- A new reagent for efficient synthesis of nitriles from aldoximes using methoxymethyl bromide
-
This study outlines an efficient, high-yielding, and rapid method by which to access diverse nitriles from aldoximes with methoxymethyl bromide (MOM-Br) in THF. It represents the first application of MOM-Br as a deoximation reagent to synthesize nitriles. The reaction was performed at reflux to ensure excellent yield (79-96%) of the nitriles within 20-45 minutes. Furthermore, this method has been successfully applied to the synthesis of the synthesis precursor of aromatic, heteroaromatic, cyclic, and acyclic aliphatic.
- ULUDAG, Nesimi,GIDEN, Ozge NUR
-
p. 993 - 998
(2021/02/05)
-
- Direct C(sp3)-H Cyanation Enabled by a Highly Active Decatungstate Photocatalyst
-
A highly efficient, direct C(sp3)-H cyanation was developed under mild photocatalytic conditions. The method enabled the direct cyanation of various C(sp3)-H substrates with excellent functional group tolerance. Notably, complex natural products and bioactive compounds were efficiently cyanated.
- Kim, Kunsoon,Lee, Seulchan,Hong, Soon Hyeok
-
supporting information
p. 5501 - 5505
(2021/07/26)
-
- A Titanium-Catalyzed Reductive α-Desulfonylation
-
A titanium(III)-catalyzed desulfonylation gives access to functionalized alkyl nitrile building blocks from α-sulfonyl nitriles, circumventing traditional base-mediated α-alkylation conditions and strong single electron donors. The reaction tolerates numerous functional groups including free alcohols, esters, amides, and it can be applied also to the α-desulfonylation of ketones. In addition, a one-pot desulfonylative alkylation is demonstrated. Preliminary mechanistic studies indicate a catalyst-dependent mechanism involving a homolytic C?S cleavage.
- Kern, Christoph,Selau, Jan,Streuff, Jan
-
supporting information
p. 6178 - 6182
(2021/03/16)
-
- A Molecular Iron-Based System for Divergent Bond Activation: Controlling the Reactivity of Aldehydes
-
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
-
p. 7176 - 7185
(2021/06/30)
-
- Method for dehydrating primary amide into nitriles under catalysis of cobalt
-
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.
- -
-
Paragraph 0096-0098
(2021/06/21)
-
- Facile dehydration of primary amides to nitriles catalyzed by lead salts: The anionic ligand matters
-
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
-
-
- Iodine Promoted Conversion of Esters to Nitriles and Ketones under Metal-Free Conditions
-
We report a novel strategy to prepare valuable nitriles and ketones through the conversion of esters under metal-free conditions. By using the I2/PCl3 system, various substrates including aliphatic and aromatic esters could react with acetonitrile and arenes to afford the desired products in good to excellent yields. This method is compatible with a number of functional groups and provides a simple and practical approach for the synthesis of nitrile compounds and aryl ketones.
- Xiao, Jing,Guo, Fengzhe,Li, Yinfeng,Li, Fangshao,Li, Qiang,Tang, Zi-Long
-
p. 2028 - 2035
(2021/02/03)
-
- Ni-Catalyzed Isomerization-Hydrocyanation Tandem Reactions: Access to Linear Nitriles from Aliphatic Internal Olefins
-
A highly regioselective nickel-based catalyst system for the isomerization/hydrocyanation of aliphatic internal olefins is described. This benign tandem reaction provides facile access to a wide variety of aliphatic nitriles in good yields with excellent regioselectivities. Thanks to Lewis acid-free conditions, the protocol features board functional groups tolerance, including secondary amine and unprotected alcohol groups.
- Gao, Jihui,Ni, Jie,Yu, Rongrong,Cheng, Gui-Juan,Fang, Xianjie
-
supporting information
p. 486 - 490
(2021/02/05)
-
- An Efficient Synthesis of Nitriles from Aldoximes in the Presence of Trifluoromethanesulfonic Anhydride in Mild Conditions
-
Abstract: A new and convenient protocol has been proposed for the transformation of aldoximes to nitriles using trifluoromethanesulfonic anhydride and triethylamine. The proposed method allows a range of aldoximes, including aromatic, heterocyclic, aliphatic, and cycloaliphatic aldoximes, to be converted to the corresponding nitriles in good to excellent yields.
- Uludag, N.
-
p. 1640 - 1645
(2020/10/22)
-
- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
-
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
-
p. 378 - 385
(2020/10/02)
-
- Method for continuous preparation of nitriles in a pipelined reactor (by machine translation)
-
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)
- -
-
Paragraph 0036-0054; 0059-0097
(2020/12/14)
-
- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
-
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.
