- Copper-catalyzed transformation of alkyl nitriles to N -arylacetamide using diaryliodonium salts
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This work reports a simple and efficient method for the copper-catalyzed redox-neutral transformation of alkyl nitriles using eco-friendly diaryliodonium salts and leading to N-arylacetamides. The method features high efficiency, broad substrate scope and good functional group tolerance.
- Sallio, Romain,Payard, Pierre-Adrien,Pakulski, Pawe?,Diachenko, Iryna,Fabre, Indira,Berteina-Raboin, Sabine,Colas, Cyril,Ciofini, Ilaria,Grimaud, Laurence,Gillaizeau, Isabelle
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p. 15885 - 15889
(2021/05/19)
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- Amine Activation: Synthesis of N-(Hetero)arylamides from Isothioureas and Carboxylic Acids
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A novel method for N-(hetero)arylamide synthesis based on rarely explored amine activation, rather than classical acid activation, is reported. The activated amines are easily prepared using a three-component reaction with commercial reagents. The new method shows a broad scope including challenging amides not (efficiently) accessible via classical protocols.
- Zhu, Yan-Ping,Sergeyev, Sergey,Franck, Philippe,Orru, Romano V. A.,Maes, Bert U. W.
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supporting information
p. 4602 - 4605
(2016/09/28)
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- Transition metal and base-free synthesis of 3,3-diaryl-2-oxindoles from 2,2,N-triarylacetamides
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A transition metal and base-free synthesis of 3,3-diaryl-2-oxindoles has been developed from 2,2,N-triarylacetamides in the presence of montmorillonite K-10 in 1,2-dichlorobenzene under O2 balloon atmosphere.
- Lim, Jin Woo,Kim, Ko Hoon,Moon, Hye Ran,Kim, Jae Nyoung
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p. 784 - 787
(2016/02/03)
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- Hydrogen-Bonded Homoleptic Fluoride-Diarylurea Complexes: Structure, Reactivity, and Coordinating Power
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Hydrogen bonding with fluoride is a key interaction encountered when analyzing the mode of action of 5′-fluoro-5′-deoxyadenosine synthase, the only known enzyme capable of catalyzing the formation of a C-F bond from F-. Further understanding of the effect of hydrogen bonding on the structure and reactivity of complexed fluoride is therefore important for catalysis and numerous other applications, such as anion supramolecular chemistry. Herein we disclose a detailed study examining the structure of 18 novel urea-fluoride complexes in the solid state, by X-ray and neutron diffraction, and in solution phase and explore the reactivity of these complexes as a fluoride source in SN2 chemistry. Experimental data show that the structure, coordination strength, and reactivity of the urea-fluoride complexes are tunable by modifying substituents on the urea receptor. Hammett analysis of aryl groups on the urea indicates that fluoride binding is dependent on σp and σm parameters with stronger binding being observed for electron-deficient urea ligands. For the first time, defined urea-fluoride complexes are used as fluoride-binding reagents for the nucleophilic substitution of a model alkyl bromide. The reaction is slower in comparison with known alcohol-fluoride complexes, but SN2 is largely favored over E2, at a ratio surpassing all hydrogen-bonded complexes documented in the literature for the model alkyl bromide employed. Increased second-order rate constants at higher dilution support the hypothesis that the reactive species is a 1:1 urea-fluoride complex of type [UF]- (U = urea) resulting from partial dissociation of the parent compound [U2F]-. The dissociation processes can be quantified through a combination of UV and NMR assays, including DOSY and HOESY analyses that illuminate the complexation state and H-bonding in solution.
