- (Chloro-phenylthio-methylene)dimethylammonium chloride (CPMA): A new coupling reagent for the formation of ester and amide bond
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CPMA is an efficient agent for the formation of esters and amides from carboxylic acids. It is compatible with substrates that are sensitive to basic conditions or oxophilic reagents. The reaction proceeds without racemization of chirally labile carboxylic acids. All these advantages make CPMA a valuable adjunct to the existing arsenal of coupling reagents.
- Gomez, Laurent,Ngouela, Silvère,Gellibert, Fran?oise,Wagner, Alain,Mioskowski, Charles
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Read Online
- A mild and efficient amide formation reaction mediated by P(OEt)3 and iodine
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With the activation of P(OEt)3 and I2, carboxylic acids can smoothly react with various primary and secondary amines, affording a series of amides, including peptides without racemization. 31P NMR spectroscopy studies showed that carboxylic phosphoric mixed anhydride was the reactive intermediate and a possible mechanism was herein proposed.
- Chen, Pei-Jiang,Wang, Hai-Yang,Peng, Ai-Yun
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Read Online
- Hypervalent Iodine Reagent-Promoted Hofmann-Type Rearrangement/Carboxylation of Primary Amides
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A novel transformation of primary amides to secondary amides promoted by hypervalent iodine reagents was developed. The hypervalent iodine reagent-mediated Hofmann-type rearrangement generated an isocyanate intermediate, which was subsequently trapped by an in situ generated carboxylic acid from the hypervalent iodine reagent to provide the corresponding secondary amides. This method provided a facile and efficient route for the synthesis of secondary amides from primary amides and also revealed novel reactivities of hypervalent iodine reagents.
- Wang, Xia,Yang, Peng,Hu, Bo,Zhang, Qian,Li, Dong
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p. 2820 - 2826
(2021/02/01)
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- One-Pot Controlled Reduction of Conjugated Amides by Sequential Double Hydrosilylation Catalyzed by an Iridium(III) Metallacycle
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A single and accessible cationic iridiumIII metallacycle effectively catalyzes the one-pot sequential double hydrosilylation of challenging α,β-unsaturated secondary and tertiary amides to afford, in a controlled and straightforward way, the co
- Agbossou-Niedercorn, Francine,Corre, Yann,Djukic, Jean-Pierre,Kalocsai, Dorottya,Michon, Christophe,Nagyházi, Márton,Rysak, Vincent,Trivelli, Xavier
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supporting information
p. 6212 - 6220
(2020/10/02)
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- PRODUCTION METHOD OF AMIDE COMPOUND
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PROBLEM TO BE SOLVED: To provide a production method of an amide compound, which can use a variety of carboxylic acid halides and can produce a desired amide compound at a yield higher than a batch process by suppressing a side reaction. SOLUTION: Provided is a production method of an amide compound using a flow type reactor, in which the flow type reactor includes: a first flow path; a second flow path; a first mixing means provided at a confluent part of the first flow path and the second flow path; and a third flow path that is connected to the first mixing means and arranged on a down stream side of the first mixing means, the production method comprising: a mixing step of obtaining a mixed liquid by circulating a first liquid containing the carboxylic acid halide in the first flow path, circulating a second liquid containing an amine compound having a molecular weight of 1,000 or less, an inorganic alkali and water in the second flow path, and mixing the first liquid and the second liquid by the first mixing means to obtain a mixture; and a reaction step of obtaining an amide compound by circulating the mixed liquid in the third flow path and reacting the carboxylic acid halide and the amine compound in the third flow path. SELECTED DRAWING: Figure 1 COPYRIGHT: (C)2020,JPO&INPIT
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Paragraph 0018; 0112-0120; 0123-0126
(2020/10/08)
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- Celite-Polyaniline supported palladium catalyst for chemoselective hydrogenation reactions
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Polyaniline coated on particles of celite is used as support to load palladium catalyst. This heterogenized Celite?PANI?Pd system, is used as an efficient catalyst for chemoselective hydrogenation reactions. The catalyst is characterized by usual spectral, analytical techniques and studied for hydrogenation reactions at ambient conditions. The mild reaction conditions allow the control over the reactions and excellent selectivity is achieved in number of conversions. Hydrogenation of a carbon–carbon double bond was favored over other polar π-bond systems, while labile functional groups such as benzyl ether, benzyl esters, cyano, nitro and halogen remained unaffected. Primary amines were converted to N,N-dimethyl amines with formaldehyde, the double bond of coumarin was selectively hydrogenated without opening of the lactone functionality.
