cas 2571-52-0, 2,4,6-trimethylbenzonitrile

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Using Data Science To Guide Aryl Bromide Substrate Scope Analysis in a Ni/Photoredox-Catalyzed Cross-Coupling with Acetals as Alcohol-Derived Radical Sources
Ni/photoredox catalysis has emerged as a powerful platform for C(sp2)–C(sp3) bond formation. While many of these methods typically employ aryl bromides as the C(sp2) coupling partner, a variety of aliphatic radical sources have been investigated. In principle, these reactions enable access to the same product scaffolds, but it can be hard to discern which method to employ because nonstandardized sets of aryl bromides are used in scope evaluation. Herein, we report a Ni/photoredox-catalyzed (deutero)methylation and alkylation of aryl halides where benzaldehyde di(alkyl) acetals serve as alcohol-derived radical sources. Reaction development, mechanistic studies, and late-stage derivatization of a biologically relevant aryl chloride, fenofibrate, are presented. Then, we describe the integration of data science techniques, including DFT featurization, dimensionality reduction, and hierarchical clustering, to delineate a diverse and succinct collection of aryl bromides that is representative of the chemical space of the substrate class. By superimposing scope examples from published Ni/photoredox methods on this same chemical space, we identify areas of sparse coverage and high versus low average yields, enabling comparisons between prior art and this new method. Additionally, we demonstrate that the systematically selected scope of aryl bromides can be used to quantify population-wide reactivity trends and reveal sources of possible functional group incompatibility with supervised machine learning.
Doyle, Abigail G.,Gandhi, Shivaani S.,Jiang, Shutian,Kariofillis, Stavros K.,Martinez Alvarado, Jesus I.,?urański, Andrzej M.
supporting information
p. 1045 - 1055
(2022/01/19)

Switchable activity of a Ru catalyst bearing an annulated mesoionic carbene ligand for oxidation of primary amines
The catalytic activity of a Ru complex 1, bearing a fused π-conjugated imidazo[1,2–a][1,8]naphthyridine-based mesoionic carbene (MIC) ligand, is examined for the oxidation of primary amines. Complex 1 affords nitrile or imine depending on the nature of th
Bera, Jitendra K.,Din Reshi, Noor U,Pal, Nilay Kumar,Pal, Saikat,Pal, Sourav,Yadav, Suman
(2022/01/31)

Copper-promoted cyanation of aryl iodides with N,N-dimethyl aminomalononitrile
A copper-promoted cyanation of aryl iodides has been successfully developed by using N,N-dimethyl aminomalononitrile as the cyanide source with moderate toxicity and better stability. This reaction features broad substrate scope, excellent reaction yields, readily available catalyst, and simple reaction conditions.
Liu, Si-Zhan,Li, Jing,Xue, Cao-Gen,Xu, Xue-Tao,Lei, Lin-Sheng,Huo, Chen-Yu,Wang, Zhen,Wang, Shao-Hua
supporting information

(2021/02/01)

Method for catalyzing oxidation of amines to generate nitrile by using nonmetal mesoporous nitrogen-doped carbon material
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; 0025

(2021/05/08)

H3PO4 catalyzed one-pot synthesis of 1,3-diphenyl-1H-pyrazole-4-carbaldehyde to novel 1,3-diphenyl-1H-pyrazole-4-carbonitrile
Abstract: One-pot condensation of pyrazole-4-aldehydes and hydroxylamine hydrochloride to form the corresponding oxime using formic acid as a medium and further dehydration of oxime using a catalytic amount of orthophosphoric acid to afford novel pyrazole-4-carbonitrile. This protocol serves as an ortho-phosphoric acid-catalyzed one-pot conversion of aldehyde to nitrile. Most remarkable features of this method are metal-free, cost-effective, atom efficiency with excellent yield (98–99%). This process will serve as a robust and scalable tool for the synthesis of valuable and versatile precursor (nitriles). This precursor will pave the way for the synthesis of various medicinally important valuable compounds. Graphic abstract: [Figure not available: see fulltext.].
Choudhare, Tukaram S,Netankar, Prashant D,Shirsath, Sagar E,Wagare, Devendra S
(2021/07/10)

