- Carboxylic Acid Deoxyfluorination and One-Pot Amide Bond Formation Using Pentafluoropyridine (PFP)
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This work describes the application of pentafluoropyridine (PFP), a cheap commercially available reagent, in the deoxyfluorination of carboxylic acids to acyl fluorides. The acyl fluorides can be formed from a range of acids under mild conditions. We also demonstrate that PFP can be utilized in a one-pot amide bond formation via in situ generation of acyl fluorides. This one-pot deoxyfluorination amide bond-forming reaction gives ready access to amides in yields of ≤94%.
- Brittain, William D. G.,Cobb, Steven L.
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p. 5793 - 5798
(2021/08/01)
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- Visible-Light-Promoted Iron-Catalyzed N-Arylation of Dioxazolones with Arylboronic Acids
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A visible-light-promoted and simple iron salt-catalyzed N-arylation was achieved efficiently under external photosensitizer-free conditions. Arylboronic acids and bench-stable dioxazolones were used for this cross-coupling reaction. This reaction features high reactivity, wide substrate scope, good functional group tolerance, simple operation procedure, and mild reaction conditions. Preliminary mechanistic investigations were conducted to support a radical pathway. This method may contribute to shift the paradigm of iron-catalyzed C-N bond construction and nitrene transfer chemistry.
- Tang, Jing-Jing,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
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p. 13955 - 13961
(2021/11/20)
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- Practical one-pot amidation of N -Alloc-, N -Boc-, and N -Cbz protected amines under mild conditions
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A facile one-pot synthesis of amides from N-Alloc-, N-Boc-, and N-Cbz-protected amines has been described. The reactions involve the use of isocyanate intermediates, which are generated in situ in the presence of 2-chloropyridine and trifluoromethanesulfonyl anhydride, to react with Grignard reagents to produce the corresponding amides. Using this reaction protocol, a variety of N-Alloc-, N-Boc-, and N-Cbz-protected aliphatic amines and aryl amines were efficiently converted to amides with high yields. This method is highly effective for the synthesis of amides and offers a promising approach for facile amidation.
- Hong, Wan Pyo,Tran, Van Hieu,Kim, Hee-Kwon
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p. 15890 - 15895
(2021/05/19)
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- Triflic anhydride mediated synthesis of 3,4-dihydroquinazolines: A three-component one-pot tandem procedure
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A one-pot three-component tandem reaction involving a key Pictet-Spengler-like annulation step has been developed, providing an efficient method for the synthesis of 3,4-dihydroquinazolines in moderate to good yields from amides, aldehydes, and amines. The multicomponent triflic anhydride mediated reaction tolerates the installation of numerous functional groups, affording extensive diversity about the heterocyclic scaffold.
- Magyar, Christina L.,Wall, Tyler J.,Davies, Steven B.,Campbell, Molly V.,Barna, Haven A.,Smith, Sydney R.,Savich, Christopher J.,Mosey, R. Adam
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supporting information
p. 7995 - 8000
(2019/09/06)
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- Base-Promoted Amidation and Esterification of Imidazolium Salts via Acyl C-C bond Cleavage: Access to Aromatic Amides and Esters
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Imidazolium salts have been effectively employed as suitable acyl transfer agents in amidation and esterification in organic synthesis. The weak acyl C(O)-C imidazolium bond was exploited to generate acyl electrophiles, which further react with amines and alcohols to afford amides and esters. The broad substrate scope of anilines and benzylic amines and base-promoted conditions are the benefits of this route. Interestingly, phenol, benzylic alcohols, and a biologically active alcohol can also be subjected to esterification under the optimized conditions.
- Karthik, Shanmugam,Muthuvel, Karthick,Gandhi, Thirumanavelan
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p. 738 - 751
(2019/01/24)
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- Solvent- and transition metal-free amide synthesis from phenyl esters and aryl amines
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A general, economical, and environmentally friendly method of amide synthesis from phenyl esters and aryl amines was developed. This new method has significant advantages compared to previously reported palladium-catalyzed approaches. The reaction is performed transition metal- and solvent-free, using a cheap and environmentally benign base, NaH. This approach enabled us to obtain target amides in high yields with high atom economy.
- Rzhevskiy, Sergey A.,Ageshina, Alexandra A.,Chesnokov, Gleb A.,Gribanov, Pavel S.,Topchiy, Maxim A.,Nechaev, Mikhail S.,Asachenko, Andrey F.
