- An unprecedented cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides
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A novel and facile cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides was developed for the synthesis of aryl amides. It was unprecedented that C[sbnd]N bond formation product was selectively generated without the common N[sbnd]O bond formation product. Aroyl peroxides act as the sole aroylation reagent without additional base or oxidant. The reactions proceeded under mild conditions and showed broad substrates scope with a series of primary amines and aroyl peroxides.
- Li, Dong,Li, Jiale,Li, Juanjuan,Yuan, Songdong,Zhang, Qian
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supporting information
(2020/09/16)
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- Nickel-catalyzed reductive amidation of aryl-triazine ethers
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The reaction of activated phenolic compounds, 2,4,6-triaryloxy-1,3,5-triazine (aryl-triazine ethers), with various isocyanates or carbodiimides in the presence of a nickel pre-catalyst resulted in the synthesis of aryl amides in good to excellent yields.
- Heravi, Majid M.,Panahi, Farhad,Iranpoor, Nasser
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supporting information
p. 1992 - 1995
(2020/02/22)
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- Hydrogen Bond Directed ortho-Selective C?H Borylation of Secondary Aromatic Amides
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Reported is an iridium catalyst for ortho-selective C?H borylation of challenging secondary aromatic amide substrates, and the regioselectivity is controlled by hydrogen-bond interactions. The BAIPy-Ir catalyst forms three hydrogen bonds with the substrate during the crucial activation step, and allows ortho-C?H borylation with high selectivity. The catalyst displays unprecedented ortho selectivities for a wide variety of substrates that differ in electronic and steric properties, and the catalyst tolerates various functional groups. The regioselective C?H borylation catalyst is readily accessible and converts substrates on gram scale with high selectivity and conversion.
- Bai, Shao-Tao,Bheeter, Charles B.,Reek, Joost N. H.
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supporting information
p. 13039 - 13043
(2019/07/31)
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- A solid-supported arylboronic acid catalyst for direct amidation
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An efficient heterogeneous amidation catalyst has been prepared by co-polymerisation of styrene, DVB with 4-styreneboronic acid, which shows wide substrate applicability and higher reactivity than the equivalent homogeneous phenylboronic acid, suggesting potential cooperative catalytic effects. The catalyst can be easily recovered and reused; suitable for use in packed bed flow reactors.
- Du, Yihao,Barber, Thomas,Lim, Sol Ee,Rzepa, Henry S.,Baxendale, Ian R.,Whiting, Andrew
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supporting information
p. 2916 - 2919
(2019/03/27)
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- An efficient transformation of methyl ethers and nitriles to amides catalyzed by Iron(III) perchlorate hydrate
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An efficient and inexpensive synthesis of N-substituted amides from the reaction of nitriles with methyl ethers catalyzed by Fe(ClO4)3·H2O is described. Fe(ClO4)3·H2O is an economically efficient catalyst for the Ritter Reaction under solvent-free conditions. A range of methyl ethers (benzyl, sec-alkyl and tert-butyl ethers) were reacted with nitriles to provide the corresponding amides in high–excellent yields.
- Yin, Guibo,Yan, Bin,Chen, Junqing,Ji, Min
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p. 1355 - 1363
(2019/04/30)
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- An efficient, one-pot transamidation of 8-aminoquinoline amides activated by tertiary-butyloxycarbonyl
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The efficient, one-pot access to the transamidation of 8-aminoquinoline (8-AQ), notorious for its harsh removal conditions, has been widely employed as an auxiliary in C–H functionalization reactions due to its strong directing ability. In this study, the facile and mild Boc protection of the corresponding 8-AQ amide was critical to activate the amide C(acyl)–N bond by twisting its geometry to lower the amidic resonance energy. Both aryl and alkyl amines proceeded transamidation in one-pot, user-friendly conditions with excellent yields.
