529-65-7Relevant academic research and scientific papers
Nickel-Catalyzed Hydrodeoxygenation of Aryl Sulfamates with Alcohols as Mild Reducing Agents
Matsuo, Kasumi,Kuriyama, Masami,Yamamoto, Kosuke,Demizu, Yosuke,Nishida, Koyo,Onomura, Osamu
, p. 4449 - 4460 (2021/08/25)
The nickel-catalyzed hydrodeoxygenation of aryl sulfamates has been developed with alcohols as mild reductants. A variety of functional groups and heterocycles were tolerated in this reaction system to give the desired products in high yields. In addition, the gram-scale process and stepwise cine-substitution were also achieved with high efficiency.
Meta Selective C-H Borylation of Sterically Biased and Unbiased Substrates Directed by Electrostatic Interaction
Chaturvedi, Jagriti,Haldar, Chabush,Bisht, Ranjana,Pandey, Gajanan,Chattopadhyay, Buddhadeb
, p. 7604 - 7611 (2021/05/26)
An electrostatically directed meta borylation of sterically biased and unbiased substrates is described. The borylation follows an electrostatic interaction between the partially positive and negative charges between the ligand and substrate. With this strategy, it has been demonstrated that a wide number of challenging substrates, especially 4-substituted substrates, can selectively be borylated at the meta position. Moreover, unsubstituted substrates also displayed excellent meta selectivity. The reaction employs a bench-stable ligand and proceeds at a milder temperature, precluding the need to synthesize a bulky and sophisticated ligand/template.
Method for promoting acylation of amine or alcohol by carbon dioxide
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Paragraph 0033-0034, (2021/05/29)
The invention relates to a method for promoting acylation of amine or alcohol by carbon dioxide, which comprises the following steps of: mixing an amine compound, carboxylate or thiocarboxylate compound and a reaction solvent under the action of carbon dioxide, and reacting to obtain an amide compound, or under the action of carbon dioxide, mixing the alcohol compound, the thiocarboxylate compound and the reaction solvent [gamma]-valerolactone, and reacting to obtain the ester compound. According to the invention, under the promotion action of carbon dioxide, carboxylate or thiocarboxylate is used as an acylation reagent, and amine and alcohol are converted into amide and ester compounds in the absence of a transition metal catalyst, so that acylation reagents such as acyl chloride or anhydride with irritation and corrosivity are avoided; and the method has the advantages of simple operation, mild reaction conditions, high tolerance of substrate functional groups, strong applicability and high yield, and provides an efficient, reliable and economical preparation method for synthesis of amide and ester compounds.
N-Alkylation of N-trimethylsilyl derivatives of lactams, amides, and imides with alkyl sulfonates
Baukov, Yu. I.,Kramarova, E. P.,Negrebetsky, Vad. V.,Shagina, A. D.,Shipov, A. G.,Tarasenko, D. V.
, p. 398 - 400 (2020/04/15)
The reaction of N-trimethylsilyl derivatives of amides and imides with alkyl sulfonates on heating affords the corresponding N-alkyl derivatives and trimethylsilyl sulfonates.
Amide Bond Formation Catalyzed by Recyclable Copper Nanoparticles Supported on Zeolite Y under Mild Conditions
Moglie, Yanina,Buxaderas, Eduardo,Mancini, Agustina,Alonso, Francisco,Radivoy, Gabriel
, p. 1487 - 1494 (2019/02/16)
A series of catalysts based on supported copper nanoparticles have been prepared and tested in the amide bond formation from tertiary amines and acid anhydrides, in the presence of tert-butyl hydroperoxide as an oxidant. Copper nanoparticles on zeolite Y (CuNPs/ZY) was found to be the most efficient catalyst for the synthesis of amides, working in acetonitrile as solvent, under ligand- and base-free conditions in air. The products were obtained in good to excellent yields and in short reaction times. The CuNPs/ZY system also exhibited higher catalytic activity than some commercially available copper and iron sources and it was reused in ten reaction cycles without any further pre-treatment. This methodology has been successfully scaled-up to a gram scale with no detriment to the yield.
N-Ethynylation of Anilides Decreases the Double-Bond Character of Amide Bond while Retaining trans-Conformation and Planarity
Yamasaki, Ryu,Morita, Kento,Iizumi, Hiromi,Ito, Ai,Fukuda, Kazuo,Okamoto, Iwao
supporting information, p. 10118 - 10122 (2019/07/05)
Activated amide bonds have been attracting intense attention; however, most of the studied moieties have twisted amide character. To add a new strategy to activate amide bonds while maintaining its planarity, we envisioned the introduction of an alkynyl group on the amide nitrogen to disrupt amide resonance by nN→Csp conjugation. In this context, the conformations and properties of N-ethynyl-substituted aromatic amides were investigated by DFT calculations, crystallography, and NMR spectroscopic analysis. In contrast to the cis conformational preference of N-ethyl- and vinyl-substituted acetanilides, N-ethynyl-substituted acetanilide favors the trans conformation in the crystal and in solution. It also has a decreased double bond character of the C(O)?N bond, without twisting of the amide. N-Ethynyl-substituted acetanilides undergo selective C(O)?N bond or N?C(sp) bond cleavage reactions and have potential applications as activated amides for coupling reactions or easily cleavable tethers.