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p. 1536 - 1540
(2019/01/24)
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- Synthesis of Amides by Mild Palladium-Catalyzed Aminocarbonylation of Arylsilanes with Amines Enabled by Copper(II) Fluoride
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A general Pd-catalyzed synthesis of amides by oxidative aminocarbonylation of arylsilanes under mild conditions was accomplished for the first time. The reaction is promoted by a commercially available copper(II) fluoride, which acts as a dual silane activator and mild oxidant, enabling highly efficient aminocarbonylation of versatile arylsilanes at atmospheric CO pressure. The reaction is tolerant of a wide range of arylsilanes and various sensitive halide functional groups as well as a broad scope of amines are compatible with this oxidative process using cheap CO. A significant aspect involves the increased efficiency by the catalyst system. The reaction represents a segue into the powerful Pd-catalyzed oxidative transformations of organosilanes.
- Zhang, Jin,Hou, Yanyan,Ma, Yangmin,Szostak, Michal
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p. 338 - 345
(2019/01/10)
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- Synthesis of Secondary Amides through the Palladium(II)-Catalyzed Aminocarbonylation of Arylboronic Acids with Amines or Hydrazines and Carbon Dioxide
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A new Pd-catalyzed aminocarbonylation of arylboronic acids with amines or phenylhydrazines has been developed. Various secondary amides were produced from readily available substrates and cheap common metal catalysts in a CO atmosphere (balloon). Remarkably, we presents the first example of aminocarbonylations between arylboronic acids and phenylhydrazines.
- Zhang, Jin,Ma, Yuqiang,Ma, Yangmin
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supporting information
p. 1720 - 1725
(2018/04/24)
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- PROCESS FOR DIRECT AMIDATION OF AMINES VIA RH(I)-CATALYZED ADDITION OF BOROXINES
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This invention relates to a process for making an amide by directly reacting a ferf-butyloxycarbonyl or carboxybenzyl N substituted amine with a boroxine derivative in the presence of a rhodium(l) catalyst, in the presence of a solvent an optionally in the presence of a base. The process provides means to react protected amines to amides using th boroganic reagent without the deprotection of an amine such that it can be directly converted from protected form in on step, and results in good yields in amide formation even for sterically hindered amines. Potassium fluoride is the preferre base in the reaction run in dioxane. Typical rhodium catalysts that can be used include rhodium(l) complex monomer and dimers such as chloro(1,5-cyclooctadiene) rhodium(l) dimer ("[CI(cod)Rh]2") or bis(1,5-cyclooctadiene)rhodium(l trifluoromethanesulfonate ("(cod)2Rh(OTf)").
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Page/Page column 11; 12
(2017/03/28)
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- Copper(i)-catalyzed amidation reaction of organoboronic esters and isocyanates
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A simple and efficient methodology for the preparation of amides from easily available organoboronic esters and isocyanates has been accomplished using a ligand-free copper(i) catalyst. The reaction system demonstrated a broad substrate scope and provided convenient access to a wide variety of secondary amides.
- Salim Lew, Tedrick Thomas,Wen Lim, Diane Shu,Zhang, Yugen
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p. 5140 - 5143
(2015/12/05)
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- Direct Amidation of N-Boc- and N-Cbz-Protected Amines via Rhodium-Catalyzed Coupling of Arylboroxines and Carbamates
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N-Boc- and N-Cbz-protected amines are directly converted into amides by a novel rhodium-catalyzed coupling of arylboroxines and carbamates, replacing the traditional two-step deprotection-condensation sequence. Both protected anilines and aliphatic amines are efficiently transformed into a wide variety of secondary benzamides, including sterically hindered and electron-deficient amides, as well as in the presence of acid-labile and reducible functional groups.
- Lim, Diane S. W.,Lew, Tedrick T. S.,Zhang, Yugen
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supporting information
p. 6054 - 6057
(2016/01/09)
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- Copper catalyzed N-arylation between aryl halides and nitriles in water: An efficient tandem synthesis of benzanilides
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A series of benzanilide compounds were synthesized through copper-catalyzed tandem reactions. With the assistance of ionic liquid as phase transfer catalyst, aryl halides, and nitriles underwent a hydrolysis/coupling pathway to form benzanilides in water. Advantages of this reaction include the use of water as the environmental friendly solvent, short reaction time, and the tolerance of various functional groups. A proposed mechanism based on control experiments is also presented.
- Wang, Jichao,Yin, Xinchi,Wu, Jun,Wu, Datong,Pan, Yuanjiang
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p. 10463 - 10469
(2013/11/19)
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- Octanuclear Cu(I)-dithiophosphates: An efficient catalyst system for N-arylation of azoles, amines, and amides
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The formation of a C-N bond via the cross-couplings of aryl iodides with azoles, aryl amine, and amides can be successfully achieved in decent yield by the utilization of both [Cu8(H){S2P(OiPr) 2}6]+ and [Cu8{S2P(OEt) 2}6]2+ as the pre-catalysts.
