- Facile synthesis of nitriles from aromatic aldehydes using DMSO-I2
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Nitriles have been prepared from different aromatic aldehydes by a one-pot process using hydroxylamine hydrocloride and molecular iodine in the presence of dimethylsulphoxide. Copyright Taylor & Francis Group, LLC.
- Gaikwad, Digambar D.,Renukdas, Sameer V.,Kendre, Babasaheb V.,Shisodia, Suresh U.,Borade, Ravikumar M.,Shinde, Praveen S.,Chaudhary, Sunil S.,Pawar, Rajendra P.
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- Cyanide-Free Cyanation of sp2 and sp-Carbon Atoms by an Oxazole-Based Masked CN Source Using Flow Microreactors
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This work reports a cyanide-free continuous-flow process for cyanation of sp2 and sp carbons to synthesize aryl, vinyl and acetylenic nitriles from (5-methyl-2-phenyloxazol-4-yl) boronic acid [OxBA] reagent as a sole source of carbon-bound mask
- Sharma, Brijesh M.,Nikam, Arun V.,Lahore, Santosh,Ahn, Gwang-Noh,Kim, Dong-Pyo
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supporting information
(2022/02/25)
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- Method for catalyzing oxidation of amines to generate nitrile by using nonmetal mesoporous nitrogen-doped carbon material
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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.
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Paragraph 0019; 0039
(2021/05/08)
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- Design of an Electron-Withdrawing Benzonitrile Ligand for Ni-Catalyzed Cross-Coupling Involving Tertiary Nucleophiles
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The design of new ligands for cross-coupling is essential for developing new catalytic reactions that access valuable products such as pharmaceuticals. In this report, we exploit the reactivity of nitrile-containing additives in Ni catalysis to design a benzonitrile-containing ligand for cross-coupling involving tertiary nucleophiles. Kinetic and Hammett studies are used to elucidate the role of the optimized ligand, which demonstrate that the benzonitrile moiety acts as an electron-acceptor to promote reductive elimination over β-hydride elimination and stabilize low-valent Ni. With these conditions, a protocol for decyanation-metalation and Ni-catalyzed arylation is conducted, enabling access to quaternary α-arylnitriles from disubstituted malononitriles.
- Edjoc, Racquel K.,Mills, L. Reginald,Rousseaux, Sophie A. L.
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p. 10422 - 10428
(2021/07/26)
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- Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
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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.
- Ruan, Shixiang,Ruan, Jiancheng,Chen, Xinzhi,Zhou, Shaodong
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- Efficient nitriding reagent and application thereof
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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.
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Paragraph 0230-0232
(2021/03/31)
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- A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
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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.
- Chatterjee, Basujit,Jena, Soumyashree,Chugh, Vishal,Weyhermüller, Thomas,Werlé, Christophe
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p. 7176 - 7185
(2021/06/30)
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- Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
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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.
- Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
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- Method for continuous preparation of nitriles in a pipelined reactor (by machine translation)
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The method comprises the following steps that a tin catalyst is coated on the inner wall of the pipeline reactor; and the method comprises the following steps: coating a tin catalyst on the inner wall of the pipeline reactor. The amide solution and the catalytic auxiliary agent are mixed and then sent to a pipeline reactor, and the amide is dehydrated to generate nitrile at the reaction pressure of 0.1 - 2.0 mpa and 100 - 200 °C reaction temperature. The resulting reaction product was separated to give the crude product of the nitrile to which the amide corresponded. In the pipeline reactor, the corresponding nitrile is continuously prepared under the action of the tin catalyst, a dehydrating agent is not needed, byproducts only are water, and three wastes are reduced. (by machine translation)
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Paragraph 0036-0047; 0056-0057
(2020/12/14)
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- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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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.
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Paragraph 0034-0039; 0172-0177
(2020/09/16)
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- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
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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.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
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p. 378 - 385
(2020/10/02)
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- Chlorotropylium Promoted Conversions of Oximes to Amides and Nitriles
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Chlorotropylium chloride as a catalyst for the transformations of oximes, ketones, and aldehydes to their corresponding amides and nitriles in excellent yields (up to 99 %) and in short reaction times (mostly 10–15 min). Oximes were electrophilically attacked on the hydroxyl oxygen by chlorotropylium. The produced tropylium oxime ethers were the key intermediates, of which the ketoxime ether led to amide through Beckmann rearrangement, and the aldoxime ether led to nitrile by nitrogen base DBU assisted formal dehydration. This chlorotropylium activation protocol offered general, mild, and efficient avenues bifurcately from oximes to both amides and nitriles by one organocatalyst.