- -
-
Paragraph 0034-0039; 0261-0266
(2020/09/16)
-
- Preparation method of nitrile compounds with formamide as cyanide source
-
The invention discloses a preparation method of nitrile compounds. According to the preparation method, formamide used as a cyanide source undergoes a hydrocyanation reaction with various types of olefins under the action of a nickel catalyst to generate various nitrile compounds, wherein a reaction temperature is 60-160 DEG C and reaction time is 6-36 hours. The method overcomes the defects thata traditional olefin hydrocyanation reaction is complex in operation, needs to use a highly toxic cyanide source as a reaction raw material and the like. According to the method, simple, cheap, greenand non-toxic formamide is used as a cyano source, other dehydrating agents (such as phosphorus pentoxide and phosphorus oxychloride) do not need to be added, and cyano anions are generated through spontaneous dehydration of formamide under the catalysis of Lewis acid and undergo a hydrocyanation reaction with olefin in situ to generate nitrile compounds; reaction conditions are simple, operationis easy, and economical performance and high efficiency are realized; meanwhile, the method is applicable to various monosubstituted and disubstituted aliphatic and aromatic olefins, and shows good substrate universality; the nitrile compounds are insensitive to air, moisture and light and high in yield; and the preparation method is simple in product separation and purification and has good application prospects.
- -
-
Paragraph 0015-0023; 0024-0087; 0089; 0091
(2020/03/09)
-
- 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)
- -
-
Paragraph 0033-0054; 0061-0066
(2020/12/15)
-
- Reductive cyanation of organic chlorides using CO2 and NH3 via Triphos–Ni(I) species
-
Cyano-containing compounds constitute important pharmaceuticals, agrochemicals and organic materials. Traditional cyanation methods often rely on the use of toxic metal cyanides which have serious disposal, storage and transportation issues. Therefore, there is an increasing need to develop general and efficient catalytic methods for cyanide-free production of nitriles. Here we report the reductive cyanation of organic chlorides using CO2/NH3 as the electrophilic CN source. The use of tridentate phosphine ligand Triphos allows for the nickel-catalyzed cyanation of a broad array of aryl and aliphatic chlorides to produce the desired nitrile products in good yields, and with excellent functional group tolerance. Cheap and bench-stable urea was also shown as suitable CN source, suggesting promising application potential. Mechanistic studies imply that Triphos-Ni(I) species are responsible for the reductive C-C coupling approach involving isocyanate intermediates. This method expands the application potential of reductive cyanation in the synthesis of functionalized nitrile compounds under cyanide-free conditions, which is valuable for safe synthesis of (isotope-labeled) drugs.
- Dong, Yanan,Li, Yuehui,Yang, Peiju,Zhao, Shizhen
-
-
- Ni-Catalyzed hydrocyanation of alkenes with formamide as the cyano source
-
CN generation from formamide dehydration! A novel Ni-catalyzed hydrocyanation of various alkenes to provide aliphatic nitriles is developed by generating hydrocyanic acid in situ from safe and readily available formamide. Excellent linear or branched regio-selectivity, wide substrate scope, cheap and stable nickel salt as a pre-catalyst, a safe cyano source, slow generation of CN to obviate catalyst deactivation and convenient experimental operation would render this hydrocyanation attactive for laboratory synthesis of aliphatic nitriles.
- Shu, Xiao,Jiang, Yuan-Yuan,Kang, Lei,Yang, Luo
-
supporting information
p. 2734 - 2738
(2020/06/17)
-
- A by the aldoxime nitrile method (by machine translation)
-
The invention relates to shown in the following formula by the aldoxime nitrile method: The method comprises the steps: first at room temperature will be dimethyl sulfoxide (0.01 equiv) and oxalyl chloride (1.2 equiv) in acetonitrile are added in turn, then drop [...] (1.0 equiv) acetonitrile solution, stirring at the room temperature reaction 2 - 12 is H, to obtain the corresponding nitrile compounds, yield 85 - 95%. In the reaction system by adding triethylamine, the reaction time can be shortened. (by machine translation)
- -
-
Paragraph 0015; 0016
(2019/01/21)
-
- A new reagent for efficient synthesis of nitriles from aldoximes using methoxymethyl bromide
-
This study outlines an efficient, high-yielding, and rapid method by which to access diverse nitriles from aldoximes with methoxymethyl bromide (MOM-Br) in THF. It represents the first application of MOM-Br as a deoximation reagent to synthesize nitriles. The reaction was performed at reflux to ensure excellent yield (79-96percent) of the nitriles within 20-45 minutes. Furthermore, this method has been successfully applied to the synthesis of the synthesis precursor of aromatic, heteroaromatic, cyclic, and acyclic aliphatic.