- Wu, Wengang,Yi, Jun,Xu, Huipeng,Li, Shuangjun,Yuan, Rongxin
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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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- FeCl2·4H2O catalyzed ritter reaction with nitriles and halohydrocarbons
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An efficient and inexpensive synthesis of N-substituted amides from the Ritter reaction of nitriles with various halohydrocarbons catalyzed by FeCl2·4H2O is described. FeCl2·4H2O economically efficiently catalyzed the Ritter reaction under solvent-free conditions. A range of halohydrocarbons (benzyl, tert-butyl and sec-alkyl halohydrocarbons) were coupled with nitriles to provide the corresponding amides in high to excellent yields.
- Feng, Cheng-Liang,Yin, Gui-Bo,Yan, Bin,Chen, Jun-Qing,Ji, Min
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p. 345 - 353
(2019/02/12)
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- Nickel-Catalyzed Phosphine Free Direct N-Alkylation of Amides with Alcohols
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Herein, we developed an operational simple, practical, and selective Ni-catalyzed synthesis of secondary amides. Application of renewable alcohols, earth-abundant and nonprecious nickel catalyst facilitates the transformations, releasing water as byproduct. The catalytic system is tolerant to a variety of functional groups including nitrile, allylic ether, and alkene and could be extended to the synthesis of bis-amide, antiemetic drug Tigan, and dopamine D2 receptor antagonist Itopride. Preliminary mechanistic studies revealed the participation of a benzylic C-H bond in the rate-determining step.
- Das, Jagadish,Banerjee, Debasis
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p. 3378 - 3384
(2018/03/26)
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- Functional Group Transposition: A Palladium-Catalyzed Metathesis of Ar-X σ-Bonds and Acid Chloride Synthesis
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We describe the development of a new method to use palladium catalysis to form functionalized aromatics: via the metathesis of covalent σ-bonds between Ar-X fragments. This transformation demonstrates the dynamic nature of palladium-based oxidative addition/reductive elimination and offers a straightforward approach to incorporate reactive functional groups into aryl halides through exchange reactions. The reaction has been exploited to assemble acid chlorides without the use of high energy halogenating or toxic reagents and, instead, via the metathesis of aryl iodides with other acid chlorides.
- De La Higuera Macias, Maximiliano,Arndtsen, Bruce A.
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supporting information
p. 10140 - 10144
(2018/08/23)
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- Fe(ClO 4) 3 ·h 2 O-Catalyzed Ritter Reaction: A Convenient Synthesis of Amides from Esters and Nitriles
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An efficient and inexpensive synthesis of N-substituted amides from the Ritter reaction of nitriles with esters catalyzed by Fe(ClO 4) 3 ·H 2 O is described. Fe(ClO 4) 3 ·H 2 O is an economically efficient catalyst for the Ritter reaction under solvent-free conditions. Reactions of a range of esters (benzyl, sec-alkyl, and tert-butyl esters) with nitriles (primary, secondary, tertiary, and aryl nitriles) were performed to provide the corresponding amides in high to excellent yields.
- Feng, Chengliang,Yan, Bin,Yin, Guibo,Chen, Junqing,Ji, Min
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p. 2257 - 2264
(2018/10/20)
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- Amide Boc de-protection method
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The invention discloses an amide Boc de-protection method. The amide Boc de-protection method includes carrying out reaction on Boc protected amide III and amine IV under the condition of the presenceof palladium catalysts to generate new amide V. 8-aminoquinoline can be used as a guide group to be applied to chemical reaction, a process for synthesizing the new amide by means of de-protection isprovided, protecting groups can be easily removed by means of palladium catalysis, the new amide can be generated, and the reaction is high in efficiency. The amide Boc de-protection method has the advantages of environmental friendliness, recyclability and the like.
- -
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Paragraph 0035; 0121; 0122; 0123
(2018/09/13)
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- Synthesis of acyl fluorides via photocatalytic fluorination of aldehydic C-H bonds
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Acyl fluorides are versatile acylating agents owing to their unique stability. Their synthesis, however, can present challenges and is typically accomplished through deoxyfluorination of carboxylic acids. Here, we demonstrate that acyl fluorides can be prepared directly from aldehydes via a C(sp2)-H fluorination reaction involving the inexpensive photocatalyst sodium decatungstate and electrophilic fluorinating agent N-fluorobenzenesulfonimide. This convenient fluorination strategy enables direct conversion of aliphatic and aromatic aldehydes into acylating agents.