- Xu, Jiaxi,Gao, Yu,Li, Zhenjiang,Liu, Jingjing,Guo, Tianfo,Zhang, Lei,Wang, Haixin,Zhang, Zhihao,Guo, Kai
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p. 311 - 315
(2020/01/25)
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- SO2F2-Mediated one-pot cascade process for transformation of aldehydes (RCHO) to cyanamides (RNHCN)
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A simple, mild and practical cascade process for the direct conversion of aldehydes to cyanamides was developed featuring a wide substrate scope and great functional group tolerability. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable cyanamides in a pot, atom, and step-economical manner with a green nitrogen source. This protocol will serve as a robust tool for the installation of the cyanamide moiety in various complicated molecules.
- Ding, Chengrong,Ge, Shuting,Wei, Junjie,Zhang, Guofu,Zhao, Yiyong
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p. 17288 - 17292
(2020/05/18)
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- NHC-catalyzed silylative dehydration of primary amides to nitriles at room temperature
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Herein we report an abnormal N-heterocyclic carbene catalyzed dehydration of primary amides in the presence of a silane. This process bypasses the energy demanding 1,2-siloxane elimination step usually required for metal/silane catalyzed reactions. A detailed mechanistic cycle of this process has been proposed based on experimental evidence along with computational study.
- Ahmed, Jasimuddin,Hota, Pradip Kumar,Maji, Subir,Mandal, Swadhin K.,Rajendran, N. M.
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supporting information
p. 575 - 578
(2020/01/29)
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- Method for continuous preparation of nitriles by amides (by machine translation)
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The method comprises the following steps: preparing a lead salt supported by a molecular sieve by a lead salt and a molecular sieve through an impregnation method; and filling a molecular sieve-loaded lead catalyst into a fixed bed reactor. The amide or amide solution is sent into a fixed bed reactor from the top of the fixed bed to be subjected to catalytic dehydration, and the obtained reaction product is led out from the bottom of the fixed bed. The reaction product is separated to obtain the crude product of the nitrile corresponding to the amide. A fixed bed continuous production process is adopted, the reaction process is simple, the production efficiency is high, the product post-treatment is simple, and industrial production is easy to realize. (by machine translation)
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Paragraph 0033-0054; 0061-0065
(2020/12/15)
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- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
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The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
- Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
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supporting information
p. 281 - 285
(2020/01/28)
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- Nitrosation of Cyanamide: Preparation and Properties of the Elusive E- and Z-N'-Cyanodiazohydroxides
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Nitrosation of cyanamide leads to unstable E/Z-cyanodiazohydroxides that easily deprotonate to E/Z-cyanodiazotates. Pursuing observations of E. Drechsel 145 years ago, the structure and reactivity of those products was determined, mainly in aqueous solution. Depending on the pH, three different thermal decomposition pathways give either N2O + HCN or N2 + HNCO. They were evaluated experimentally and by quantum mechanical calculations.
- Guethner, Thomas,Huber, Evi,Sans, Juergen,Thalhammer, Franz
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supporting information
(2020/04/29)
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- Photocatalytic Conversion of Benzyl Alcohols/Methyl Arenes to Aryl Nitriles via H-Abstraction by Azide Radical
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This report presents the visible-light-assisted synthesis of aryl nitriles from easily accessible alcohols or methyl arenes in the presence of O2. Organic photoredox catalyst, 4CzIPN (1,2,3,5-tetrakis(carbazol-9-yl)-4,6-dicyanobenzene), induces single electron transfer (SET) from azide N3? and generates azide radical N3?.The photogenerated N3? abstracts H atom from α-C?H bond of benzylic system, which provides aldehyde and hydrazoic acid (HN3) in situ. This reaction subsequently forms azido alcohol intermediate that transforms into nitrile with the assistance of triflic acid (Br?nsted acid). A range of alcohols and methyl arenes successfully underwent cyanation at room temperature with good to excellent yields and showed good functional group tolerance.
- Shee, Maniklal,Shah, Sk. Sheriff,Singh, N. D. Pradeep
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supporting information
p. 14070 - 14074
(2020/10/12)
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- Cascade Process for Direct Transformation of Aldehydes (RCHO) to Nitriles (RCN) Using Inorganic Reagents NH2OH/Na2CO3/SO2F2 in DMSO
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A simple, mild, and practical process for direct conversion of aldehydes to nitriles was developed feathering a wide substrate scope and great functional group tolerability (52 examples, over 90% yield in most cases) using inorganic reagents (NH2OH/Na2CO3/SO2F2) in DMSO. This method allows for transformations of readily available, inexpensive, and abundant aldehydes to highly valuable nitriles in a pot, atom, and step-economical manner without transition metals. This protocol will serve as a robust tool for the installation of cyano-moieties to complicated molecules.