- Uludag, Nesimi,Nur Giden, Ozge
-
p. 993 - 998
(2020/06/27)
-
- Direct Synthesis of Nitriles from Carboxylic Acids Using Indium-Catalyzed Transnitrilation: Mechanistic and Kinetic Study
-
Aliphatic and aromatic carboxylic acids can be quantitatively converted to the corresponding nitriles in the presence of catalysts using acetonitrile both as a solvent and reactant at 200 °C. This transformation is based on the acid-nitrile exchange (i.e., transnitrilation) and uses a nontoxic and water resistant catalyst, indium trichloride (InCl3). The mechanism of the transnitrilation was investigated both experimentally and computationally and compared to the previously proposed mechanism. In contrast to the usually assumed formation of amide as an intermediate, transnitrilation is an equilibrium reaction and proceeds via an equilibrated Mumm reaction with the formation of an imide as an intermediate. A simple and reversible mechanism was proposed for this reaction, which was validated by kinetics measurement and by density functional theory calculations of the reaction intermediates and reaction mechanisms.
- Vanoye, Laurent,Hammoud, Ahmad,Gérard, Hélène,Barnes, Alexandra,Philippe, Régis,Fongarland, Pascal,De Bellefon, Claude,Favre-Réguillon, Alain
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p. 9705 - 9714
(2019/10/14)
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- Oxidant free conversion of alcohols to nitriles over Ni-based catalysts
-
Organic nitriles are significant and versatile industrial feedstocks, but their conventional synthetic protocols require hazardous starting materials and/or harsh reaction conditions posing environmental and health risks. Herein, we established a Ni-based catalytic system to convert primary alcohols to nitriles with ammonia gas as the sole nitrogen source under oxidant-free conditions at merely 190-230 °C. Based on isotope labelling experiments, in situ DRIFTS and control experiments, the reaction pathway was identified to follow a dehydrogenation-imination-dehydrogenation sequence, with α-carbon C-H bond breakage as the rate determining step. Ni is superior to all noble metal catalysts tested, due to its excellent dehydrogenation ability that is not inhibited by NH3. The support plays an auxiliary role, promoting the reaction between aldehyde and ammonia to form imine as a critical intermediate. Ni/Al2O3 catalyst prepared via a deposition-precipitation method, featuring both excellent dispersion of metallic Ni and suitable acid sites, enabled alcohol transformation into nitrile under unprecedented low temperature. Various alcohols were converted into their corresponding nitriles in high conversions and yields (both up to 99%), while the catalyst kept 90% of its original activity after 48 hours in the stability test, highlighting the wide applicability and the robustness of the catalytic system.
- Wang, Yunzhu,Furukawa, Shinya,Zhang, Zhang,Torrente-Murciano, Laura,Khan, Saif A.,Yan, Ning
-
-
- Identification of an Active NiCu Catalyst for Nitrile Synthesis from Alcohol
-
Development of heterogeneous catalysts for alcohol transformation into nitriles under oxidant-free conditions is a challenge. Considering the C-H activation on α-carbon of primary alcohols is the rate-determining step, decreasing the activation energy of C-H activation is critical in order to enhance the catalytic activity. Several NiM/Al2O3 bimetallic catalysts were synthesized and scrutinized in catalytic transformation of 1-butanol to butyronitrile. Ni-Cu was identified as a suitable combination with the optimized Ni0.5Cu0.5/Al2O3 catalyst exhibiting 10 times higher turnover frequency than Ni/Al2O3 catalyst. X-ray absorption spectroscopy (XAS) and high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) revealed that the NiCu particles in the catalyst exist in the form of homogeneous alloys with an average size of 8.3 nm, providing an experimental foundation to build up a catalyst model for further density functional theory (DFT) calculations. Calculations were done over a series of NiM catalysts, and the experimentally observed activity trend could be rationalized by the Br?nsted-Evans-Polanyi (BEP) principle, i.e., catalysts that afford reduced reaction energy also feature lower activation barriers. The calculated activation energy (Ea) for C-H activation with coadsorbed NH3 dropped from 63.4 kJ/mol on pure Ni catalyst to 49.9 kJ/mol on the most active NiCu-2 site in NiCu bimetallic catalyst, in good agreement with the experimentally measured activation energy values. The Ni0.5Cu0.5/Al2O3 catalyst was further employed to convert 11 primary alcohols into nitriles with high to near-quantitative yields, at a Ni loading 10 times less than that of the conventional Ni/Al2O3 catalyst.
