4589-12-2Relevant academic research and scientific papers
Optimization of Synthetically Versatile Pyridylidene Amide Ligands for Efficient Iridium-Catalyzed Water Oxidation
Navarro, Miquel,Smith, Christene A.,Li, Mo,Bernhard, Stefan,Albrecht, Martin
, p. 6386 - 6398 (2018)
The synthetic versatility of pyridylidene amide (PYA) ligands has been exploited to prepare and evaluate a diverging series of iridium complexes containing C,N-bidentate chelating aryl-PYA ligands for water oxidation catalysis. The phenyl-PYA lead structu
In Situ Formation of Cationic π-Allylpalladium Precatalysts in Alcoholic Solvents: Application to C-N Bond Formation
Steinsoultz, Philippe,Bailly, Aurélien,Wagner, Patrick,Oliva, Estefania,Schmitt, Martine,Grimaud, Laurence,Bihel, Frédéric
, p. 560 - 567 (2022/01/03)
We report an efficient Buchwald-Hartwig cross-coupling reaction in alcoholic solvent, in which a low catalyst loading showed excellent performance for coupling aryl halides (I, Br, and Cl) with a broad set of amines, amides, ureas, and carbamates under mild conditions. Mechanistically speaking, in a protic and polar medium, extremely bulky biarylphosphine ligands interact with the dimeric precatalyst [Pd(π-(R)-allyl)Cl]2 to form the corresponding cationic complexes [Pd(π-(R)-allyl)(L)]Cl in situ and spontaneously. The resulting precatalyst further evolves under basic conditions into the corresponding L-Pd(0) catalyst, which is commonly employed for cross-coupling reactions. This mechanistic study highlights the prominent role of alcoholic solvents for the formation of the active catalyst.
Single-pot tandem oxidative/C-H modification amidation process using ultrasmall PdNP-encapsulated porous organosilica nanotubes
Gholipour, Behnam,Liu, Xiao,Rostamnia, Sadegh,Zonouzi, Afsaneh
, p. 4276 - 4287 (2022/02/16)
Herein, we studied a single-pot method with a dual catalysis process towards the conversion of primary aromatic alcohols to amides using ultrasmall PdNPs of controlled uniform size (1.8 nm) inside hybrid mesoporous organosilica nanotubes (MO-NTs). The cat
Metal-free oxidative decarbonylative halogenation of fused imidazoles
Kumar, Gulshan,Shankar, Ravi,Singh, Davinder,Tali, Javeed Ahmad
, p. 20551 - 20555 (2021/11/23)
An efficient strategy has been developed for the deformylative halogenation of carbaldehyde imidazo-fused heterocycles in the presence of TBHP controlled by temperature. A convenient and sequential functionalization (C8 to C3) portrays the synthetic utility of the current method.N-Heterocycle benzamide products were also observedviathe ring opening of imidazopyridines through the cleavage of C-C bond at high temperatures. Features of this method include temperature-controlled excellent regioselectivity, mild conditions and functional group tolerance.
Visible-light-induced direct construction of amide bond from carboxylic acids with amines in aqueous solution
Wang, Jin,Hou, Huiqing,Hu, Yongzhi,Lin, Jin,Wu, Min,Zheng, Zhiqiang,Xu, Xiuzhi
supporting information, (2021/02/09)
A novel visible-light-promoted N-acylation for the synthesis of amides from easily available carboxylic acids with amines in the presence of I2 within 2.5 h in aqueous solution has been developed. Using sunlight as the visible light source greatly reduces the cost of experiments and produces almost no toxic effects. Hence, this study provides an alternative catalytic system for the construction of a wide range of amides with readily available materials. Moreover, the strategy was successfully applied in the preparation of N-(3-(2,6-dimethoxyphenoxy)-7-nitroquinoxalin-2-yl)benzohydrazide, which displayed a signification anti-proliferation effect on A549, MCF-7 and HCT116 cell lines.
Method for preparing amide compound by photocatalysis of nitrogen-containing heterocyclic compound
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Paragraph 0083; 0084; 0093; 0094, (2021/06/06)
The invention provides a method for preparing an amide compound by photocatalysis of a nitrogen-containing heterocyclic compound. The method comprises the following steps: mixing the nitrogen-containing heterocyclic compound, organic carboxylic acid and tetrahalomethane in a solvent, adding a catalyst, and reacting under the illumination condition to prepare the amide compound. According to the invention, the organic carboxylic acid, the nitrogen-containing heterocyclic compound containing reactive hydrogen on nitrogen atoms and the tetrahalomethane are used as raw materials, so the raw materials are wide in source, low in cost and high in safety, and large-scale production is facilitated; the halogen simple substance is co-produced in the reaction process, the added value is high, a large amount of waste is prevented from being generated, and the method has high atom economy and environmental friendliness; light conditions are adopted to replace traditional heating and high-pressure conditions, the reaction conditions are mild, environmental pollution is reduced, and the reaction cost is reduced; the method has the advantages of good substrate applicability, mild process conditions, environmental protection, simple process, simple and feasible operation method, and facilitation of popularization and application.