Electrophilic Amination with Nitroarenes
Rauser, Marian,Ascheberg, Christoph,Niggemann, Meike
supporting information, p. 11570 - 11574 (2017/09/11)
An exceptionally general electrophilic amination, which directly transforms commercially available nitroarenes into alkylated aromatic aminoboranes with zinc organyl compounds was developed. The reaction starts with a two-step partial reduction of the nitro group to a nitrenoid, which is used in situ as the electrophilic amination reagent. To facilitate isolation, the resulting air- and moisture-sensitive aminoboranes were reacted with a range of electrophiles. The method not only represents a direct transformation of nitro compounds into electrophilic amination reagents but also provides an elegant alternative to dehydrocoupling methods for the generation of aminoboranes.
Method for preparing N-aryl tertiary amide with substituted Meldrum's acid as acylating agent in water phase
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Paragraph 0014; 0034, (2017/04/22)
The invention discloses a method for preparing N-aryl tertiary in a water phase. According to the method, water is used as the solvent, and substituted Meldrum's acid and N-aryl secondary amine react at 80-100 DEG C for 1-10 h to obtain the N-aryl tertiary. The molar ratio of substituted Meldrum's acid to N-aryl secondary amine is 1:10-10:1. The reaction concentration of substituted Meldrum's acid or N-aryl secondary amine is 0.5-4 mol/L. The method overcomes the defect that in the prior art, acyl chloride, anhydride, dehydration coupling reagent, organic solvent, phase transfer catalyst or metal catalyst needs to be adopted, and has the advantages that by using substituted Meldrum's acid as an acylating agent, pre-activating of carboxylic acid or using of a dehydration coupling reagent is avoided; due to the fact that substituted Meldrum's acid is easy to prepare, using of certain carboxylic acid and activated derivatives which are hard to get or expensive is avoided; water is used as the solvent, so that using of toxic organic solvent is avoided; no acid, alkali or metal catalyst is adopted, so that influences of acid and alkali on sensitive groups and equipment and metal ion residues in products are avoided. The synthesis method can play an important role in industrial production of N-aryl tertiary, especially N-aryl tertiary of complex carboxylic acid.
N-Acyl-N-(4-chlorophenyl)-4-nitrobenzenesulfonamides: Highly selective and efficient reagents for acylation of amines in water
Ebrahimi, Sara,Saiadi, Safoura,Dakhilpour, Simin,Mirsattari, Seyed Nezamoddin,Massah, Ahmad Reza
, p. 95 - 104 (2016/04/26)
A variety of N-acyl-N-(4-chlorophenyl)-4-nitrobenzenesulfonamides (1a-e) were synthesized in one pot from 4-chloroaniline under solvent-free conditions and have been developed as chemoselective N-acylation reagents. Selective protection of primary amines in the presence of secondary amines, acylation of aliphatic amines in the presence of aryl amines, and monofunctionalization of primary-secondary diamines as well as selective N-acylation of amino alcohols using these reagents are described. All of the acylation reactions were carried out in water as a green solvent. High stability and easy preparation of these acylating reagents are other advantages of this method.
Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings
Rovira, Mireia,Soler, Marta,Güell, Imma,Wang, Ming-Zheng,Gómez, Laura,Ribas, Xavi
supporting information, p. 7315 - 7325 (2016/09/09)
The copper-catalyzed arylation of nucleophiles has been established as an efficient methodology for the formation of C-C and C-heteroatom bonds. Considering the advances during the last two decades, the ligand choice plays a key role in such transformations and can strongly influence the catalytic efficiency. The applicability of these Ullmann-type coupling reactions regarding the orthogonal selectivity of different functional groups constitutes a challenging subject for current synthetic strategies. Herein, we report a useful toolkit of Cu-based catalysts for the chemoselective arylation of a wide-range of nucleophiles in competitive reactions using aryl iodides and bromides. We show in this work that the arylation of all kinds of amides can be orthogonal to that of amines (aliphatic or aromatic) and phenol derivatives. This high chemoselectivity can be governed by the use of different ligands, yielding the desired coupling products under mild conditions. The selectivity trends are maintained for electronically biased iodobenzene and bromobenzene electrophiles. Radical clock experiments discard the occurrence of radical-based mechanisms.