- Fang, Wan-Yin,Qin, Hua-Li
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p. 5803 - 5812
(2019/05/14)
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- A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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A new transition-metal-free one-pot cascade process for the direct conversion of alcohols to nitriles was developed without introducing an “additional carbon atom”. This protocol allows transformations of readily available, inexpensive, and abundant alcohols to highly valuable nitriles.
- Jiang, Ying,Sun, Bing,Fang, Wan-Yin,Qin, Hua-Li
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supporting information
p. 3190 - 3194
(2019/05/21)
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- Solvent-Tailored Pd3P0.95 nano catalyst for amide-nitrile inter-conversion, the hydration of nitriles and transfer hydrogenation of the CO bond
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For the first time, a one pot thermolysis of [Pd(PPh3)2Cl2] prepared by reacting Ph3P with PdCl2 in a 2:1 molar ratio in MeOH at 280 °C in a trioctylphosphine (TOP) and oleylamine(OA)-octadecane(ODE) mixture (1:1) was used to prepare quantum dots (QDs; size ～2-3 nm) and nanoparticles (NPs; size ～13-14 nm), respectively, of composition Pd3P0.95. TEM, SEM-EDX, powder-XRD and XPS (for QDs only) were used to authenticate the two nanophases. 31P{1H}NMR experiments performed to monitor the progress of thermolysis reactions revealed that the phosphorus present in the Pd3P0.95 QDs had come from TOP, whereas in Pd3P0.95 NPs, its source is triphenylphosphine. The nature of the solvent did not affect the chemical composition of the nano-phase but controlled its size. Probably, solvent dependent, unique, single source precursors (SSPs) of palladium were generated in situ, and controlled the size. The catalytic activity of both Pd3P0.95 QDs and NPs was explored. The QDs were found to be efficient as a catalyst for the amide-nitrile interconversion at room temperature (yield up to 92% in 4 h), hydration of nitriles and transfer hydrogenation (TH) of carbonyl compounds with yields up to 96% in 3-4 h. The yields and reaction rates of amide-nitrile inter-conversion and TH when catalyzed by Pd3P0.95 QDs were found to be higher compared to the ones observed with the Pd/C catalyst. The binding energy of Pd(3d) in the X-ray photoelectron spectrum (XPS) of Pd3P0.95 indicated an electron transfer from the metal to phosphorus, resulting in electron deficient palladium, which facilitates the coordination of a substrate to Pd and drives the reaction. The reusability of Pd3P0.95 QDs for the interconversion was found to be up to 4-Times, while for the transfer hydrogenation of carbonyl compounds it was up to 6-Times, but with a diminished yield. Pd3P0.95 NPs were found to be less active (yield up to 36% in optimized reaction conditions) in comparison to Pd3P0.95 QDs. The mercury poisoning test suggested that the catalysis predominantly proceeded heterogeneously on the surface of the QDs. The PXRD and XPS results did not suggest a significant variation in the phase of QDs after the third catalytic cycle. The bleeding of Pd during catalysis (determined by flame AAS) and the agglomeration of QDs as supported by the SEM-EDX and TEM results are probably responsible for the reduction in the catalytic activity of QDs after reusing three times.
- Sharma, Alpesh K.,Joshi, Hemant,Bhaskar, Renu,Singh, Ajai K.
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supporting information
p. 10962 - 10970
(2019/07/31)
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- Immobilized palladium nanoparticles on a cyclodextrin-polyurethane nanosponge (Pd-CD-PU-NS): An efficient catalyst for cyanation reaction in aqueous media
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Immobilized palladium nanoparticles on a cyclodextrin-polyurethane nanosponge (Pd-CD-PU-NS) were found to be an efficient heterogeneous catalyst in the cyanation reaction of aryl halides in aqueous media. This catalyst system is containing palladium nanoparticles with a size of ～7 nm. Moreover, the CD-PU-NS support formed microsphere-shaped structures with a size of ～100–200 nm. The TEM images show that Pd nanoparticles were formed in near spherical shape morphology and were immobilized in the structure of the CD-PU-NS support. Under our optimized reaction conditions, aryl cyanides were obtained in high yields in the presence of the Pd-CD-PU-NS catalyst. Our results demonstrated that the Pd-CD-PU-NS catalyst is highly effective in the cyanation reaction in aqueous media. Furthermore, the catalyst could be simply extracted from the reaction mixture, providing an efficient methodology for the synthesis of aryl cyanides. The Pd-CD-PU-NS catalyst could be recycled four times with almost consistent catalytic efficiency.