- Meanwell, Michael,Lehmann, Johannes,Eichenberger, Marc,Martin, Rainer E.,Britton, Robert
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p. 9985 - 9988
(2018/09/11)
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- Convenient synthesis of amides by Zn(ClO4)2·6H2O catalysed Ritter reaction with nitriles and halohydrocarbons
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A convenient and high yielding procedure for the synthesis of amides by the Ritter reaction of nitriles and halohydrocarbons in the presence of Zn(ClO4)2·6H2O as a highly stable, effective and available catalyst is described.
- Feng, Chengliang,Yin, Guibo,Yan, Bin,Chen, Junqing,Ji, Min
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supporting information
p. 383 - 386
(2018/08/21)
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- Method for preparing amide compound from 2-diazo-1, 3-dicarbonyl compound as acylating agent
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The invention provides a method for preparing an amide compound from a 2-diazo-1, 3-dicarbonyl compound as an acylating agent under non-metallic catalysis and neutral conditions. The method uses 2-diazo-1, 3-dicarbonyl compound as a raw material and carries out different benzoyl protection on different amino compounds so that a series of amide compounds are prepared. The method is carried out under neutral conditions, prevents the limitation of reaction substrates under conventional alkaline conditions, and has mild reaction conditions, high reaction efficiency and a simple operation method. The method provides a new and convenient method for preparation of amide compounds and protection of amino groups and can be used in the fields of chemical medicine, biology and materials.
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Paragraph 0052; 0090-0095
(2017/08/28)
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- A simple and greener approach for the amide bond formation employing FeCl3 as a catalyst
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Catalytic use of FeCl3 in the presence of glacial AcOH for the direct amidation of acid with amine in toluene has been described in this paper. The protocol worked well for the less nucleophilic aniline and its variants which gave the best results under the present reaction conditions. Amidation of bromoacetic acid and sterically hindered amino acid also proceed effectively to yield the corresponding amides. The protocol is catalytic and circumvents the use of stoichiometric amounts of reagents. The reaction led to water soluble by-products and thus makes the product isolation easier.
- Basavaprabhu,Muniyappa, Krishnamurthy,Panguluri, Nageswara Rao,Veladi, Panduranga,Sureshbabu, Vommina V.
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supporting information
p. 7746 - 7749
(2015/10/12)
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- A general continuous flow method for palladium catalysed carbonylation reactions using single and multiple tube-in-tube gas-liquid microreactors
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A series of continuous flow chemistry processes that facilitate the palladium-catalysed carbonylation of aryl and vinyl iodides and aryl bromides with a range of alkoxy, hydroxy and amino nucleophiles is reported. Harnessing a semipermeable Teflon AF-2400 Tube-in-Tube assembly, these reactors permit the controlled transport of carbon monoxide into solution at elevated pressure to generate homogeneous flow streams, avoiding some potential issues associated with segmented flow gas-liquid reactors. As the volume of pressurised gas contained within the device is low, the hazards associated with this are potentially mitigated relative to comparable batch processes. We also show how the incorporation of a second in-line gas-flow reactor allows for the sequential introduction of two gases (carbon monoxide and a gaseous nucleophile) into the reaction stream. A Teflon AF-2400 Tube-in-Tube reactor facilitates the use of carbon monoxide in continuous-flow C-C bond forming reactions providing esters, amides, carboxylic acids, lactones and lactams. Two reactors can be used in series to permit the sequential addition of two reactive gases (CO and Me2NH) into the flow stream.
- Gross, Ulrike,Koos, Peter,O'brien, Matthew,Polyzos, Anastasios,Ley, Steven V.