- Wang, Yunzhu,Furukawa, Shinya,Yan, Ning
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p. 6681 - 6691
(2019/07/12)
-
- OXIDATIVE CONVERSION OF ALIPHATIC ALDEHYDES TO NITRILES USING OXOAMMONIUM SALT
-
The present invention relates to an oxidative transformation method of aliphatic benzaldehydes to nitriles using NH_4OAc through oxoammonium salts. By using stoichiometric amounts of oxoammonium salts to establish optimal reaction conditions associated with the oxidative conversion of aliphatic benzaldehydes to nitriles, high yields of nitrile can be selectively obtained, and the oxoammonium salts used can be oxidized and reused in a simple method.COPYRIGHT KIPO 2020
- -
-
Paragraph 0055-0063; 0136-0142
(2019/12/10)
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- Primary amides to amines or nitriles: A dual role by a single catalyst
-
We report a manganese-catalyzed hydrosilylative reduction of various primary amides to amines (25 examples). On simple modification of the reaction conditions such as in the presence of a catalytic amount of secondary amide, the same catalyst can transform the primary amides into intermediate nitrile compounds (16 examples) in excellent yields. This is the first example where such a controlled catalytic transformation of primary amides to amines or nitriles with a single catalyst has been demonstrated.
- Das, Hari S.,Das, Shyamal,Dey, Kartick,Singh, Bhagat,Haridasan, Rahul,Das, Arpan,Ahmed, Jasimuddin,Mandal, Swadhin K.
-
supporting information
p. 11868 - 11871
(2019/10/11)
-
- A BEt3-Base catalyst for amide reduction with silane
-
Reported herein is the development of a simple but practical catalytic system for the selective reduction of amides with hydrosilane or hydrosiloxane. Low-cost and readily available triethylborane (1.0 M in THF), in combination with a catalytic amount of an alkali metal base, was found to catalyze the reduction of all three amide classes (tertiary, secondary, and primary amides) to form amines under mild conditions. In addition, the selective transformation of secondary amides to aldimines and primary amides to nitriles can also be achieved by using a proper combination of BEt3 and base. The scope of these BEt3-base-catalyzed amide hydrosilylation reactions has been explored in depth. Preliminary results of mechanistic studies suggest a modified Piers' silane Si-H···B activation mode wherein the hydride abstraction by BEt3 is promoted by the coordination of an alkoxide or hydroxide anion to the Si center.
- Yao, Wubing,Fang, Huaquan,He, Qiaoxing,Peng, Dongjie,Liu, Guixia,Huang, Zheng
-
-
- A BEt3-Base Catalyst for Amide Reduction with Silane
-
Reported herein is the development of a simple but practical catalytic system for the selective reduction of amides with hydrosilane or hydrosiloxane. Low-cost and readily available triethylborane (1.0 M in THF), in combination with a catalytic amount of an alkali metal base, was found to catalyze the reduction of all three amide classes (tertiary, secondary, and primary amides) to form amines under mild conditions. In addition, the selective transformation of secondary amides to aldimines and primary amides to nitriles can also be achieved by using a proper combination of BEt3 and base. The scope of these BEt3-base-catalyzed amide hydrosilylation reactions has been explored in depth. Preliminary results of mechanistic studies suggest a modified Piers' silane Si-H···B activation mode wherein the hydride abstraction by BEt3 is promoted by the coordination of an alkoxide or hydroxide anion to the Si center.
- Yao, Wubing,Fang, Huaquan,He, Qiaoxing,Peng, Dongjie,Liu, Guixia,Huang, Zheng
-
p. 6084 - 6093
(2019/05/24)
-
- Nickel-Catalyzed Decarbonylative Cyanation of Acyl Chlorides
-
Ni-catalyzed decarbonylative cyanation of acyl chlorides with trimethylsilyl cyanide has been achieved. This transformation is applicable to the synthesis of an array of nitrile compounds bearing a wide range of functional groups under neutral conditions. The step-by-step experimental studies revealed that the reaction sequences of the present catalytic reaction are oxidative addition, transmetalation, decarbonylation, and reductive elimination.
- Wang, Zhenhua,Wang, Xiu,Ura, Yasuyuki,Nishihara, Yasushi
-
supporting information
p. 6779 - 6784
(2019/08/26)
-
- Synthesis of Nitriles from Primary Amides or Aldoximes under Conditions of a Catalytic Swern Oxidation
-
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
-
p. 12939 - 12944
(2018/10/20)
-
- Development and Utilization of a Palladium-Catalyzed Dehydration of Primary Amides to Form Nitriles
-
A palladium(II) catalyst, in the presence of Selectfluor, enables the efficient and chemoselective transformation of primary amides into nitriles. The amides can be attached to aromatic rings, heteroaromatic rings, or aliphatic side chains, and the reactions tolerate steric bulk and electronic modification. Dehydration of a peptaibol containing three glutamine groups afforded structure-activity relationships for each glutamine residue. Thus, this dehydration can act similarly to an alanine scan for glutamines via synthetic mutation.