- Khajeh Dangolani, Soheila,Sharifat, Sara,Panahi, Farhad,Khalafi-Nezhad, Ali
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supporting information
p. 256 - 265
(2019/06/07)
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- Catalytic oxidative conversion of aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8: A practical approach to febuxostat
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A novel approach to convert aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8 has been developed. Both alkyl and aryl nitriles were obtained in good to excellent yields. Electron-withdrawing and electron-donating groups, such as fluoro, chloro, bromo, nitro, ester, cyano, trifluoromethyl and alkoxy were tolerated. Notably, febuxostat and its intermediate, ethyl 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-5-thiazolecarboxylate, were obtained in excellent yields.
- Chen, Han,Sun, Sijia,Xi, Haoying,Hu, Kaifang,Zhang, Ning,Qu, Jingping,Zhou, Yuhan
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supporting information
p. 1434 - 1436
(2019/05/01)
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- Visible-light-driven catalytic oxidation of aldehydes and alcohols to nitriles by 4-acetamido-tempo using ammonium carbamate as a nitrogen source
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A mild and efficient route to prepare nitriles from aldehydes by combining photoredox catalysis with oxoammonium cations is reported. The reaction is performed using ammonium carbamate as the nitrogen source. The practicality of the method is increased by the extension of the dual catalytic system to one-pot two-step conversion of alcohols to nitriles.
- Nandi, Jyoti,Leadbeater, Nicholas E.
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supporting information
p. 9182 - 9186
(2019/11/05)
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- Selectivity-tunable amine aerobic oxidation catalysed by metal-free N,O-doped carbons
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Herein, we present a series of N,O-doped mesoporous carbons obtained at different pyrolysis temperatures as the first metal-free catalysts which successfully switch between imine and nitrile products for amine oxidation. Systematic characterization studies and control experiments revealed that the C-O group on the surface could function as a catalytically active site for nitrile synthesis and the N-doping environment was essential.
- Li, Yingguang,Shang, Sensen,Wang, Lianyue,Lv, Ying,Niu, Jingyang,Gao, Shuang
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supporting information
p. 12251 - 12254
(2019/10/21)
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- Cyanation of Anilines to Aryl Nitriles Using tert-Butyl Isocyanide: A Simple and Copper-free Procedure
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In this manuscript, a simple and copper-free procedure for the synthesis of aryl nitrile derivatives from anilines is described. Under the improved protocol, the anilines were reacted with tert-butyl isocyanide under a mild reaction condition without the use of solvents and copper catalyst to synthesize benzonitriles. This copper-free Sandmeyer-type reaction could tolerate a range of anilines bearing different functional groups and also can be conducted even without the exclusion of air. In addition, this method has afforded the aryl nitriles in moderate to good yields (52–81%). The obtained results in this study reveal that the tert-butyl isocyanide as a potential cyanide source for the cyanation reaction.
- Chia, Poh Wai,Yong, Fu Siong Julius,Mohamad, Habsah,Kan, Su-Yin
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supporting information
p. 939 - 942
(2019/08/21)
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- Synthesis of Nitriles from Primary Amides or Aldoximes under Conditions of a Catalytic Swern Oxidation
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The preparation of nitriles from primary amides or aldoximes was achieved by using oxalyl chloride with a catalytic amount of dimethyl sulfoxide in the presence of Et3N. The reactions were complete within 1 h after addition at room temperature. A diverse range of cyano compounds were obtained in good to excellent yields, including aromatic, heteroaromatic, cyclic, and acyclic aliphatic species.
- Ding, Rui,Liu, Yongguo,Han, Mengru,Jiao, Wenyi,Li, Jiaqi,Tian, Hongyu,Sun, Baoguo
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p. 12939 - 12944
(2018/10/20)
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- A radical cyclization cascade of 2-alkynylbenzonitriles with sodium arylsulfinates
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A convenient radical cyclization cascade procedure for the construction of sulfonated indenones from 2-alkynylbenzonitriles and sodium arylsulfinates has been explored under mild reaction conditions. The present methodology offers a low-cost and operationally straightforward approach to synthesizing various sulfonated indenones in moderate to good yields by simple use of cheap sodium persulfate as an oxidant and environmentally benign water as a co-solvent.
- Zhou, Bang,Chen, Wenqi,Yang, Yuzhong,Yang, Yuan,Deng, Guobo,Liang, Yun
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supporting information
p. 7959 - 7963
(2018/11/21)
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- Dehydration of Amides to Nitriles under Conditions of a Catalytic Appel Reaction
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A highly expedient protocol for a catalytic Appel-type dehydration of amides to nitriles has been developed that employs oxalyl chloride and triethylamine along with triphenylphosphine oxide as a catalyst. The reactions are usually complete in less than 10 min with only a 1 mol % catalyst loading. The reaction scope includes aromatic, heteroaromatic, and aliphatic amides, including derivatives of α-hydroxy and α-amino acids.
- Shipilovskikh, Sergei A.,Vaganov, Vladimir Yu.,Denisova, Elena I.,Rubtsov, Aleksandr E.,Malkov, Andrei V.
