4210-32-6Relevant academic research and scientific papers
Copper-mediated conversion of alkynes into nitriles via iodotriazoles
Kori, Ryosuke,Murakami, Keigo,Nishiyama, Yoshitake,Toma, Tatsuya,Yokoshima, Satoshi
, p. 278 - 280 (2021/03/08)
We disclose our studies on a copper-mediated reaction of alkynes with trimethylsilyl azide to afford nitriles, and proposed a reaction mechanism, which involves an iodoalkyne and an iodotriazole as intermediates.
Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
, (2020/12/09)
The synthesis of nitrile under mild conditions was achieved via dehydration of primary amide using lead salts as catalyst. The reaction processes were intensified by not only adding surfactant but also continuously removing the only by-product, water from the system. Both aliphatic and aromatic nitriles can be prepared in this manner with moderate to excellent yields. The reaction mechanisms were obtained with high-level quantum chemical calculations, and the crucial role the anionic ligand plays in the transformations were revealed.
Method for dehydrating primary amide into nitriles under catalysis of cobalt
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Paragraph 0105-0107, (2021/06/21)
The invention provides a method for dehydrating primary amide into nitrile. The method comprises the following steps: mixing primary amide (II), silane, sodium triethylborohydride, aminopyridine imine tridentate nitrogen ligand cobalt complex (I) and a reaction solvent under the protection of inert gas, carrying out reacting at 60-100 DEG C for 6-24 hours, and post-treating reaction liquid to obtain a nitrile compound (III). According to the invention, an effective method for preparing nitrile compounds by cobalt-catalyzed primary amide dehydration reaction by using the novel aminopyridine imine tridentate nitrogen ligand cobalt complex catalyst is provided; and compared with existing methods, the method has the advantages of simple operation, mild reaction conditions, wide application range of reaction substrates, high selectivity, stable catalyst, high efficiency, and relatively high practical application value in synthesis.
Dual Nickel/Photoredox-Catalyzed Deaminative Cross-Coupling of Sterically Hindered Primary Amines
Dorsheimer, Julia R.,Ashley, Melissa A.,Rovis, Tomislav
supporting information, p. 19294 - 19299 (2021/11/23)
We report a method to activate α-3° amines for deaminative arylation via condensation with an electron-rich aldehyde and merge this reactivity with nickel metallaphotoredox to generate benzylic quaternary centers, a common motif in pharmaceuticals and natural products. The reaction is accelerated by added ammonium salts. Evidence is provided in support of two roles for the additive: inhibition of nickel black formation and acceleration of the overall reaction rate. We demonstrate a robust scope of amine and haloarene coupling partners and show an expedited synthesis of ALK2 inhibitors.
Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
supporting information, p. 3723 - 3728 (2021/04/07)
We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
Chatterjee, Basujit,Jena, Soumyashree,Chugh, Vishal,Weyhermüller, Thomas,Werlé, Christophe
, p. 7176 - 7185 (2021/06/30)
The direct synthesis of amides and nitriles from readily available aldehyde precursors provides access to functional groups of major synthetic utility. To date, most reliable catalytic methods have typically been optimized to supply one product exclusively. Herein, we describe an approach centered on an operationally simple iron-based system that, depending on the reaction conditions, selectively addresses either the C=O or C-H bond of aldehydes. This way, two divergent reaction pathways can be opened to furnish both products in high yields and selectivities under mild reaction conditions. The catalyst system takes advantage of iron's dual reactivity capable of acting as (1) a Lewis acid and (2) a nitrene transfer platform to govern the aldehyde building block. The present transformation offers a rare control over the selectivity on the basis of the iron system's ionic nature. This approach expands the repertoire of protocols for amide and nitrile synthesis and shows that fine adjustments of the catalyst system's molecular environment can supply control over bond activation processes, thus providing easy access to various products from primary building blocks.
Highly Efficient Oxidative Cyanation of Aldehydes to Nitriles over Se,S,N-tri-Doped Hierarchically Porous Carbon Nanosheets
Hua, Manli,Song, Jinliang,Huang, Xin,Liu, Huizhen,Fan, Honglei,Wang, Weitao,He, Zhenhong,Liu, Zhaotie,Han, Buxing
supporting information, p. 21479 - 21485 (2021/08/23)
Oxidative cyanation of aldehydes provides a promising strategy for the cyanide-free synthesis of organic nitriles. Design of robust and cost-effective catalysts is the key for this route. Herein, we designed a series of Se,S,N-tri-doped carbon nanosheets with a hierarchical porous structure (denoted as Se,S,N-CNs-x, x represents the pyrolysis temperature). It was found that the obtained Se,S,N-CNs-1000 was very selective and efficient for oxidative cyanation of various aldehydes including those containing other oxidizable groups into the corresponding nitriles using ammonia as the nitrogen resource below 100 °C. Detailed investigations revealed that the excellent performance of Se,S,N-CNs-1000 originated mainly from the graphitic-N species with lower electron density and synergistic effect between the Se, S, N, and C in the catalyst. Besides, the hierarchically porous structure could also promote the reaction. Notably, the unique feature of this metal-free catalyst is that it tolerated other oxidizable groups, and showed no activity on further reaction of the products, thereby resulting in high selectivity. As far as we know, this is the first work for the synthesis of nitriles via oxidative cyanation of aldehydes over heterogeneous metal-free catalysts.
Efficient nitriding reagent and application thereof
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Paragraph 0193-0196, (2021/03/31)
The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
Development and Molecular Understanding of a Pd-Catalyzed Cyanation of Aryl Boronic Acids Enabled by High-Throughput Experimentation and Data Analysis
De Jesus Silva, Jordan,Bartalucci, Niccolò,Jelier, Benson,Grosslight, Samantha,Gensch, Tobias,Schünemann, Claas,Müller, Bernd,Kamer, Paul C. J.,Copéret, Christophe,Sigman, Matthew S.,Togni, Antonio
, (2021/11/10)
A synthetic method for the palladium-catalyzed cyanation of aryl boronic acids using bench stable and non-toxic N-cyanosuccinimide has been developed. High-throughput experimentation facilitated the screen of 90 different ligands and the resultant statistical data analysis identified that ligand σ-donation, π-acidity and sterics are key drivers that govern yield. Categorization into three ligand groups – monophosphines, bisphosphines and miscellaneous – was performed before the analysis. For the monophosphines, the yield of the reaction increases for strong σ-donating, weak π-accepting ligands, with flexible pendant substituents. For the bisphosphines, the yield predominantly correlates with ligand lability. The applicability of the designed reaction to a wider substrate scope was investigated, showing good functional group tolerance in particular with boronic acids bearing electron-withdrawing substituents. This work outlines the development of a novel reaction, coupled with a fast and efficient workflow to gain understanding of the optimal ligand properties for the design of improved palladium cross-coupling catalysts.
Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile
Liu, Si-Zhan,Li, Jing,Xue, Cao-Gen,Xu, Xue-Tao,Lei, Lin-Sheng,Huo, Chen-Yu,Wang, Zhen,Wang, Shao-Hua
supporting information, (2021/02/01)
A copper-promoted cyanation of aryl iodides has been successfully developed by using N,N-dimethyl aminomalononitrile as the cyanide source with moderate toxicity and better stability. This reaction features broad substrate scope, excellent reaction yields, readily available catalyst, and simple reaction conditions.