- Al-Huniti, Mohammed H.,Rivera-Chávez, José,Colón, Katsuya L.,Stanley, Jarrod L.,Burdette, Joanna E.,Pearce, Cedric J.,Oberlies, Nicholas H.,Croatt, Mitchell P.
-
p. 6046 - 6050
(2018/09/27)
-
- Boosting Hydrogen Production by Anodic Oxidation of Primary Amines over a NiSe Nanorod Electrode
-
For electrocatalytic water splitting, the sluggish anodic oxygen evolution reaction (OER) restricts the cathodic hydrogen evolution reaction (HER). Therefore, developing an alternative anodic reaction with accelerating kinetics to produce value-added chemicals, especially coupled with HER, is of great importance. Now, a thermodynamically more favorable primary amine (?CH2?NH2) electrooxidation catalyzed by NiSe nanorod arrays in water is reported to replace OER for enhancing HER. The increased H2 production can be obtained at cathode; meanwhile, a variety of aromatic and aliphatic primary amines are selectively electrooxidized to nitriles with good yields at the anode. Mechanistic investigations suggest that NiII/NiIII may serve as the redox active species for the primary amines transformation. Hydrophobic nitrile products can readily escape from aqueous electrolyte/electrode interface, avoiding the deactivation of the catalyst and thus contributing to continuous gram-scale synthesis.
- Chong, Xiaodan,Huang, Yi,Liang, Yu,Liu, Cuibo,Zhang, Bin
-
supporting information
p. 13163 - 13166
(2018/09/21)
-
- Double Dehydrogenation of Primary Amines to Nitriles by a Ruthenium Complex Featuring Pyrazole Functionality
-
A ruthenium(II) complex bearing a naphthyridine-functionalized pyrazole ligand catalyzes oxidant-free and acceptorless selective double dehydrogenation of primary amines to nitriles at moderate temperature. The role of the proton-responsive entity on the ligand scaffold is demonstrated by control experiments, including the use of a N-methylated pyrazole analogue. DFT calculations reveal intricate hydride and proton transfers to achieve the overall elimination of 2 equiv of H2.
- Dutta, Indranil,Yadav, Sudhir,Sarbajna, Abir,De, Subhabrata,H?lscher, Markus,Leitner, Walter,Bera, Jitendra K.
-
supporting information
p. 8662 - 8666
(2018/07/09)
-
- Stable and reusable nanoscale Fe2O3-catalyzed aerobic oxidation process for the selective synthesis of nitriles and primary amides
-
The sustainable introduction of nitrogen moieties in the form of nitrile or amide groups in functionalized molecules is of fundamental interest because nitrogen-containing motifs are found in a large number of life science molecules, natural products and materials. Hence, the synthesis and functionalization of nitriles and amides from easily available starting materials using cost-effective catalysts and green reagents is highly desired. In this regard, herein we report the nanoscale iron oxide-catalyzed environmentally benign synthesis of nitriles and primary amides from aldehydes and aqueous ammonia in the presence of 1 bar O2 or air. Under mild reaction conditions, this iron-catalyzed aerobic oxidation process proceeds to synthesise functionalized and structurally diverse aromatic, aliphatic and heterocyclic nitriles. Additionally, applying this iron-based protocol, primary amides have also been prepared in a water medium.
- Murugesan, Kathiravan,Senthamarai, Thirusangumurugan,Sohail, Manzar,Sharif, Muhammad,Kalevaru, Narayana V.,Jagadeesh, Rajenahally V.
-
supporting information
p. 266 - 273
(2018/01/12)
-
- A metal-free direct C (sp3)-H cyanation reaction with cyanobenziodoxolones
-
A metal-free protocol of direct C(sp3)-H cyanation with cyanobenziodoxolones functioning as both cyanating reagents and oxidants was developed. Unactivated substrates, such as alkanes, ethers and tertiary amines, were thereby transformed to the corresponding nitriles in moderate to high yields. Mechanistic studies indicated that the cyanation proceeded with two potential pathways, which is highly dependent on the substrates: (1) a free radical case for alkanes and ethers and (2) an oxidative case for tertiary amines.
- Sun, Ming-Xue,Wang, Yao-Feng,Xu, Bao-Hua,Ma, Xin-Qi,Zhang, Suo-Jiang
-
supporting information
p. 1971 - 1975
(2018/03/23)
-
- Facile and efficient preparation of nitriles through FeCl4–IL–SiO2-catalyzed direct oxidation of alcohols with hydrogen peroxide
-
Abstract: A series of silica-supported functionalized ionic liquids catalysts have been prepared and tested in the oxidative conversion of alcohols to nitriles with H2O2 as the oxidant. The features of this heterogeneous reaction system were studied by tuning various reaction parameters including catalyst selection, amount of the catalyst, and effect of solvents. Among the catalysts, FeCl4–IL–SiO2 exhibited the highest efficiency in direct oxidation of alcohols to nitriles under the optimized condition along with good recycle performance. Also, a possible catalytic mechanism is provided. Graphical abstract: [Figure not available: see fulltext.]