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supporting information
p. 728 - 731
(2018/02/09)
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- Combining Oxoammonium Cation Mediated Oxidation and Photoredox Catalysis for the Conversion of Aldehydes into Nitriles
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A method to oxidize aromatic aldehydes to nitriles has been developed. It involves a dual catalytic system of 4-acetamido-TEMPO and visible-light photoredox catalysis. The reaction is performed using ammonium persulfate as both the terminal oxidant and nitrogen source.
- Nandi, Jyoti,Witko, Mason L.,Leadbeater, Nicholas E.
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supporting information
p. 2185 - 2190
(2018/09/29)
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- A general electrochemical strategy for the Sandmeyer reaction
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Herein we report a general electrochemical strategy for the Sandmeyer reaction. Using electricity as the driving force, this protocol employs a simple and inexpensive halogen source, such as NBS, CBrCl3, CH2I2, CCl4, LiCl and NaBr for the halogenation of aryl diazonium salts. In addition, we found that these electrochemical reactions could be performed using anilines as the starting material in a one-pot fashion. Furthermore, the practicality of this process was demonstrated in the multigram scale synthesis of aryl halides using highly inexpensive graphite as the electrode. A series of detailed mechanism studies have been performed, including radical clock and radical scavenger study, cyclic voltammetry analysis and in situ electron paramagnetic resonance (EPR) analysis.
- Liu, Qianyi,Sun, Beiqi,Liu, Zheng,Kao, Yi,Dong, Bo-Wei,Jiang, Shang-Da,Li, Feng,Liu, Guoquan,Yang, Yang,Mo, Fanyang
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p. 8731 - 8737
(2018/12/10)
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- Catalytic Promiscuity of Galactose Oxidase: A Mild Synthesis of Nitriles from Alcohols, Air, and Ammonia
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We report an unprecedented catalytically promiscuous activity of the copper-dependent enzyme galactose oxidase. The enzyme catalyses the one-pot conversion of alcohols into the related nitriles under mild reaction conditions in ammonium buffer, consuming ammonia as the source of nitrogen and dioxygen (from air at atmospheric pressure) as the only oxidant. Thus, this green method does not require either cyanide salts, toxic metals, or undesired oxidants in stoichiometric amounts. The substrate scope of the reaction includes benzyl and cinnamyl alcohols as well as 4- and 3-pyridylmethanol, giving access to valuable chemical compounds. The oxidation proceeds through oxidation from alcohol to aldehyde, in situ imine formation, and final direct oxidation to nitrile.
- Vilím, Jan,Knaus, Tanja,Mutti, Francesco G.
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supporting information
p. 14240 - 14244
(2018/10/15)
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- An effective preparation of both 1,3-diketones and nitriles from alkynones with oximes as hydroxide sources
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An effective phosphine-catalyzed protocol has been established for the syntheses of 1,3-diketones and nitriles from alkynones with oximes as hydroxide surrogates. This method features the use of a phosphine catalyst, compatibility with various functional groups and ambient temperature, which makes this approach very practical. A plausible mechanism was proposed.
- Chen, Pei,Zhang, Qian-Qian,Guo, Jia,Chen, Lu-Lu,Wang, Yan-Bo,Zhang, Xiao
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p. 6958 - 6966
(2018/10/02)
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- Method for synthesizing aromaticnitrile by using metalloporphyrin to catalyze aromatic olefin
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The invention discloses a method for synthesizing aromaticnitrile by using metalloporphyrin to catalyze aromatic olefin. The method is characterized in that an aromatic alkene compound or an aromaticheterocyclic alkene compound and nitrite are reacted to generate an aromaticnitrile compound or an aromatic heterocyclic nitrile compound under the catalyzing function of the metalloporphyrin by a one-step method in air atmosphere and an acid solution system. The method has the advantages that (1) the reaction conditions are moderate, the operation is simple, the control is easy, and the yield rate is higher; (2) the high-efficiency metalloporphyrin catalyst is used, but the poisonous CN (carbon-nitrogen) negative ion reagent is not used, so that the pollution to the environment is decreased;(3) the prices of raw materials, nitrogen sources, acid reagents and the like are low, the obtaining is easy, the production cost is obviously reduced, and the method can be popularized and applied toindustrialized production.