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supporting information
p. 6418 - 6430
(2016/02/18)
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- The α-effect in hydrazinolysis of 4-chloro-2-nitrophenyl x-substituted-benzoates: Effect of substituent x on reaction mechanism and the α-effect
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Second-order rate constants (kN) have been measured spectrophotometrically for the reaction of 4-chloro-2- nitrophenyl X-substituted-benzoates (6a-6h) with a series of primary amines including hydrazine in 80 mol % H2O/20 mol % DMSO at 25.0°C. The Bronsted-type plot for the reaction of 4-chloro-2-nitrophenyl benzoate (6d) is linear with βnuc = 0.74 when hydrazine is excluded from the correlation. Such a linear Bronsted-type plot is typical for reactions reported previously to proceed through a stepwise mechanism in which expulsion of the leaving group occurs in the rate-determining step (RDS). The Hammett plots for the reactions of 6a-6h with hydrazine and glycylglycine are nonlinear. In contrast, the Yukawa-Tsuno plots exhibit excellent linear correlations with ?X = 1.29-1.45 and r = 0.53-0.56, indicating that the nonlinear Hammett plots are not due to a change in RDS but are caused by resonance stabilization of the substrates possessing an electron-donating group (EDG). Hydrazine is ca. 47-93 times more reactive than similarly basic glycylglycine toward 6a-6h (e.g., the α-effect). The α-effect increases as the substituent X in the benzoyl moiety becomes a stronger electronwithdrawing group (EWG), indicating that destabilization of the ground state (GS) of hydrazine through the repulsion between the nonbonding electron pairs on the two N atoms is not solely responsible for the substituent-dependent α-effect. Stabilization of transition state (TS) through five-membered cyclic TSs, which would increase the electrophilicity of the reaction center or the nucleofugality of the leaving group, contributes to the α-effect observed in this study.
- Kim, Min-Young,Kim, Tae-Eun,Lee, Jieun,Um, Ik-Hwan
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p. 2271 - 2276
(2014/09/29)
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- A simple base-mediated amidation of aldehydes with azides
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A practical and efficient amidation reaction involving aromatic aldehydes and various azides under mild conditions is described. A broad spectrum of functional groups was tolerated, and the amides were synthesized in moderate to excellent yields, presenting an attractive alternative to the currently available synthetic methods.
- Kulkarni, Sameer S.,Hu, Xiangdong,Manetsch, Roman
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supporting information
p. 1193 - 1195
(2013/03/13)
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- Selective catalytic sp3 C-O bond cleavage with C-N bond formation in 3-alkoxy-1-propanols
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The ruthenium catalyzed selective sp3 C-O cleavage with amide formation was reported in reactions of 3-alkoxy-1-propanol derivatives and amines. The cleavage only occurs at the C3-O position even with 3-benzyloxy-1-propanol. Based on the experimental results, O-bound and C-bound Ru enolate complexes were proposed as key intermediates for the unique selective sp3 C-O bond cleavage in 3-alkoxy-1-propanols.
- Chen, Cheng,Hong, Soon Hyeok
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supporting information; experimental part
p. 2992 - 2995
(2012/07/28)
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- A reversible safety-catch method for the hydrogenolysis of N-benzyl moieties
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The benzyl groups of β-hydroxy-N-benzyl sulfonamides are labile toward hydrogenolysis-unlike N-benzyl sulfonamides lacking the β-hydroxy moiety. We find that N-acyl-N-benzyl sulfonamides undergo hydrogenolysis under very mild conditions. Based upon these observations, we developed a reversible safety-catch method using tert-butoxycarbonyl moieties to activate N-benzyl sulfonamides toward hydrogenolysis. We also explored the utility of the safety-catch activation method for other nitrogen-based functionality such as N-benzyl carboxamides, imides, and related functionality.
- Johnson II, David C.,Widlanski, Theodore S.
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p. 8483 - 8487
(2007/10/03)
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- Potential Central Nervous System Active Agents. 1. Synthesis of Aromatic N-Benzyl Amides
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The preparation and spectral properties (IR, MS, NMR) are given for 18 aromatic N-benzyl amides, variously substituted on the acyl part, including four new ones and an (E)-cinnamide derivative.The amides were prepared by heating the appropriate N-benzylammonium salt in o-xylene, or from the reaction of the corresponding acid chloride with benzylamine.The occurrence of an intense peak in their mass spectra, which corresponds to the loss of the N-acyl substituent without hydrogen transfer, is reported.
- Agwada, Vincent C.
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p. 479 - 481
(2007/10/02)
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