of tertiary amides under Hydrosilylation conditions
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Diethylzinc (Et2Zn) can be used as an efficient and chemoselective catalyst for the reduction of tertiary amides under mild reaction conditions employing cost-effective polymeric silane (PMHS) as the hydride source. Crucial for the catalytic activity was the addition of a substoichiometric amount of lithium chloride to the reaction mixture. A series of amides containing different additional functional groups were reduced to their corresponding amines, and the products were isolated in good-to-excellent yields.
- Kovalenko, Oleksandr O.,Volkov, Alexey,Adolfsson, Hans
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supporting information
p. 446 - 449
(2015/03/05)
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- Catalytic bio-chemo and bio-bio tandem oxidation reactions for amide and carboxylic acid synthesis
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A catalytic toolbox for three different water-based one-pot cascades to convert aryl alcohols to amides and acids and cyclic amines to lactams, involving combination of oxidative enzymes (monoamine oxidase, xanthine dehydrogenase, galactose oxidase and laccase) and chemical oxidants (TBHP or CuI(cat)/H2O2) at mild temperatures, is presented. Mutually compatible conditions were found to afford products in good to excellent yields. This journal is
- Bechi, Beatrice,Herter, Susanne,McKenna, Shane,Riley, Christopher,Leimkühler, Silke,Turner, Nicholas J.,Carnell, Andrew J.
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supporting information
p. 4524 - 4529
(2014/12/11)
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- A general copper-mediated nucleophilic 18F fluorination of arenes
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Molecules labeled with fluorine-18 are used as radiotracers for positron emission tomography. An important challenge is the labeling of arenes not amenable to aromatic nucleophilic substitution (SNAr) with [ 18F]F-. In the
- Tredwell, Matthew,Preshlock, Sean M.,Taylor, Nicholas J.,Gruber, Stefan,Huiban, Mickael,Passchier, Jan,Mercier, Joel,Genicot, Christophe,Gouverneur, Veronique
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supporting information
p. 7751 - 7755
(2014/08/05)
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- The direct amidation of α-diketones with amines via TBHP-promoted oxidative cleavage of C(sp2)-C(sp2) bonds
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A novel and efficient direct amidation of α-diketones with amines via TBHP-promoted oxidative cleavage of C(sp2)-C(sp2) bonds has been developed. The strategy provides an alternative approach to amides under metal-free conditions.
- Zhao, Qiong,Li, Hongji,Wang, Lei
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supporting information
p. 6772 - 6779
(2013/10/01)
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- Iron-catalysed oxidative amidation of alcohols with amines
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A new iron-catalysed oxidative amidation of differently substituted benzylic alcohols with mono- and di-substituted amines was developed. The Royal Society of Chemistry 2013.
- Gaspa, Silvia,Porcheddu, Andrea,De Luca, Lidia
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supporting information
p. 3803 - 3807
(2013/07/26)
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- Aerobic oxidative amidation of aromatic and cinnamic aldehydes with secondary amines by CuI/2-pyridonate catalytic system
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A simple and convenient CuI/2-pyridonate catalytic system for the oxidative amidation of aldehydes with secondary amines has been developed. With this system, a variety of useful arylamides have been synthesized in moderate to good yields in the presence of small amount of copper catalyst and the pyridonate ligand, generating only water as a coproduct. Synthesis of cinnamamides was also achieved by the reactions of cinnamaldehydes with secondary amines in moderate yields. Air was successfully employed as a green oxidant in this catalytic system, achieving a safe and atom-efficient system for the synthesis of amides.
- Zhu, Mingwen,Fujita, Ken-Ichi,Yamaguchi, Ryohei
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p. 9102 - 9109,8
(2012/12/11)
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- Synthesis and structural diversity of heterobimetallic lanthanide-potassium complexes and catalytic activity for amidation of aldehydes with amines
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Four heterobimetallic lanthanide-potassium complexes stabilized by the carbon-bridged bis(phenolate) ligand MBMP2- (MBMP = 2,2′-methylene bis(6-tert-butyl-4-methylphenolate)), [{(MBMP) 2La(THF)2}2K][K(THF)6] (1), [(MBMP)Nd(μ-MBMP)K(THF)]2 (2), [(THF)2Sm(MBMP) 2K(THF)2] (3), and [(THF)2Yb(MBMP) 2K(THF)3] (4), were synthesized, and their structural features were provided. It was found that the ionic radii of lanthanide metals have a profound effect on the structures of the heterobimetallic complexes. Complexes 1 to 4 are efficient catalysts for amidation reactions of aldehydes with amines to produce amides in good to excellent yields under mild conditions.
- Xu, Bin,Huang, Lingling,Yang, Zijian,Yao, Yingming,Zhang, Yong,Shen, Qi
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experimental part
p. 3588 - 3595
(2011/09/12)
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- Hydrogen peroxide mediated efficient amidation and esterification of aldehydes: Scope and selectivity
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An efficient method for the amidation and esterification of aldehydes utilizing hydrogen peroxide as an oxidant has been developed. Cyclic amines and primary alcohols selectively reacted with aromatic aldehydes under mild conditions to yield the corresponding amides and esters.
- Tank, Rekha,Pathak, Uma,Vimal, Manorama,Bhattacharyya, Shubhankar,Pandey, Lokesh Kumar
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p. 3350 - 3354
(2012/01/06)
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- Anionic bridged bis(amidinate) lithium lanthanide complexes: Efficient bimetallic catalysts for mild amidation of aldehydes with amines
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Anionic bridged bis(amidinate) lithium lanthanide complexes have been found to be efficient catalysts for the amidation of aldehydes with amines under mild conditions. The activity follows the order : yttrium neodymium europium ytterbium. The catalysts are available for the formation of benzamides derived from pyrrolidine, piperidine, and morpholine with good to excellent yields. In comparison with the corresponding neutral complexes, the anionic complexes show higher activity and a wider range of scope for the amines. A cooperation of the lanthanide and lithium metals in this process is proposed to contribute to the high activity of the present catalyst.
- Wang, Junfeng,Li, Junmei,Xu, Fan,Shen, Qi
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supporting information; experimental part
p. 1363 - 1370
(2009/12/09)
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- Heterobimetallic lanthanide/sodium phenoxides: Efficient catalysts for amidation of aldehydes with amines
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Heterobimetallic lanthanide/sodium phenoxides were found to be efficient catalysts for amidation of aldehydes with amines under mild conditions. The reactivity follows the order Nd 2C6H3O iPr) 2C6H3O 2C 6H3O for phenoxide groups. In comparison with the corresponding monometallic complexes, heterobimetallic complexes show higher activity and a wider range of scope of amines. A cooperation of lanthanide and sodium in this process is proposed to contribute to the high activity of the present catalyst.
- Li, Junmei,Xu, Fan,Zhang, Yong,Shen, Qi
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supporting information; experimental part
p. 2575 - 2577
(2009/07/18)
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- Microwave-enhanced aminocarbonylations in water
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(Chemical Equation Presented) Aryl bromides can be rapidly converted to the corresponding secondary and tertiary benzamides in water. By using Mo(CO) 6 as the source of carbon monoxide, aminocarbonylations were conducted under air after only 10
- Wu, Xiongyu,Larhed, Mats
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p. 3327 - 3329
(2007/10/03)
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- SUBSTITUTED PIPERIDINES AS HISTAMINE H3 RECEPTOR LIGANDS
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The present invention relates to novel piperidine ether derivatives having affinity for the histamine H3 receptor, processes for their preparation, to compositions containing them and to their use in the treatment of neurological and psychiatric disorders.
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(2010/02/10)
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