- Patel, Heta A.,Rawat, Maitreyee,Patel, Arun L.,Bedekar, Ashutosh V.
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- Facile direct synthesis of amides from trichloroethyl esters using catalytic DBU
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A practical method for the direct synthesis of amide compounds is described. Using small quantities of DBU as a catalyst, the direct conversion of 2,2,2-trichloroethyl esters to their corresponding amides was readily achieved. Based on this protocol, various amide compounds were successfully synthesized in high yield, suggesting a promising approach for the practical one-pot aminolysis from 2,2,2-trichloroethyl protected esters.
- La, Minh Thanh,Kim, Hee-Kwon
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p. 1135 - 1141
(2018/11/25)
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- Broadly Applicable Ytterbium-Catalyzed Esterification, Hydrolysis, and Amidation of Imides
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An efficient, broadly applicable, operationally simple, and divergent process for the transformation of imides into a range of carboxylic acid derivatives under mild conditions is reported. By simply using catalytic amounts of ytterbium(III) triflate as a Lewis acid promoter in the presence of alcohols, water, amines, or N,O-dimethylhydroxylamine, a broad range of imides is smoothly and readily converted to the corresponding esters, carboxylic acids, amides, and Weinreb amides in good yields. This method notably enables an easy cleavage of oxazolidinone-based auxiliaries.
- Guissart, Céline,Barros, Andre,Rosa Barata, Luis,Evano, Gwilherm
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supporting information
p. 5098 - 5102
(2018/09/13)
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- A Practical and General Amidation Method from Isocyanates Enabled by Flow Technology
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The addition of carbon nucleophiles to isocyanates represents a conceptually flexible and efficient approach to the preparation of amides. This general synthetic strategy has, however, been relatively underutilized owing to narrow substrate tolerance and the requirement for less favourable reaction conditions. Herein, we disclose a high-yielding, mass-efficient, and scalable method with appreciable functional group tolerance for the formation of amides by reaction of Grignard reagents with isocyanates. Through the application of flow chemistry and the use of substoichiometric amounts of CuBr2, this process has been developed to encompass a broad range of substrates, including reactants found to be incompatible with previously published procedures.
- Williams, Jason D.,Kerr, William J.,Leach, Stuart G.,Lindsay, David M.
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supporting information
p. 12126 - 12130
(2018/09/11)
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- A comparative study of amide-bond forming reagents in aqueous media – Substrate scope and reagent compatibility
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A survey of amidation reagents demonstrating DIC-HOPO, DMT-MM, COMU-collidine, TPTU-NMI, EEDQ, CDI and EDC-Oxyma to be effective for the coupling of carboxylic acids with amines in the presence of water and the absence of problematic dipolar aprotic solvents is reported. DMT-MM was shown to provide the best yields for the coupling of a secondary amine, TPTU-NMI and COMU-collidine for aniline, whilst the combination of DIC with HOPO afforded the broadest substrate scope and the highest yields for a sterically demanding carboxylic acid.
- Badland, Matthew,Crook, Robert,Delayre, Bastien,Fussell, Steven J.,Gladwell, Iain,Hawksworth, Michael,Howard, Roger M.,Walton, Robert,Weisenburger, Gerald A.
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p. 4391 - 4394
(2017/10/20)
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- Practical Synthesis of Amides via Copper/ABNO-Catalyzed Aerobic Oxidative Coupling of Alcohols and Amines
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A modular Cu/ABNO catalyst system has been identified that enables efficient aerobic oxidative coupling of alcohols and amines to amides. All four permutations of benzylic/aliphatic alcohols and primary/secondary amines are viable in this reaction, enabling broad access to secondary and tertiary amides. The reactions exhibit excellent functional group compatibility and are complete within 30 min-3 h at rt. All components of the catalyst system are commercially available.
- Zultanski, Susan L.,Zhao, Jingyi,Stahl, Shannon S.
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supporting information
p. 6416 - 6419
(2016/06/09)
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- Rhodium-catalyzed oxidative amidation of allylic alcohols and aldehydes: Effective conversion of amines and anilines into amides
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The rhodium-catalyzed oxidative amidation of allylic alcohols and aldehydes is reported. In situ generated [(BINAP)Rh]BF4 catalyzes the one-pot isomerization/oxidative amidation of allylic alcohols or direct amidation of aldehydes using acetone or styrene as the hydrogen acceptor. The conditions are general, affording good to excellent yields with a wide array of amine and aniline nucleophiles, and chemoselective, other alcohols do not participate in the oxidation reaction. Utilization of biphasic conditions is critical, as they promote an equilibrium between the imine/enamine byproducts and the hemiaminal, which can undergo oxidation to the amide.