- Hu, Yu-Lin,Wang, Bing Tong,Fang, Dong
-
p. 233 - 243
(2017/01/05)
-
- Synthesis of nitriles from aerobic oxidation of amines catalyzed by ruthenium supported on activated carbon
-
Nitriles were synthesized from the aerobic oxidation of amines over commercially available catalysts, which were activated carbon-supported ruthenium catalysts (Ru/AC). The 5%Ru/AC catalyst can tolerate a wide range of substrates, such as aromatic, aliphatic, and heterocyclic amines, and afford the target nitriles in good-to-excellent yields. The 5%Ru/AC catalyst was easily recovered and no ruthenium leaking took place in the catalytic run.
- Niu, Baoqiang,Lu, Fei,Zhang, Hong-Yu,Zhang, Yuecheng,Zhao, Jiquan
-
supporting information
p. 330 - 333
(2017/02/23)
-
- Ligand controlled switchable selectivity in ruthenium catalyzed aerobic oxidation of primary amines
-
A ligand controlled catalytic system for the aerobic oxidation of 1° amines to nitriles and imines has been developed where the varying π-acidic feature of BIAN versus phen in the frameworks of ruthenium catalysts facilitates switchable selectivity.
- Ray, Ritwika,Chandra, Shubhadeep,Yadav, Vishal,Mondal, Prasenjit,Maiti, Debabrata,Lahiri, Goutam Kumar
-
supporting information
p. 4006 - 4009
(2017/04/11)
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- Oxoammonium salt-mediated oxidative nitriles synthesis from aldehydes with ammonium acetate
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An efficient and scalable route for the synthesis of nitriles was developed by oxoammonium salt (4-acetamido-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) mediated oxidative conversion of aldehydes with NH4OAc. A variety of aliphatic aldehydes as well as benzaldehydes were converted into the corresponding nitriles in high yields. The nitroxyl radical which is the reduced species of the used oxoammonium salt was recovered by simple acid-base extraction for the recycling.
- Kim, Myeong Jin,Mun, Junyoung,Kim, Jinho
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supporting information
p. 4695 - 4698
(2017/11/17)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a manufacturing method of nitrile. Compared with the prior art, the manufacturing method has the characteristics of significantly reduced using amount of an ammonia source, low environmental pressure, low energy consumption, low production cost, high purity and yield of a nitrile product and the like, and nitrile with a more complex structure can be obtained. The invention also relates to a method for manufacturing corresponding amine from nitrile.
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Paragraph 0143-0147; 0158; 0180; 0191; 0213; 0224; 0243
(2017/10/22)
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- Process for the Catalytic Reversible Alkene-Nitrile Interconversion
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The present invention refers to processes for catalytic reversible alkene-nitrile interconversion through controllable HCN-free transfer hydrocyanation.
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Page/Page column 15
(2017/09/02)
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- Continuous Flow Synthesis under High-Temperature/High-Pressure Conditions Using a Resistively Heated Flow Reactor
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A cheap, easy-to-build, and effective resistively heated reactor for continuous flow synthesis at high temperature and pressure is herein presented. The reactor is rapidly heated directly using an electric current and is capable of rapidly delivering temperatures and pressures up to 400 °C and 200 bar, respectively. High-temperature and high-pressure applications of this reactor were safely performed and demonstrated by selected transformations such as esterifications, transesterifications, and direct carboxylic acid to nitrile reactions using supercritical ethanol, methanol, and acetonitrile. Reaction temperatures were between 300 and 400 °C with excellent conversions and good to excellent isolated product yields. Examples of Diels-Alder reactions were also carried out at temperatures up to 300 °C in high yield. No additives or catalysts were used in the reactions.
- Adeyemi, Ahmed,Bergman, Joakim,Br?nalt, Jonas,S?vmarker, Jonas,Larhed, Mats
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supporting information
p. 947 - 955
(2017/07/26)
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- Tin or gallium-catalyzed cyanide-transition metal-free synthesis of nitriles from aldehydes or oximes
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Tin or gallium chloride catalyzed transformation of oximes or aldehydes to nitriles is described. Various nitriles were obtained in up to 99% of yields. The gram-scale reaction or the optically active dinitrile was also available. This synthetically useful method has avoided toxic organic or inorganic cyanides as well as transition or noble metal catalysts.