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Paragraph 0121-0125
(2018/03/01)
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- Trinuclear complexes of palladium(II) with chalcogenated N-heterocyclic carbenes: Catalysis of selective nitrile-primary amide interconversion and Sonogashira coupling
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3-Methyl-1-(2-(phenylthio/seleno)ethyl)-1H-benzo[d]imidazol-3-ium iodide (L1/L2), a precursor of sulfated/selenated N-heterocyclic carbene, was synthesized by the reaction of benzimidazole with 1,2-dichloroethane followed by treatment with PhS/SeNa and MeI. The reaction of L1/L2 with Ag2O followed by treatment with [Pd(CH3CN)2Cl2] (metal to ligand ratio 3:2), i.e. transmetallation, resulted in trinuclear palladium(ii) complexes [Pd3(L1/L2-HI)2(CH3CN)Cl6] (1-2). The complexes were characterized with 1H, 13C{1H} and 77Se{1H} NMR (2 only), elemental analyses, HR-MS and single-crystal X-ray diffraction. The geometry of three Pd atoms in each complex is nearly square planar. The Pd-S/Se, Pd-C, Pd-N and Pd-Cl bond distances (?) in 1/2 are 2.3179(19)/2.4312(10), 1.968(7)/1.952(4), 2.073(8)/2.079(4) and 2.2784(19)-2.298(2)/2.292(2)-2.3003(15), respectively. In both the complexes, all Cl are trans to each other. For the central Pd atom, two benzimidazole rings are also trans to each other. The C-H?Cl non-covalent interactions result in a three-dimensional network. The moisture and air insensitive trinuclear Pd(ii) complexes 1 and 2 are thermally stable and efficient as a catalyst for nitrile-amide interconversion and amine-free Sonogashira C-C coupling (in the presence of CuI). The optimum temperature is 80 °C for the interconversion and 110 °C for the coupling. The catalytic protocols are applicable to both aliphatic and aromatic amides/nitriles. The optimum catalyst loading is 1 mol% for the C-C coupling and 0.5 to 1 mol% for the interconversion. K2CO3 as a base gives the best result for Sonogashira C-C coupling. In the conversion of nitriles to amides, the formation of an acid was not detected. After using once, 1/2 can carry out the conversion of ten fresh lots of nitriles to amides with almost the same efficiency. The real catalytic species for the interconversion and coupling appear to be based on Pd(ii) and Pd(0), respectively.
- Dubey, Pooja,Gupta, Sonu,Singh, Ajai K.
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p. 13065 - 13076
(2017/10/13)
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- Heterogeneous cobalt catalysts for selective oxygenation of alcohols to aldehydes, esters and nitriles
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Efficient and green oxygenation of alcohols to the corresponding aldehydes, esters and nitriles was developed with high selectivity. Functional alcohols, including some heterocyclic and allylic alcohols can be oxygenated to the corresponding aldehydes, esters and nitriles respectively. Moreover, the catalyst can be recycled and reused without significant deactivation. Noteworthy, the Co@NC (800-2h) catalyzed oxygenation of alcohols can be regulated easily by changing the reaction conditions, and then the corresponding aldehydes, esters and nitriles can be obtained in high yields respectively.
- Mao, Fei,Qi, Zhengliang,Fan, Haipeng,Sui, Dejun,Chen, Rizhi,Huang, Jun
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p. 1498 - 1503
(2017/01/18)
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- One-Pot, Metal-Free Conversion of Anilines to Aryl Bromides and Iodides
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A metal-free synthesis of aryl bromides and iodides from anilines via halogen abstraction from bromotrichloromethane and diiodomethane is described. This one-pot reaction affords aryl halides from the corresponding anilines in moderate to excellent yields without isolation of diazonium salts. The transformation has short reaction times, a simple workup, and insensitivity to moisture and air and avoids excess halogenation. DFT calculations support a SRN1 mechanism. This method represents a convenient alternative to the classic Sandmeyer reaction.
- Leas, Derek A.,Dong, Yuxiang,Vennerstrom, Jonathan L.,Stack, Douglas E.
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supporting information
p. 2518 - 2521
(2017/05/24)
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- A method for preparing of the benzonitrile derivatives
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The invention discloses a preparation method of a cyanobenzene derivative. The cyanobenzene derivative is prepared by taking phenylacetic acid or the derivative thereof as well as urea as raw materials, copper salt as a catalyst and oxygen as an oxidizing agent. According to the preparation method disclosed by the invention, by adopting copper salt as the catalyst and oxygen as the oxidizing agent without an extra cocatalyst, the raw materials phenylacetic acid or the derivative thereof are easy to purchase in the market, low in cost and various in type, and urea as the source of cyanogen is low in toxicity, low in price, mild in reaction condition and environmentally friendly, and has a good functional group compatibility.
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Paragraph 0021; 0022; 0023; 0054; 0055; 0056; 0057
(2016/10/17)
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- Synthesis of nitriles from aldehydes with trimethylphenylammonium tribromide and ammonium acetate
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Various aromatic and heterocyclic aldehydes were easily converted to respective nitriles with the combination of trimethylphenylammonium tribromide and ammonium acetate in good yields at room temperature.
