- CuCl/TMEDA/nor-AZADO-catalyzed aerobic oxidative acylation of amides with alcohols to produce imides
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Although aerobic oxidative acylation of amides with alcohols would be a good complement to classical synthetic methods for imides (e.g., acylation of amides with activated forms of carboxylic acids), to date, there have been no reports on oxidative acylation to produce imides. In this study, we successfully developed, for the first time, an efficient method for the synthesis of imides through aerobic oxidative acylation of amides with alcohols by employing a CuCl/TMEDA/nor-AZADO catalyst system (TMEDA = teramethylethylendiamine; nor-AZADO = 9-azanoradamantane N-oxyl). The proposed acylation proceeds through the following sequential reactions: aerobic oxidation of alcohols to aldehydes, nucleophilic addition of amides to the aldehydes to form hemiamidal intermediates, and aerobic oxidation of the hemiamidal intermediates to give the corresponding imides. This catalytic system utilizes O2 as the terminal oxidant and produces water as the sole by-product. An important point for realizing this efficient acylation system is the utilization of a TMEDA ligand, which, to the best of our knowledge, has not been employed in previously reported Cu/ligand/N-oxyl systems. Based on experimental evidence, we consider that plausible roles of TMEDA involve the promotion of both hemiamidal oxidation and regeneration of an active CuII-OH species from a CuI species. Here promotion of hemiamidal oxidation is particularly important. Employing the proposed system, various types of structurally diverse imides could be synthesized from various combinations of alcohols and amides, and gram-scale acylation was also successful. In addition, the proposed system was further applicable to the synthesis of α-ketocarbonyl compounds (i.e., α-ketoimides, α-ketoamides, and α-ketoesters) from 1,2-diols and nucleophiles (i.e., amides, amines, and alcohols).
- Kataoka, Kengo,Wachi, Keiju,Jin, Xiongjie,Suzuki, Kosuke,Sasano, Yusuke,Iwabuchi, Yoshiharu,Hasegawa, Jun-Ya,Mizuno, Noritaka,Yamaguchi, Kazuya
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p. 4756 - 4768
(2018/06/07)
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- Zirconium-catalysed N-acylation of lactams using unactivated carboxylic acids
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A large number of chemicals including surfactants, nootropic drugs and pesticides contain an N-acylated lactam moiety in their molecular structure. In this work, the direct, catalytic N-acylation of a number of lactams with various unactivated carboxylic
- Hulsbosch, Joris,Claes, Laurens,De Vos, Dirk E.
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supporting information
p. 1646 - 1650
(2018/04/06)
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- I2/Aqueous TBHP-Catalyzed Coupling of Amides with Methylarenes/Aldehydes/Alcohols: Metal-Free Synthesis of Imides
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We present a metal-free method for the synthesis of imides by the direct coupling of NH-amides with methylarenes under iodine/aqueous TBHP conditions. The optimized conditions worked very well with benzaldehydes and benzyl alcohol and furnished the corresponding imides in good to excellent yields. A series of control and radical scavenger experiments were also performed, which suggested the involvement of radical pathways. The labeling experiment in the presence of 18O-labeled H2O suggested water as a source of oxygen in the imides.
- Aruri, Hariprasad,Singh, Umed,Kumar, Sanjay,Kushwaha, Manoj,Gupta, Ajai Prakash,Vishwakarma, Ram A.,Singh, Parvinder Pal
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supporting information
p. 3638 - 3641
(2016/08/16)
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- Construction of tertiary chiral centers by Pd-catalyzed asymmetric allylic alkylation of prochiral enolate equivalents
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Abstract The palladium-catalyzed decarboxylative allylic alkylation of enol carbonates derived from lactams and ketones is described. Employing these substrates with an electronically tuned Pd catalyst system trisubstituted chiral centers are produced. These stereocenters have been previously challenging to achieve using Pd complex/chiral P-N ligand systems.
- Kita, Yusuke,Numajiri, Yoshitaka,Okamoto, Noriko,Stoltz, Brian M.
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p. 6349 - 6353
(2015/08/18)
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- Fe-Catalysed oxidative C-H/N-H coupling between aldehydes and simple amides
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A novel oxidative coupling of aldehydes with simple amides, most likely involving a radical process, was achieved through the use of an iron catalyst. Various amides were utilized as substrates to easily construct imides by coupling with aldehydes. A catalytic cycle involving the benzoyl halide intermediate is proposed based on our experimental results. This journal is the Partner Organisations 2014.
- Wang, Jing,Liu, Chao,Yuan, Jiwen,Lei, Aiwen
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supporting information
p. 4736 - 4739
(2014/05/06)
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- Construction of nitrogen-fused tetrahydroquinolines via a domino reaction
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An efficient domino approach for the diastereoselective synthesis of polyfunctionalized nitrogen-fused tetrahydroquinoline frameworks under mild conditions has been developed. The scope and limitation of this transformation were investigated by using a range of readily accessible enamides and benzyl azides. This method is also applicable to the formation of 2,3-functionalized enamides.
- Gigant, Nicolas,Gillaizeau, Isabelle
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supporting information
p. 4622 - 4625
(2012/10/29)
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- Highly efficient copper-catalyzed amidation of aldehydes by C-H activation
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We have developed a highly efficient method for the copper-catalyzed amidation of aldehydes in the presence of N-bromosuccinimide (NBS). This method is simple, economical, and has practical advantages for synthesis of imides.
- Wang, Long,Fu, Hua,Jiang, Yuyang,Zhao, Yufen
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experimental part
p. 10722 - 10726
(2009/12/03)
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- Process for the preparation of diacylimides
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The present invention relates to a process for the preparation of compounds of the formula 1 by reacting a secondary acid amide of the formula 2 with an acid chloride of the formula 3 in the presence of N,N-diisopropyl-N-ethylamine. R1, R2 and R3 are alky
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- Synthesis of cyclic and acyclic imides, sulfonimides, and N-carbobenzyloxyamides by ketene trapping
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A convenient and general method for the synthesis of cyclic and acyclic imides, sulfonimides, and N-benzyloxycarbonyl amides via the inter- and intramolecular trapping of ketenes has been developed.Heating the corresponding amido, sulfonamido, and carbama
- MaGee, David I.,Ramaseshan, Mahesh,Leach, James D.
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p. 2111 - 2118
(2007/10/03)
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- OXIDATION OF ORGANIC NITROGEN COMPOUNDS BY MEANS OF RUTHENIUM TETROXIDE: SELECTIVE PREPARATION OF N-SUBSTITUTED LACTAMS
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1-Formyl-, 1-acetyl-, and 1-benzoyl-perhydro-azepines and -azocines are oxidized by RuO4 to the corresponding N-acyllactams; the 1-benzyl analogues also undergo major endocyclic oxidation to 1-benzyllactams.
- Tangari, Nicola,Giovine, Maria,Morlacchi, Flaviano,Vetuschi, Claudio
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p. 325 - 328
(2007/10/02)
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- FACILE METHOD FOR THE ACYLATION OF ALCOHOLS AND AMIDES BY THE USE OF 1,1'-DIMETHYLSTANNOCENE AND ACYL CHLORIDES
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Acylation of alcohols and amides was effected under mild conditions by the use of 1,1'-dimethylstannocene and acyl chlorides, giving the corresponding esters and imides in good to excellent yields.
- Mukaiyama, Teruaki,Ichikawa, Junji,Asami, Masatoshi
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p. 293 - 296
(2007/10/02)
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