- Zhuang, Yan-Jun,Liu, Jie,Kang, Yan-Biao
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supporting information
p. 5700 - 5702
(2016/11/28)
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- Nanocrystalline CeO2 as a Highly Active and Selective Catalyst for the Dehydration of Aldoximes to Nitriles and One-Pot Synthesis of Amides and Esters
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The dehydration of aldoximes into nitriles has been performed in the presence of various metal oxides with different acid-base properties (Al2O3, TiO2, CeO2, MgO). The results showed that a nanocrystalline CeO2 was the most active catalyst. An in situ IR spectroscopy study supports a polar elimination mechanism in the dehydration of aldoxime on metal oxide catalysts, in which Lewis acid sites and basic sites are involved. The Lewis acid sites intervene in the adsorption of the oxime on the catalyst surface while surface base sites are responsible for the C1-H bond cleavage. Thus, the acid-base properties of nanocrystalline CeO2 are responsible for the high catalytic activity and selectivity. A variety of aldoximes including alkyl and cycloalkyl aldoximes have been dehydrated into the corresponding nitriles in good yields (80-97%) using nanosized ceria which moreover resulted in a stable and reusable catalyst. Additionally, it has been showed that a variety of pharmacologically important products such as picolinamide and picolinic acid alkyl ester derivatives can be obtained in good yields from 2-pyridinaldoxime in a one-pot process using the nanoceria as catalyst.
- Rapeyko, Anastasia,Climent, Maria J.,Corma, Avelino,Concepción, Patricia,Iborra, Sara
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p. 4564 - 4575
(2016/07/12)
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- Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles
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Synergism among several intertwined catalytic cycles allows for selective, room temperature oxidation of primary amines to the corresponding nitriles in 85-98 % isolated yield. This metal-free, scalable, operationally simple method employs a catalytic quantity of 4-acetamido-TEMPO (ACT; TEMPO=2,2,6,6-tetramethylpiperidine N-oxide) radical and the inexpensive, environmentally benign triple salt oxone as the terminal oxidant under mild conditions. Simple filtration of the reaction mixture through silica gel affords pure nitrile products.
- Lambert, Kyle M.,Bobbitt, James M.,Eldirany, Sherif A.,Kissane, Liam E.,Sheridan, Rose K.,Stempel, Zachary D.,Sternberg, Francis H.,Bailey, William F.
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supporting information
p. 5156 - 5159
(2016/04/09)
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- Synthesis of nitriles from amines using nanoscale Co3O4-based catalysts via sustainable aerobic oxidation
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The selective oxidation of amines for the benign synthesis of nitriles under mild conditions is described. Key to success for this transformation is the application of reusable cobalt oxide-based nanocatalysts. The resulting nitriles constitute key precursors and central intermediates in organic synthesis.
- Natte, Kishore,Jagadeesh, Rajenahally V.,Sharif, Muhammad,Neumann, Helfried,Beller, Matthias
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supporting information
p. 3356 - 3359
(2016/04/09)
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- Simple Copper Catalysts for the Aerobic Oxidation of Amines: Selectivity Control by the Counterion
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We describe the use of simple copper-salt catalysts in the selective aerobic oxidation of amines to nitriles or imines. These catalysts are marked by their exceptional efficiency, operate at ambient temperature and pressure, and allow the oxidation of amines without expensive ligands or additives. This study highlights the significant role counterions can play in controlling selectivity in catalytic aerobic oxidations.
- Xu, Boran,Hartigan, Elizabeth M.,Feula, Giancarlo,Huang, Zheng,Lumb, Jean-Philip,Arndtsen, Bruce A.
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supporting information
p. 15802 - 15806
(2016/12/16)
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- Aliphatic nitrile catalytic oxidation synthesis method
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The invention discloses an aliphatic nitrile catalytic oxidation synthesis method. With aliphatic aldehyde serving as reaction substrate, 2, 2, 6, 6-tetramethylpiperidine-1-oxygen radical (TEMPO), alkali metal salt and tert-butyl nitrite (TBN) as catalysts, hexamethyl-disilazane (HMDS) as the nitrogen source and oxygen as an oxidizing agent, the reaction substrate is reacted in organic solvent at normal pressure at the temperature of 25-50 DEG C, and aftertreatment is performed after reaction to obtain the aliphatic nitrile. The method is easy and safe to operate, and environment cost is lowered.
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Paragraph 0027
(2016/10/17)
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- Deboronative cyanation of potassium alkyltrifluoroborates: Via photoredox catalysis
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A photoredox catalytic method was developed for the direct cyanation of alkyltrifluoroborates. This reaction provides a new and useful transformation of the easily available alkyltrifluoroborates. The photocatalytic reaction can tolerate a variety of functional groups with mild reaction conditions. Mechanistic investigations are consistent with the present reaction following a radical pathway.
