- Palladium-Catalyzed Hydrocarbonylative C-N Coupling of Alkenes with Amides
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An efficient palladium-catalyzed hydrocarbonylative C-N coupling of alkenes with amides has been developed. The reaction was performed via hydrocarbonylation of alkenes, followed by acyl metathesis with amides. Both intermolecular and intramolecular react
- Zhou, Xibing,Zhang, Guoying,Gao, Bao,Huang, Hanmin
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supporting information
p. 2208 - 2212
(2018/04/30)
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- Amidation reaction of carboxylic acid with formamide derivative using SO3?pyridine
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The amidation reaction of carboxylic acid derivatives was developed using sulfur trioxide pyridine complex (SO3?py) as a commercially available and easily handled oxidant. This method could be applied to the reaction of various aromatic and aliphatic carboxylic acids, including optically active ones, with formamide derivatives to afford the corresponding amides in good to high yields.
- Kawano, Shota,Saito, Kodai,Yamada, Tohru
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supporting information
p. 584 - 586
(2018/04/12)
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- Flexible and Chemoselective Oxidation of Amides to α-Keto Amides and α-Hydroxy Amides
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A suite of flexible and chemoselective methods for the transition-metal-free oxidation of amides to α-keto amides and α-hydroxy amides is presented. These highly valuable motifs are accessed in good to excellent yields and stereoselectivities with high functional group tolerance. The utility of the method is showcased by the formal synthesis of a potent histone deacetylase inhibitor.
- De La Torre, Aurélien,Kaiser, Daniel,Maulide, Nuno
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supporting information
p. 6578 - 6581
(2017/05/29)
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- Chemoselective Intermolecular Cross-Enolate-Type Coupling of Amides
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A new approach for the synthesis of 1,4-dicarbonyl compounds is reported. Chemoselective activation of amide carbonyl functionality and subsequent umpolung via N-oxide addition generates an electrophilic enolonium species that can be coupled with a wide range of nucleophilic enolates. The method conveys broad functional group tolerance on both components, does not suffer from formation of homocoupling byproducts and avoids the use of transition metal catalysts.
- Kaiser, Daniel,Teskey, Christopher J.,Adler, Pauline,Maulide, Nuno
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supporting information
p. 16040 - 16043
(2017/11/22)
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- Palladium-Catalyzed Aminocarbonylation of Aliphatic Alkenes with N,N-Dimethylformamide as an in Situ Source of CO
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The palladium-catalyzed aminocarbonylation of aliphatic alkenes is presented for the first time without the need for external CO pressure. N,N-dimethylformamide (DMF) is used as an in situ source of both the required carbon monoxide and the amine substrate. The applied palladium catalytic system is well-known for a number of carbonylation reactions, including those with CO surrogates and tandem isomerizing carbonylations. The reaction pathway was investigated and proved to proceed by an acid-catalyzed DMF decomposition to CO and dimethyl amine with subsequent aminocarbonylation of the alkene. Pressure-versus-time curves gave more insight into the correlation between acid concentration and aminocarbonylation activity. Aliphatic alkenes (terminal and internal) are transformed, also in commercial glassware, into the corresponding linear N,N-dimethylamides with excellent selectivities. Hence, amide synthesis by aminocarbonylation moves closer to application in standard organic laboratories. Do-it-yourself CO production: The aminocarbonylation of alkenes for aliphatic amide synthesis is presented for the first time using N,N-dimethylamine as an in situ source of both, the required CO and dimethylamine. Excellent selectivities to the linear product are ensured by isomerizing carbonylation applying a [Pd]/1,2-DTBPMB system. 1,2-DTBPMB=1,2-bis((di-tert-butylphos- phino)methyl)benzene.
- Seidensticker, Thomas,Furst, Marc R. L.,Frauenlob, Robin,Vondran, Johanna,Paetzold, Eckhard,Kragl, Udo,Vorholt, Andreas J.