- Sayama, Shinsei
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p. 1796 - 1802
(2016/11/06)
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- Electrochemical synthesis of nitriles from aldehydes using TEMPO as a mediator
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A novel electrochemical route to generate nitriles from aldehydes under mild conditions using a catalytic amount of TEMPO (2,2,6,6-tetramethylpiperidinyl-l-oxy) as the mediator and hexamethyldisilazane as the nitrogen source in the presence of acetic acid has been developed. A variety of aromatic, heteroaromatic and aliphatic aldehydes have been converted to their corresponding nitriles in good to excellent yields. A plausible reaction mechanism is proposed based on the cyclic voltammetry, in situ FTIR and the identification of intermediates.
- Chen, Qiguo,Fang, Chaojie,Shen, Zhenlu,Li, Meichao
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- Improved schmidt conversion of aldehydes to nitriles using azidotrimethylsilane in 1,1,1,3,3,3-Hexafluoro-2-Propanol
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The Schmidt reaction of aromatic aldehydes using a substoichiometric amount (40 mol %) of triflic acid is described. Low catalyst loading was enabled by a strong hydrogen-bond-donating solvent hexafluoro-2-propanol (HFIP). This improved protocol tolerates a broad scope of aldehydes with diverse functional groups and the corresponding nitriles were obtained in good to high yields without the need for aqueous work up.
- Motiwala, Hashim F.,Yin, Qin,Aubé, Jeffrey
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- Method for preparing nitrile by alcohol oxidation
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The invention provides a method for preparing nitrile by alcohol oxidation. The method comprises the following steps: mixing substrate alcohol which is shown as formula (I), a catalyst, a cocatalyst TEMPO, a ligand, an alkaline matter, 25 weight percent to 28 weight percent of ammonium hydroxide and a solvent; reacting for 2 to 24 hours with stirring in an oxygen atmosphere at 25 to 100 DEG C, and performing aftertreatment on reaction liquid to obtain a product nitrile which is shown in a formula (II). The method provided by the invention is environment friendly, wide in substrate application range, high in yield and mild in reaction conditions, has the preparation scale from grams to over hundreds of grams, and also has relatively high practical application value.
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Paragraph 0043; 0060; 0061
(2017/01/23)
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- Chemoselective Radical Dehalogenation and C-C Bond Formation on Aryl Halide Substrates Using Organic Photoredox Catalysts
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Despite the number of methods available for dehalogenation and carbon-carbon bond formation using aryl halides, strategies that provide chemoselectivity for systems bearing multiple carbon-halogen bonds are still needed. Herein, we report the ability to tune the reduction potential of metal-free phenothiazine-based photoredox catalysts and demonstrate the application of these catalysts for chemoselective carbon-halogen bond activation to achieve C-C cross-coupling reactions as well as reductive dehalogenations. This procedure works both for conjugated polyhalides as well as unconjugated substrates. We further illustrate the usefulness of this protocol by intramolecular cyclization of a pyrrole substrate, an advanced building block for a family of natural products known to exhibit biological activity.
- Poelma, Saemi O.,Burnett, G. Leslie,Discekici, Emre H.,Mattson, Kaila M.,Treat, Nicolas J.,Luo, Yingdong,Hudson, Zachary M.,Shankel, Shelby L.,Clark, Paul G.,Kramer, John W.,Hawker, Craig J.,Read De Alaniz, Javier
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p. 7155 - 7160
(2016/08/30)
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- Cleavage of the Carbon–Carbon Triple Bonds of Arylacetylenes for the Synthesis of Arylnitriles without a Metal Catalyst
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Cleavage of the carbon–carbon triple bonds of alkynes was achieved, which led to the synthesis of arylnitriles under transition-metal-free conditions. A vast range of terminal alkyne substrates underwent this reaction to provide the corresponding nitriles in moderate to good yields with good functional group tolerance.
- Lin, Yuanguang,Song, Qiuling
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p. 3056 - 3059
(2016/07/12)
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- Visible light catalysis synthesis method of aryl cyanide
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The invention discloses a visible light catalysis synthesis method of aryl cyanide. The method comprises the following steps: putting aryl halide, potassium ferrocyanide and alkali in an organic solvent; in the condition of magnetic stirring, starting a visible light source with power of 100-500W; irradiating with light intensity of 0.2-0.8W/cm until the reaction is over while controlling the reaction temperature at 25-85 DEG C; and carrying out a catalytic reaction for 1-12h by using a nano precious metal supported photocatalyst to synthesize the aryl cyanide. The photocatalysis cyaniding process can be shown by a general formula (I), wherein the X group is Br or I; and the R group is selected from electron attracting groups such as nitryl, acetyl and carboxyl and electron donating groups such as methoxy and methyl. In the invention, nontoxic green potassium ferrocyanide is used as a cyanogen source for synthesizing aryl cyanide, the highly toxic cyanides widely used in original methods are replaced, and thus the problem of environmental pollution in the aryl cyanide synthesis is reduced. The photocatalysis cyaniding reaction has the advantages of mild reaction conditions, stability and high efficiency, simplicity in operation, environmental friendliness, high product conversion rate and good selectivity.