A convenient reagent for the conversion of aldoximes into nitriles and isonitriles
For the dehydroxylation of aldoximes with 4-nitro-1-((trifluoromethyl)sulfonyl)-imidazole (NTSI), slight modifications of reaction conditions resulted in significantly different reaction paths to provide either nitriles or isonitriles. The challenging conversion of aldoximes into isonitriles was achieved under mild conditions.
Zhang, Wei,Lin, Jin-Hong,Zhang, Pengfei,Xiao, Ji-Chang
supporting information
p. 6221 - 6224
(2020/06/29)

Nitrosation of Cyanamide: Preparation and Properties of the Elusive E- and Z-N'-Cyanodiazohydroxides
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
supporting information

(2020/04/29)

Transformation of aromatic bromides into aromatic nitriles with n-BuLi, pivalonitrile, and iodine under metal cyanide-free conditions
Various aromatic nitriles could be obtained in good yields by the treatment of aryl bromides with n-butyllithium and then pivalonitrile, followed by the treatment with molecular iodine at 70 °C, without metal cyanides under transition-metal-free conditions. The present reaction proceeds through the radical β-elimination of imino-nitrogen-centered radicals formed from the reactions of imines and N-iodoimines under warming conditions.
Uchida, Ko,Togo, Hideo
(2019/09/04)

Ni-Catalyzed Reductive Cyanation of Aryl Halides and Phenol Derivatives via Transnitrilation
Herein, we report a Ni-catalyzed reductive coupling for the synthesis of benzonitriles from aryl (pseudo)halides and an electrophilic cyanating reagent, 2-methyl-2-phenyl malononitrile (MPMN). MPMN is a bench-stable, carbon-bound electrophilic CN reagent that does not release cyanide under the reaction conditions. A variety of medicinally relevant benzonitriles can be made in good yields. Addition of NaBr to the reaction mixture allows for the use of more challenging aryl electrophiles such as aryl chlorides, tosylates, and triflates. Mechanistic investigations suggest that NaBr plays a role in facilitating oxidative addition with these substrates.
Mills, L. Reginald,Graham, Joshua M.,Patel, Purvish,Rousseaux, Sophie A. L.
supporting information
p. 19257 - 19262
(2019/12/02)

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)

Catalytic Dehydrosulfurization of Thioamides to Nitriles by Gold Nanoparticles Supported on Carbon Nanotubes
A gold-carbon nanotube nanohybrid was shown to act as an efficient heterogeneous catalyst in the smooth and selective conversion of thioamides to the corresponding nitriles. The reaction was performed under mild conditions (room temperature, atmospheric pressure of oxygen) using only a gold loading of 0.35 mol %. Substituted aromatic or aliphatic nitriles were produced in very good to excellent yields and the catalyst could be easily recycled and reused over several consecutive cycles with no loss in dehydrosulfurization performances.
Gopi, Elumalai,Geertsen, Valérie,Gravel, Edmond,Doris, Eric
p. 5758 - 5761
(2019/05/21)

Triphenylbismuth Dichloride-Mediated Conversion of Thioamides to Nitriles
Thioamides were efficiently converted to nitriles using the pentavalent triphenylbismuth dichloride in combination with triethylamine. The reaction involved the dehydrosulfurization of primary thioamides to afford substituted aromatic or aliphatic nitriles in good to excellent yields. The process was also successfully extended to the synthesis of cyanamides starting from the corresponding thioureas and of thiocyanates from dithiocarbamates.
Gopi, Elumalai,Gravel, Edmond,Doris, Eric
supporting information
p. 4043 - 4045
(2019/06/24)

Ligand-Promoted Non-Directed C?H Cyanation of Arenes
This article reports the first example of a 2-pyridone accelerated non-directed C?H cyanation with an arene as the limiting reagent. This protocol is compatible with a broad scope of arenes, including advanced intermediates, drug molecules, and natural products. A kinetic isotope experiment (kH/kD=4.40) indicates that the C?H bond cleavage is the rate-limiting step. Also, the reaction is readily scalable, further showcasing the synthetic utility of this method.
Liu, Luo-Yan,Yeung, Kap-Sun,Yu, Jin-Quan
supporting information
p. 2199 - 2202
(2019/01/24)