N-Ammonium Ylide Mediators for Electrochemical C-H Oxidation
Saito, Masato,Kawamata, Yu,Meanwell, Michael,Navratil, Rafael,Chiodi, Debora,Carlson, Ethan,Hu, Pengfei,Chen, Longrui,Udyavara, Sagar,Kingston, Cian,Tanwar, Mayank,Tyagi, Sameer,McKillican, Bruce P.,Gichinga, Moses G.,Schmidt, Michael A.,Eastgate, Martin D.,Lamberto, Massimiliano,He, Chi,Tang, Tianhua,Malapit, Christian A.,Sigman, Matthew S.,Minteer, Shelley D.,Neurock, Matthew,Baran, Phil S.
supporting information, p. 7859 - 7867 (2021/05/26)
The site-specific oxidation of strong C(sp3)-H bonds is of uncontested utility in organic synthesis. From simplifying access to metabolites and late-stage diversification of lead compounds to truncating retrosynthetic plans, there is a growing need for new reagents and methods for achieving such a transformation in both academic and industrial circles. One main drawback of current chemical reagents is the lack of diversity with regard to structure and reactivity that prevents a combinatorial approach for rapid screening to be employed. In that regard, directed evolution still holds the greatest promise for achieving complex C-H oxidations in a variety of complex settings. Herein we present a rationally designed platform that provides a step toward this challenge using N-ammonium ylides as electrochemically driven oxidants for site-specific, chemoselective C(sp3)-H oxidation. By taking a first-principles approach guided by computation, these new mediators were identified and rapidly expanded into a library using ubiquitous building blocks and trivial synthesis techniques. The ylide-based approach to C-H oxidation exhibits tunable selectivity that is often exclusive to this class of oxidants and can be applied to real-world problems in the agricultural and pharmaceutical sectors.
N-pyridinylbenzamides: an isosteric approach towards new antimycobacterial compounds
Nawrot, Daria,Suchánková, Eli?ka,Jan?ourek, Ond?ej,Kone?ná, Klára,Bárta, Pavel,Dole?al, Martin,Zitko, Jan
, p. 686 - 700 (2020/11/30)
A series of N-pyridinylbenzamides was designed and prepared to investigate the influence of isosterism and positional isomerism on antimycobacterial activity. Comparison to previously published isosteric N-pyrazinylbenzamides was made as an attempt to draw structure–activity relationships in such type of compounds. In total, we prepared 44 different compounds, out of which fourteen had minimum inhibitory concentration (MIC) values against Mycobacterium tuberculosis H37Ra below 31.25?μg/ml, most promising being N-(5-chloropyridin-2-yl)-3-(trifluoromethyl)benzamide (23) and N-(6-chloropyridin-2-yl)-3-(trifluoromethyl)benzamide (24) with MIC?=?7.81?μg/ml (26?μm). Five compounds showed broad-spectrum antimycobacterial activity against M. tuberculosis H37Ra, M. smegmatis and M. aurum. N-(pyridin-2-yl)benzamides were generally more active than N-(pyridin-3-yl)benzamides, indicating that N-1 in the parental structure of N-pyrazinylbenzamides might be more important for antimycobacterial activity than N-4. Marginal antibacterial and antifungal activity was observed for title compounds. The hepatotoxicity of title compounds was assessed in vitro on hepatocellular carcinoma cell line HepG2, and they may be considered non-toxic (22 compounds with IC50 over 200?μm).
Carboxylic Acid Deoxyfluorination and One-Pot Amide Bond Formation Using Pentafluoropyridine (PFP)
Brittain, William D. G.,Cobb, Steven L.
supporting information, p. 5793 - 5798 (2021/08/01)
This work describes the application of pentafluoropyridine (PFP), a cheap commercially available reagent, in the deoxyfluorination of carboxylic acids to acyl fluorides. The acyl fluorides can be formed from a range of acids under mild conditions. We also demonstrate that PFP can be utilized in a one-pot amide bond formation via in situ generation of acyl fluorides. This one-pot deoxyfluorination amide bond-forming reaction gives ready access to amides in yields of ≤94%.
Nature inspired singlet oxygen generation to access α-amino carbonyl compounds: Via 1,2-acyl migration
Schilling, Waldemar,Zhang, Yu,Sahoo, Prakash Kumar,Sarkar, Samir Kumar,Gandhi, Sivaraman,Roesky, Herbert W.,Das, Shoubhik
supporting information, p. 379 - 387 (2021/01/28)
We have discovered chlorophyll catalyzed 1,2-acyl migration reactions to achieve α-amino carbonyl compounds directly from the enaminones. In general, singlet oxygen is generated during photosynthesis in the photosystem II center. This singlet oxygen can readily react with the unsaturated double bonds present in biomolecules. This reactivity intrigued us to apply this concept towards unsaturated enaminones and others to achieve highly valuable compounds. Indeed, this photosensitizer is very cheap, commercially available, main group metal based and provided excellent efficiency for singlet oxygen mediated chemistry by achieving high turnover number (TON) > 300 with a high turnover frequency (TOF) of 50 h-1. Finally, a combination of DFT calculations and detailed mechanistic experiments provided the exact role of the photosensitizer and clear insights into the reaction.