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Paragraph 0036; 0037
(2017/02/28)
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- Direct synthesis of nitriles from cleavage of C=C double bond with nitrite as the nitrogen source and oxidant
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The transformation of the C=C bond of olefin to nitriles has been developed, using easily available NaNO2 as both the nitrogen source and oxidant. Several aryl, heterocyclic nitriles with various substituting groups could be successfully prepared in good to high yields. Based upon experimental observations, a possible reaction mechanism is proposed.
- Liu, Qiang,Fang, Bao,Bai, Xiaohui,Liu, Yuan,Wu, Yao,Xu, Guiming,Guo, Cancheng
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supporting information
p. 2620 - 2623
(2016/06/01)
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- Cobalt/nitrophenolate-catalyzed selective conversion of aldoximes into nitriles or amides
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A novel cobalt/nitrophenolate complex has been synthesized, characterized and studied for their catalytic activities. Conversion of aldoximes to nitriles can be performed via in situ conditions from cobalt(II) acetate and 2,4-dinitrophenol. The rearrangement of aldoximes to amides via cobalt(II) acetate and 2-nitro-1-naphthol has also been demonstrated. A complete reversal of transformation was accomplished by modifying the cobalt salt and careful choice of both the nitrophenol ligand and reaction conditions.
- Jang, Wonseok,Kim, Se Eun,Yang, Cheol Mo,Yoon, Sungwoo,Park, Myunghwan,Lee, Junseong,Kim, Youngjo,Kim, Min
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p. 120 - 123
(2015/02/02)
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- A highly efficient electrochemical route for the conversion of aldehydes to nitriles
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Using NH4I as the supporting electrolyte as well as the precursor of an I2 promoter and nitrogen source, a highly efficient electrochemical route was developed to convert aldehydes to nitriles with excellent yields under mild reaction conditions. This electrochemical process could effectively avoid the direct use of NH3 gas, molecular iodine, and oxidants.
- Qu, Qinghui,Gao, Xiaofang,Gao, Jian,Yuan, Gaoqing
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p. 747 - 750
(2015/04/14)
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- A mild and efficient method for the conversion of aldehydes into nitriles and thiols into disulfides using an ionic liquid oxidant
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A simple, mild and high yielding method for the conversion of various aldehydes to nitriles has been developed using an ionic liquid reagent, hexamethylene bis(N-methylimidazolium) bis(dichloroiodate) (HMBMIBDCI), in combination with aqueous ammonia in CH3CN at room temperature. Moreover, the treatment of aromatic and aliphatic thiols with HMBMIBDCI resulted in the corresponding disulfides in solvent-free condition at room temperature.
- Hosseinzadeh, Rahman,Golchoubian, Hamid,Nouzarian, Mahboobe
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p. 4713 - 4725
(2015/06/30)
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- Utility of Nitrogen Extrusion of Azido Complexes for the Synthesis of Nitriles, Benzoxazoles, and Benzisoxazoles
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The utility of the nitrogen extrusion reaction of azido complexes, generated in situ from the corresponding aldehydes or ketones with TMSN3 in the presence of ZrCl4 or TfOH, has been described. These azido complexes could undergo three different pathways, depending on the substrates. First, azido methanolate complexes or imine diazonium ions could lead to benzisoxazole products via an intramolecular nucleophilic substitution. Second, imine diazonium ions could also undergo either the elimination of proton to provide nitrile products in good to excellent yields or an aryl migration, followed by an intramolecular nucleophilic addition, to give benzoxazole products in good yields.
- Nimnual, Phongprapan,Tummatorn, Jumreang,Thongsornkleeb, Charnsak,Ruchirawat, Somsak
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p. 8657 - 8667
(2015/09/15)
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- Electroorganic synthesis of nitriles via a halogen-free domino oxidation-reduction sequence
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A direct electroorganic sequence yielding nitriles from oximes in undivided cells is reported. Despite the fact that intermediate nitrile oxides might be formed, the method is viable to prepare benzonitriles without substituents ortho to the aldoxime moiety. This constant current method is easy to perform for a broad scope of substrates and employs common electrodes, such as graphite and lead.
- Hartmer, Marius F.,Waldvogel, Siegfried R.
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supporting information
p. 16346 - 16348
(2015/11/16)
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