- Wu, Cheng-Chieh,Lee, Bo-Han,Liao, Ping-Kuei,Fang, Ching-Shiang,Liu
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experimental part
p. 480 - 484
(2012/07/30)
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- Copper catalyzed coupling of aryl chlorides, bromides and iodides with amines and amides
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A copper(i) catalyzed procedure for carbon-nitrogen bond formation utilizing aryl halides and either amines, including amino acids and diphenylamine, or aliphatic and aromatic amides is described. The Royal Society of Chemistry.
- Xu, Hanhui,Wolf, Christian
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supporting information; experimental part
p. 1715 - 1717
(2009/08/08)
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- Toward optimization of the linker substructure common to transthyretin amyloidogenesis inhibitors using biochemical and structural studies
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To develop potent and highly selective transthyretin (TTR) amyloidogenesis inhibitors, it is useful to systematically optimize the three substructural elements that compose a typical TTR kinetic stabilizer: the two aryl rings and the linker joining them. Herein, we evaluated 40 bisaryl molecules based on 10 unique linker substructures to determine how these linkages influence inhibitor potency and selectivity. These linkers connect one unsubstituted aromatic ring to either a 3,5-X2 or a 3,5-X2-4-OH phenyl substructure (X = Br or CH3). Coconsideration of amyloid inhibition and ex vivo plasma TTR binding selectivity data reveal that direct connection of the two aryls or linkage through nonpolar E-olefin or -CH2CH2- substructures generates the most potent and selective TTR amyloidogenesis inhibitors exhibiting minimal undesirable binding to the thyroid hormone nuclear receptor or the COX-1 enzyme. Five high-resolution TTR·inhibitor crystal structures (1.4-1.8 A?) provide insight into why such linkers afford inhibitors with greater potency and selectivity.
- Johnson, Steven M.,Connelly, Stephen,Wilson, Ian A.,Kelly, Jeffery W.
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supporting information; experimental part
p. 6348 - 6358
(2009/12/03)
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- Copper-catalyzed formation of carbon-heteroatom and carbon-carbon bonds
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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-nitrogen bond between the nitrogen atom of an amide or amine moiety and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In additional embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between a nitrogen atom of an acyl hydrazine and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. In other embodiments, the present invention relates to copper-catalyzed methods of forming a carbon-nitrogen bond between the nitrogen atom of a nitrogen-containing heteroaromatic, e.g., indole, pyrazole, and indazole, 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-oxygen bond between the oxygen atom of an alcohol and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. The present invention also relates to copper-catalyzed methods of forming a carbon-carbon bond between a reactant comprising a nucleophilic carbon atom, e.g., an enolate or malonate anion, and the activated carbon of an aryl, heteroaryl, or vinyl halide or sulfonate. Importantly, all the methods of the present invention are relatively inexpensive to practice due to the low cost of the copper comprised by the catalysts.
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- Efficient photochemical synthesis of tricyclic keto-indoles
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Tricyclic keto-indoles were synthesized by photocyclization of easily obtained enaminones in an electrocyclic photochemical reaction. The three methods reported were chosen according to the enaminone structure. The most general procedure using one-step synthesis was carried out in a benzene-methanol solution in the presence of sodium methylate. In the case of base sensitive substrates, the best method was photocyclization followed by oxidation. Besides, N-unsubstituted indoles with a five-membered ring were prepared by a photolysis reaction. All three methods are efficient and easy to perform.
- Tietcheu, Christele,Garcia, Christophe,Gardette, Daniel,Dugat, Denise,Gramain, Jean-Claude
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p. 965 - 973
(2007/10/03)
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- A general and efficient copper catalyst for the amidation of aryl halides
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An experimentally simple and inexpensive catalyst system was developed for the amidation of aryl halides by using 0.2-10 mol % of Cul, 5-20 mol % of a 1,2-diamine ligand, and K3PO4, K2CO3, or Cs2CO3 as base. Catalyst systems based on N, N′-dimethylethylenediamine or trans-N,N′-dimethyl-1,2-cyclohexanediamine were found to be the most active even though several other 1,2-diamine ligands could be used in the easiest cases. Aryl iodides, bromides, and in some cases even aryl chlorides can be efficiently amidated. A variety of functional groups are tolerated in the reaction, including many that are not compatible with Pd-catalyzed amidation or amination methodology.
- Klapars, Artis,Huang, Xiaohua,Buchwald, Stephen L.
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p. 7421 - 7428
(2007/10/03)
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