- Pfeifer, Lukas,Engle, Keary M.,Pidgeon, George W.,Sparkes, Hazel A.,Thompson, Amber L.,Brown, John M.,Gouverneur, Véronique
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supporting information
p. 13314 - 13325
(2016/10/22)
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- Electrochemical oxidation of amides of type Ph2CHCONHAr
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Anodic oxidation of N-aryl-2,2-diphenylacetamides in acetonitrile undergoes three types of bond-cleavage, one between the benzylic carbon and the carbonyl group, the second between a carbonyl and 'N', and the third between the 'N' atom and aryl group. The selectivity of the cleavage and nature of emerged products is highly dependent on the nature of substituent attached to the aryl group. For example, electron-withdrawing groups direct the benzyl-carbonyl bond-breaking whereas electron-donating substituents favor the N-aryl bond cleavage. The type of products obtained involve benzophenone, 2,2-diphenylacetamide, N-(diphenylmethylene)acetamide, N-(diphenylmethyl)acetamide, α-lactam (1-acetyl-3,3-diphenylaziridin-2-one, as a 1:1 complex with 2,4-dinitroaniline) and aniline derivatives.
- Golub, Tatiana,Becker, James Y.
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experimental part
p. 3906 - 3912
(2012/06/04)
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- Pd-catalyzed carbonylation of diazo compounds at atmospheric pressure: A catalytic approach to ketenes
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The carbonylation of carbenes through catalytic cycles is highly desirable due to the importance of ketene-mediated reactions in organic synthesis. In this investigation, a highly efficient and mild catalytic approach toward ketene intermediates has been developed based on Pd-catalyzed carbonylation of diazo compounds with CO. When α-diazocarbonyl compounds or N-tosylhydrazone salts are heated in the presence of a palladium catalyst under atmospheric pressure of CO, ketene intermediates are formed in situ, where they undergo further reactions with various nucleophiles such as alcohols, amines, or imines. The Pd-catalyzed tandem carbonylation-Staudinger cycloaddition gives β-lactam derivatives in good yields with excellent trans diastereoselectivity. The results from DFT calculation on the reaction mechanism suggest that Pd is involved in the [2 + 2] cycloaddition process and affects the diastereoselectivity of the β-lactam products by assisting isomerization of the addition intermediate. On the other hand, the acylketenes generated from the Pd-catalyzed carbonylation of α-diazoketones react with imines in a formal [4 + 2] cycloaddition manner to afford 1,3-dioxin-4-one derivatives. This straightforward carbonylation provides a new approach toward highly efficient catalytic generation of ketene species under mild conditions.
- Zhang, Zhenhua,Liu, Yiyang,Ling, Lin,Li, Yuxue,Dong, Yian,Gong, Mingxing,Zhao, Xiaokun,Zhang, Yan,Wang, Jianbo
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supporting information; experimental part
p. 4330 - 4341
(2011/06/21)
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- Palladium-catalyzed amidation-hydrolysis reaction of gem-dihaloolefins: Efficient synthesis of homologated carboxamides from ketones
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A simple and efficient palladium-catalyzed amidation-hydrolysis reaction has been developed to afford N-aryl monosubstituted carboxamides in good to excellent yields from easily accessible ketone-derived gem-dihaloolefins and aryl amines.
- Ye, Wenchao,Mo, Jun,Zhao, Tiankun,Xu, Bin
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supporting information; experimental part
p. 3246 - 3248
(2009/12/01)
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- Selective mono- and di-N-alkylation of aromatic amines with alcohols and acylation of aromatic amines using Ph3P/DDQ
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Selective N-monoalkylation of aromatic amines with 1° and 2° alcohols and conversion of aromatic amines to amides are performed immediately and in excellent yields using triphenylphosphine (PPh3) and 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) in dichloromethane at room temperature. Symmetrical and unsymmetrical N,N-dialkylation of aromatic amines are also carried out in modest yield at room temperature by this reagent system.
- Iranpoor, Nasser,Firouzabadi, Habib,Nowrouzi, Najmeh,Khalili, Dariush
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experimental part
p. 3893 - 3899
(2009/09/08)
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- An atom efficient and solvent-free synthesis of structurally diverse amides using microwaves
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An array of structurally diverse amides was synthesized efficiently by combining (primary and secondary) amines and carboxylic acids in one-pot under solvent-free microwave (MW) conditions. In most cases, no racemization was observed with optically active inputs and chiral amides were obtained in high ee or de.