- Dai, Jian-Jun,Zhang, Wen-Man,Shu, Yong-Jin,Sun, Yu-Yang,Xu, Jun,Feng, Yi-Si,Xu, Hua-Jian
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supporting information
p. 6793 - 6796
(2016/06/01)
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- Transition-Metal-Free Deacylative Cleavage of Unstrained C(sp3)-C(sp2) Bonds: Cyanide-Free Access to Aryl and Aliphatic Nitriles from Ketones and Aldehydes
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A transition-metal-free deacylative C(sp3)-C(sp2) bond cleavage for the synthetically practical oxidative amination of ketones and aldehydes to nitriles is first described, using cheap and commercially abundant NaNO2 as the oxidant and the nitrogen source. Various nitriles bearing aryl, heteroaryl, alkyl, and alkenyl groups could be smoothly obtained from ketones and aldehydes in high yields, avoiding highly toxic cyanides or transition metals.
- Ge, Jing-Jie,Yao, Chuan-Zhi,Wang, Mei-Mei,Zheng, Hong-Xing,Kang, Yan-Biao,Li, Yadong
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supporting information
p. 228 - 231
(2016/02/03)
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- Postsynthesis-Treated Iron-Based Metal-Organic Frameworks as Selective Catalysts for the Sustainable Synthesis of Nitriles
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The dehydration of aldoximes to the corresponding nitriles can be performed with excellent activity and selectivity by using iron trimesate as a homogeneous catalyst. Iron trimesate has been heterogenized by synthesizing metal-organic frameworks (MOFs) from iron trimesate, that is, Fe(BTC), and MIL-100 (Fe). These materials were active and selective aldoxime dehydration catalysts, and postsynthesis-treated MIL-100 (Fe) produced the desired nitriles with 100 conversion and selectivities >90 under mild reaction conditions and in short reaction times. X-ray photoelectron spectroscopy showed the presence of different Fe species in the catalyst, and in situ IR spectroscopy combined with catalytic results indicates that the catalytic activity is associated with Fe framework species. The postsynthesis-treated MIL-100 (Fe)-NH4F can be recycled several times and has an excellent reaction scope, which gives better catalytic results than other solid acid or base catalysts.
- Rapeyko, Anastasia,Climent, Maria J.,Corma, Avelino,Concepci?n, Patricia,Iborra, Sara
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p. 3270 - 3282
(2015/10/19)
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- Palladium(II) complexes with a phosphino-oxime ligand: Synthesis, structure and applications to the catalytic rearrangement and dehydration of aldoximes
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The treatment of [PdCl2(COD)] (COD = 1,5-cyclooctadiene) with 1 and 2 equivalents of 2-(diphenylphosphino)benzaldehyde oxime in dichloromethane at room temperature led to the selective formation of [PdCl2{κ2-(P,N)-2-Ph2PC6H4CHNOH}] (1) and [Pd{κ2-(P,N)-2-Ph2PC6H4CHNOH}2][Cl]2 (2), respectively, which represent the first examples of Pd(II) complexes containing a phosphino-oxime ligand. These compounds, whose structures were fully confirmed by X-ray diffraction methods, were active in the catalytic rearrangement of aldoximes. In particular, using 5 mol% complex 1, a large variety of aldoximes could be cleanly converted into the corresponding primary amides at 100 °C, employing water as solvent and without the assistance of any cocatalyst. Palladium nanoparticles are the active species in the rearrangement process. In addition, when the same reactions were performed employing acetonitrile as solvent, selective dehydration of the aldoximes to form the respective nitriles was observed. For comparative purposes, the catalytic behaviour of an oxime-derived palladacyclic complex has also been briefly evaluated.
- Menéndez-Rodríguez, Lucía,Tomás-Mendivil, Eder,Francos, Javier,Nájera, Carmen,Crochet, Pascale,Cadierno, Victorio
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p. 3754 - 3761
(2015/07/01)
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- "Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles
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Organic nitriles constitute key precursors and central intermediates in organic synthesis. In addition, nitriles represent a versatile motif found in numerous medicinally and biologically important compounds. Generally, these nitriles are synthesized by traditional cyanation procedures using toxic cyanides. Herein, we report the selective and environmentally benign oxidative conversion of primary amines for the synthesis of structurally diverse aromatic, aliphatic and heterocyclic nitriles using a reusable "nanorust" (nanoscale Fe2O3)-based catalysts applying molecular oxygen.
- Jagadeesh, Rajenahally V.,Junge, Henrik,Beller, Matthias
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