HETEROGENEOUS COPPER-CATALYZED AEROBIC OXIDATIVE CONVERSION OF AROMATIC ALDEHYDES TO CORRESPONDING NITRILES
The present invention relates to a method of aerobic oxidative converting aromatic aldehyde to nitrile. More specifically, the present invention relates to a method of aerobic oxidative conversion of an aromatic aldehyde to nitrile using a heterogeneous copper catalyst, and optimization of reaction conditions applied thereto. The method can obtain nitrile at high yield with respect to various substrates by synthesizing nitrile, e.g., benzonitrile from aromatic aldehyde, e.g., benzaldehyde and an ammonia source, e.g., ammonia water under an oxygen condition by using TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) and a heterogeneous copper catalyst (Cu@C) obtained by pyrolyzing HKUST-1, i.e., a type of a metal-organic framework, and enables the heterogeneous copper catalyst to be reused at least three or more times without significant loss of catalytic activities since the heterogeneous copper catalyst maintains structure thereof even under the presence of the ammonia source.COPYRIGHT KIPO 2018
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Paragraph 0090-0110; 0134; 0135

(2018/07/31)

HETEROGENEOUS COPPER-CATALYZED AEROBIC OXIDATIVE CONVERSION OF ALCOHOLS TO CORRESPONDING NITRILES
The present invention refers to a method relates to knight reel aerobic oxidation conversion to alcohol (Aerobic oxidative conversion), metal - organic framework is provided electromagnetic wave is pyrolytically cracking using non-uniform copper catalyst (Cu ? C) and TEMPO HKUST-a 1, alcohol (e.g., benzyl alcohol) aromatic aldehyde (e.g., benzaldehyde) aromatic 1 difference after conversion into ammonia source (e.g., ammonia) manner won - port (One-a pot) aromatic aldehydes (e.g., benzo knight reel) added into knight reel by switching, high yield various substrate results in obtaining uniform copper catalyst in the presence of ammonia source knight reel and said holding structure even a significant catalyst activity may be reused without loss to at least 3 or more times, using alcohol knight reel aerobic to non-uniform copper catalyzed oxidative cycle, and applied to the optimization of the reaction conditions are disclosed. (by machine translation)
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Paragraph 0115-0124; 0155; 0181

(2018/10/03)

Electrochemical C-H cyanation of electron-rich (Hetero)arenes
A straightforward method for the electrochemical C-H cyanation of arenes and heteroarenes that proceeds at room temperature in MeOH, with NaCN as the reagent in a simple, open, undivided electrochemical cell is reported. The platinum electrodes are passivated by ad-sorbed cyanide, which allows conversion of an exceptionally broad range of electron-rich substrates all the way down to dialkyl arenes. The cyanide electrolyte can be replenished with HCN, opening opportunities for salt-free industrial C-H cyanation.
Hayrapetyan, Davit,Rit, Raja K.,Kratz, Markus,Tschulik, Kristina,Goo?en, Lukas J.
supporting information
p. 11288 - 11291
(2018/10/20)

Interception of intermediates in phosphine oxidation by mesityl nitrile-: N -oxide using frustrated Lewis pairs
Phosphine oxidation by MesCNO is rapid; however, an FLP strategy intercepts the 1,3 addition products including [MesC(R3P)NOB(C6F5)3] (R = Ph 1, p-tol 2), [MesC(Mes2PH)NOB(C6F5)3] 3 (MesC(NOB(C6F5)3)Ph2P)2(CH2)n (n = 2: 4, 3: 5) and [MesC(Ph3P)NOB(C6F4H)3] 6. These species are shown to react with tBuOK or [Bu4N]F permitting the oxidation to proceed via a process involving borane dissociation. Similarly, the equilibrium established by 1 with B(C6F4H)3 and 6 with B(C6F5)3 provides experimental support for the "Cummins mechanism" for these phosphine oxidations.
Szkop, Kevin M.,Zhu, Diya,Longobardi, Lauren E.,Heck, Julian,Stephan, Douglas W.
supporting information
p. 8933 - 8939
(2018/07/25)