- Gelens, Edith,Smeets, Luc,Sliedregt, Leo A.J.M.,Van Steen, Bart J.,Kruse, Chris G.,Leurs, Rob,Orru, Romano V.A.
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p. 3751 - 3754
(2007/10/03)
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- Triphenylphosphine-2,4,4,6-tetrabromo-2,5-cyclohexadienone complex as a reagent for preparation of carboxylic acid bromides
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Triphenylphosphine-2,4,4,6-tetrabromo-2,5-cyclohexadienone complex was successfully used as a new reagent for the synthesis of carboxylic acid bromides which were isolated as individual substances or were identified by conversion into the corresponding anilides. The reaction is chemoselective, and it can be applied to polyfunctional compounds, e.g., hydroxy acids.
- Matveeva,Podrugina,Sandakova,Zefirov
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p. 1469 - 1472
(2007/10/03)
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- A simple and convenient procedure for the conversion of esters to secondary amides
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An improved procedure has been developed for the direct conversion of carboxylic esters to secondary amides by simple treatment with primary amines in presence of indium triiodide.
- Ranu, Brindaban C.,Dutta, Pinak
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p. 297 - 301
(2007/10/03)
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- Mild and selective reductions of aryl halides catalyzed by low-valent nickel complexes
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Treatment of aryl chlorides with catalytic amounts of (PPh3)2NiCl2+PPh3 in the presence of an equivalent of Me2NH·BH3 and either K2CO3 or Cs2CO3 in CH3CN under mild conditions leads to the corresponding product of reduction. Aryl bromides and iodides can also be reduced, selectively, using this reagent combination.
- Lipshutz, Bruce H.,Tomioka, Takashi,Pfeiffer, Steven S.
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p. 7737 - 7740
(2007/10/03)
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- N-acylbenzotriazoles: Neutral acylating reagents for the preparation of primary, secondary, and tertiary amides
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Readily available N-acylbenzotriazoles 2a-q efficiently acylate aqueous ammonia and primary and secondary amines to give primary, secondary, and tertiary amides in good to excellent yields. The wide applicability of the procedure is illustrated by the preparation of (i) α-hydroxyamides from α-hydroxy acids and of (ii) perfluoroalkylated amides.
- Katritzky,He,Suzuki
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p. 8210 - 8213
(2007/10/03)
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- 72. Thermal and Photochemical Reactions of 1,2-Annelated Barrelenes and Hydrobarrelenes in the Presence of Transition-Metal Carbonyls
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The -mediated retro-Diels-Alder reaction of the annelated barrelenes 1 afforded the 1H-indol-2(3H)-one derivatives 3 (Scheme 1), while the hydrobarrelene 4a, under the same conditions, was converted to the anilide 6 (Scheme 2); 4b remained unaff
- Trifonov, Latchezar S.,Orahovats, Alexander S.
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p. 648 - 652
(2007/10/02)
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- REACTIONS OF DICHLOROCARBENE WITH N-(2,2-DIPHENYLVINYLIDENE)ANILINES. 1,3-DIPOLAR DERIVATIVES OF KETENIMINE-YLIDES
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Ketenimide-ylides Ph2C=C-N(1+)(=CCl2)Ar, formed by the reaction of N-(2,2-diphenylvinylidene)anilines with dichlorocarbene, generated by heating sodium trichloroacetate in chloroform, undergoes -cycloaddition with dimethylacetylenedicarboxaylate, met
- Khlebnikov, A. F.,Novikov, M. S.,Kostikov, R. R.
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p. 1070 - 1076
(2007/10/02)
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- Effect of bis(acetylacetonato) copper(II) catalyst on the reaction of benzoylphenyldiazomethane with primary amines. A novel example of insertion of benzoylphenylcarbene into N-H bonds of amines
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Bis(acetylacetonato) coppert(II) catalysed thermal decomposition of benzoylphenyldiazomethane (1) leads to the insertion of benzoylphenylcarbene into the N-H bond of amines; the insertion products undergo facile air oxidation giving rise to ketoimines.The
- Singh, S. B.,Mehrotra, K. N.
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p. 2475 - 2478
(2007/10/02)
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