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p. 4085 - 4090
(2016/01/09)
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- Regioselective hydrocarbamoylation of 1-alkenes
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Nickel/Lewis acid cooperative catalysis derived from [Ni(cod)2], AlEt3, and N-heterocyclic carbene (NHC) effects highly regioselective hydrocarbamoylation of 1-alkenes. Variously substituted formamides and 1-alkenes can be employed to give a range of linear alkanamides regioselectively.
- Miyazaki, Yosuke,Yamada, Yuuya,Nakao, Yoshiaki,Hiyama, Tamejiro
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supporting information; experimental part
p. 298 - 300
(2012/05/20)
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- Deuteration of α,β-acetylenic esters, amides, or carboxylic acids without using deuterium gas: Synthesis of 2,2,3,3-tetradeuterioesters, amides, or acids
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An easy, simple, rapid, and nonhazardous deuteration of the C-C triple bond of α,β-acetylenic esters, amides, or acids by means of samarium diiodide in the presence of D2O, provides an efficient method for synthesizing 2,2,3,3-tetradeuterioesters, amides, or carboxylic acids, respectively. When H2O is used instead of D2O, saturated carboxylic esters, amides, or acids were isolated. A mechanism to explain these reduction reactions has been proposed.
- Concellón, José M.,Rodríguez-Solla, Humberto,Concellón, Carmen
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p. 2129 - 2131
(2007/10/03)
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- Concentration of hydrophobic organic compounds and extraction of protein using alkylammoniosulfate zwitterionic surfactant mediated phase separations (cloud point extractions)
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The zwitterionic surfactants 3-[nonyl- (or decyl-) dimethylammonio]propyl sulfate, (C9-APSO4 or C10-APSO4) were synthesized using Nilsson's procedure, and their phase separation behavior under different experimental conditions was evaluated. The results indicate that such zwitterionic surfactants can be utilized for the extraction/preconcentration of hydrophobic species in a manner akin to that previously reported for nonionic surfactants. This was demonstrated for several practical applications including the extraction/preconcentration of some steroidal hormones and vitamin E prior to high-performance liquid chromatography analysis. The zwitterionic surfactant mediated phase separation was also applied to the extraction of the hydrophobic membrane protein, bacterio-rhodopsin, from the hydrophilic cytochrome c protein, both originally present In an aqueous phase. The concentration factors for this aqueous two-phase extraction technique using C10-APSO4 ranged from 26 to 35 with recoveries In the range 88 to > 96%. Some comparative studies Indicate that the use of zwittterionic surfactants In lieu of nonionic surfactants (e.g. polyoxyethylene(7.5) nonyl phenyl ether PONPE-7.5) In such an extraction method offers some significant advantages such as purer, homogeneous surfactant preparation, minimum background absorbance at UV detection wavelengths, the two-phase region occurring at lower temperatures, and greater extraction efficiencies/concentration factors among others.
- Saitoh, Tohru,Hinze, Willie L.
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p. 2520 - 2525
(2007/10/02)
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- Reaction of N-Nitroso- and N-Nitro-N-alkylamides with Amines
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Several N-nitroso- and N-nitrocarboxamides have been characterized by 1H and 13C NMR spectroscopy.These compounds react with ammonia and aliphatic amines to afford mainly carboxamides of general formula RCONH2, RCONHR', or RCONR'R''.N-Nitrosocarboxamides and aromatic amines give poor yields of RCONHAr; by contrast, N-nitrocarboxamides and aromatic amines lead to RCONHAr in good yields.The higher thermal stability of the N-nitroamides as compared to N-nitrosoamides is advantageous in this connection; nevertheless, the principal advantage of the NNO2 group appears to be that it activates the nucleophilic attack to the carbonyl of the amide function more than the NNO group, as has been demonstrated by competitive experiments.The reaction of N-nitroso- and N-nitro-N-methylsulfonamides with ammonia and diethylamine has been studied as well; whereas N-methyl-N-nitro-p-toluenesulfonamide reacts as N-nitrocarboxamides, transnitration is predominant with N-methyl-N-nitroso-p-toluenesulfonamide.
- Garcia, Jordi,Gonzalez, Javier,Segura, Ramon,Urpi, Felix,Vilarrasa, Jaume
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p. 3322 - 3327
(2007/10/02)
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