403-54-3Relevant academic research and scientific papers
Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
, 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.
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.
Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
, (2021/01/12)
Cyanation of aryl iodides is still challenging work for chemical researchers because of harsh reaction conditions and toxic cyanide sources. Herein, we have developed a new protocol based on the combination of the catalyst Pd@CeO2, nontoxic cyanide source K4[Fe (CN)6]·3H2O, and driving force visible light irradiation. The reaction is operated at relatively moderate temperature (55°C) and exhibits good catalytic efficiency of product aryl nitriles (yields of 89.4%). Moreover, the catalyst Pd@CeO2 possesses good reusability with a slight loss of photocatalytic activity after five consecutive runs. The reaction system based on the above combination shows a wide range of functional group tolerance under the same conditions. Reaction conditions such as temperature, time, the component of catalyst, and solutions are optimized by studying cyanation of 1-iodo-4-nitrobenzene as model reaction. According to these results, the possible mechanism of Pd@CeO2-catalyzed cyanation of aryl iodides under visible light irradiation is proposed based on the influence of visible light on the catalyst and reactant compounds. In all, we provided an environmental and economic method for preparation of aryl nitriles from cyanation of aryl iodides based on the goal of green chemistry for sustainable development.
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 catalyzing oxidation of amines to generate nitrile by using nonmetal mesoporous nitrogen-doped carbon material
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Paragraph 0019; 0038, (2021/05/08)
The invention discloses a method for preparing nitrile by catalyzing amine oxidation with a non-metal mesoporous nitrogen-doped carbon material catalyst, which is applied to the field of synthesis, the material is prepared by using a nitrogen-containing organic ligand as a precursor and silica sol as a template agent, calcining in the atmosphere of inert gases such as N2 or Ar and then removing the template agent; oxygen or air is used as an oxygen source, the reaction is performed at 80-130 DEG C under the action of ammonia water in the presence of a solvent, the effect is good, and the product still keeps higher activity after being recycled for more than 8 times, and has a wide industrial application prospect. The invention provides a heterogeneous non-metal catalytic system for catalyzing amine oxidation to prepare nitrile for the first time, and compared with a reported metal catalyst, the heterogeneous non-metal catalytic system does not bring metal pollution to a product to influence the effect of cyano drugs.
Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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Paragraph 0034-0039; 0118-0123, (2020/09/16)
The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
Fluorination of arylboronic esters enabled by bismuth redox catalysis
Planas, Oriol,Wang, Feng,Leutzsch, Markus,Cornella, Josep
, p. 313 - 317 (2020/01/28)
Bismuth catalysis has traditionally relied on the Lewis acidic properties of the element in a fixed oxidation state. In this paper, we report a series of bismuth complexes that can undergo oxidative addition, reductive elimination, and transmetallation in a manner akin to transition metals. Rational ligand optimization featuring a sulfoximine moiety produced an active catalyst for the fluorination of aryl boronic esters through a bismuth (III)/bismuth (V) redox cycle. Crystallographic characterization of the different bismuth species involved, together with a mechanistic investigation of the carbonfluorine bond-forming event, identified the crucial features that were combined to implement the full catalytic cycle.
KCNT1 INHIBITORS AND METHODS OF USE
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Paragraph 000497, (2020/11/23)
The present invention is directed to, in part, compounds and compositions useful for preventing and/or treating a neurological disease or disorder, a disease or condition relating to excessive neuronal excitability, and/or a gain-of-function mutation in a gene (e.g., KCNT1). Methods of treating a neurological disease or disorder, a disease or condition relating to excessive neuronal excitability, and/or a gain-of-function mutation in a gene such as KCNT1 are also provided herein.
Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
, p. 378 - 385 (2020/10/02)
We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
Aerobic oxidation of primary benzylic amines to amides and nitriles catalyzed by ruthenium carbonyl clusters carrying N,O-bidentate ligands
Dong, Qing,Han, Zhangang,Hao, Zhiqiang,Li, Ying,Lin, Jin,Lu, Guo-Liang,Meng, Lizhen,Yan, Xinlong
, p. 3480 - 3487 (2020/04/02)
Four trinuclear ruthenium carbonyl clusters, (6-BrPyCHRO)2Ru3(CO)8 (R = 4-OCH3C6H4, 1a; R = 4-BrC6H4, 1b) and (2-OC6H4-HCN-C6H4R)2Ru3(CO)8 (R = 4-OCH3, 2a; R = 4-Br, 2b), were synthesized from the reactions of Ru3(CO)12 with the corresponding N,O-bidentate ligands (two pyridyl alcohols and two Schiff bases) respectively in a ratio of 1:2. Three new complexes 1b, 2a and 2b have been fully characterized by elemental analysis, FT-IR, NMR and X-ray crystallography. The catalytic activity of these ruthenium complexes for the aerobic oxidation of primary benzylic amines to amides and nitriles in the presence of t-BuOK was investigated, of which the Schiff base complex 2a was found to exhibit the highest activity.