- Wu, Zhao,Hull, Kami L.
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p. 969 - 975
(2016/02/05)
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- Internal redox amidation of α,β-unsaturated aldehydes in ionic liquids. The electrochemical route
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A simple, N-heterocyclic carbene (NHC) activated synthesis of amides has been performed via electrolysis, carried out under galvanostatic control, of an ionic liquid (Bmim-BF4) followed by addition to the catholyte of an α,β-unsaturated aldehyde and amine. Amides have been isolated, in good to elevated yields, in the absence of any base, co-catalyst and organic solvent. The selectivity of amidation, versus the formation of imine as by-product, has been related to the molar ratio electrogenerated NHC/aldehyde. The results, obtained using ionic liquids and electrochemical procedures, have been compared with those obtained using organic solvents and classical procedures.
- Feroci, Marta,Chiarotto, Isabella,Inesi, Achille
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p. 692 - 699
(2013/04/10)
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- Phosphorus oxychloride as an efficient coupling reagent for the synthesis of esters, amides and peptides under mild conditions
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A mild method is described for the conversion of carboxylic acids into esters, amides, as well as peptides without racemization through carboxyl activation by the reagent combination of POCl3 and DMAP. Long chain alcohols could be converted to the corresponding ester in good yields. 31P NMR spectrum was used to detect phosphorus-containing intermediates in ongoing reactions directly, and a possible mechanism has been proposed based on these results. The Royal Society of Chemistry 2013.
- Chen, Hu,Xu, Xunfu,Liu, Liu,Tang, Guo,Zhao, Yufen
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p. 16247 - 16250
(2013/09/23)
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- Substrate-selective dehydrocondensation at the interface of micelles and emulsions of common surfactants
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Scratch the surface: Dehydrocondensations between carboxylates and amines by using an amphiphilic 1,3,5-triazinylammonium-based coupling agent were accelerated by the interfacial effect of micelles and emulsions of common surfactants (see figure). The reaction of carboxylates was promoted by both anionic and nonionic surfactants, and that of amines was promoted by only a nonionic surfactant. High selectivities for more lipophilic substrates were observed in micelles or emulsions. Copyright
- Kunishima, Munetaka,Kikuchi, Kanako,Kawai, Yukio,Hioki, Kazuhito
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supporting information; experimental part
p. 2080 - 2083
(2012/05/20)
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- Amide therapeutics for the treatment of inflammatory bowel disease
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Disclosed are methods for treating or preventing inflammatory bowel disease (IBD) using amide and related compounds. Pharmaceutical compositions containing amide compounds which are useful for the treatment or prophylaxis of IBD are also disclosed.
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- New reactions of the thiocarbonyl function. The synthesis of hindered peptides
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The well-known radical chemistry of the thiocarbonyl function has been expanded to include the concerted reaction between an O-acyl derivative of N-hydroxypyridine-2(1H)-thione (a Barton PTOC ester) and a sulfenamide. The atom-economical process spawned a carboxamide and an unsymmetrical disulfide of synthetic and biological value. The reaction was successfully applied to the synthesis of sterically encumbered, urethane-protected dipeptides. The oxidation-reduction technology pertaining to the disulfide-phosphine combination facilitated the generation of transient Barton PTOC esters. In conjunction with the appropriate benzenesulfenamide, the Barton PTOC ester of benzoyl-L-leucine was shown to preserve optical integrity according to the sensitive Young test, albeit at low temperature. However, the thermodynamic forces at play are powerful and, as a result, the yields were not compromised. In all but the sterically demanding instances, the parent free amine almost matched the reaction time, yield, and enantiomeric excess of the corresponding benzenesulfenamide in its reaction with a Barton PTOC ester.
- Barton, Derek H. R.,Ferreira, J. Albert
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- N-hydroxypyridine-2(1H)-thione derivatives of carboxylic acids as activated esters. Part I. The synthesis of carboxamides
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The reaction between an acyl derivative of N-hydroxypyridine-2(1H)- thione (a Barton PTOC ester) and either an amine (primary or secondary), or the corresponding sulfenamide, led to the formation of a carboxamide in a clean transformation requiring minimal work-up and purification. The reaction with a sulfenamide is particularly useful since the only by-product, an unsymmetrical disulfide, is of both synthetic and biological value. In sterically demanding cases, Barton PTOC esters were more reactive towards benzenesulfenamides than to the corresponding free amines.
- Barton, Derek H. R.,Ferreira, J. Albert
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p. 9347 - 9366
(2007/10/03)
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