[1+1+3] Annulation of Diazoenals and Vinyl Azides: Direct Synthesis of Functionalized 1-Pyrrolines through Olefination
A dirhodium carboxylate catalyzed [1+1+3] annulation reaction of diazoenals and vinyl azides that gives synthetically important enal-functionalized 1-pyrroline derivatives was developed. The reaction involves a novel rhodium-catalyzed olefination of diazoenals with vinyl azides via electrophilic enal carbenoids, resulting in a new class of enal acrylates. The annulation reaction was used for the direct synthesis of valuable deuterated 1-pyrrolines. Structural diversification of the enal-functionalized 1-pyrrolines resulted in the biologically important pyrrolidine-fused oxaziridine, amino acid derivatives, and a 6-azabicyclo[3.2.1]octane motif present in polycyclic alkaloids.
Kanchupalli, Vinaykumar,Katukojvala, Sreenivas
p. 5433 - 5437
(2018/04/09)

Method for synthesizing aromaticnitrile by using metalloporphyrin to catalyze aromatic olefin
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 0151-0155

(2018/03/01)

AEROBIC OXIDATIVE CONVERSION OF AROMATIC ALDEHYDES TO NITRILES USING A NITROXYL/NOx CATALYST SYSTEM
The present invention relates to an aerobic oxidative conversion method for converting aromatic aldehydes into nitriles and, more particularly to, an aerobic oxidative conversion method for converting aromatic aldehydes into nitriles using a nitroxyl/NO_x catalyst system, which replaces an existing transition metal by converting aromatic aldehydes into nitriles through the oxidative conversion under oxygenic conditions by using a non-metal catalyst system including nitroxyl and NO_x to selectively acquire high-yield nitriles with respect to various substrates and meet the green chemistry, and optimization of reaction conditions applied thereto.COPYRIGHT KIPO 2017
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Paragraph 0113

(2017/11/08)

An exploding: N -isocyanide reagent formally composed of anthracene, dinitrogen and a carbon atom
Targeted as an example of a compound composed of a carbon atom together with two stable neutral leaving groups, 7-isocyano-7-azadibenzonorbornadiene, CN2A (1, A = C14H10 or anthracene) has been synthesized and spectroscopically and structurally characterized. The terminal C atom of 1 can be transferred: mesityl nitrile oxide reacts with 1 to produce carbon monoxide, likely via intermediacy of the N-isocyanate OCN2A. Reaction of 1 with [RuCl2(CO)(PCy3)2] leads to [RuCl2(CO)(1)(PCy3)2] which decomposes unselectively: in the product mixture, the carbide complex [RuCl2(C)(PCy3)2] was detected. Upon heating in the solid state or in solution, 1 decomposes to A, N2 and cyanogen (C2N2) as substantiated using molecular beam mass spectrometry, IR and NMR spectroscopy techniques.
Joost, Maximilian,Nava, Matthew,Transue, Wesley J.,Cummins, Christopher C.
supporting information
p. 11500 - 11503
(2017/10/23)

Cyclic Hydroxamic Acid Analogues of Bacterial Siderophores as Iron-Complexing Agents prepared through the Castagnoli–Cushman Reaction of Unprotected Oximes
The first application of multicomponent chemistry (the Castagnoli–Cushman reaction) toward the convenient one-step preparation of cyclic hydroxamic acids is described. Cyclic hydroxamic acids are close analogues of bacterial siderophores (iron-binding com
Bakulina, Olga,Bannykh, Anton,Dar'in, Dmitry,Krasavin, Mikhail
p. 17667 - 17673
(2017/12/26)

Nickel-Catalyzed C-CN Bond Formation via Decarbonylative Cyanation of Esters, Amides, and Intramolecular Recombination Fragment Coupling of Acyl Cyanides
An efficient nickel-catalyzed decarbonylative cyanation reaction which allows the direct functional-group interconversion of readily available esters into the corresponding nitriles was developed. This reaction successfully offers access to structurally diverse nitriles with high efficiency and excellent functional-group tolerance and provides a good alternative to classical synthetic pathways from diazonium salts or organic halide compounds.
Chatupheeraphat, Adisak,Liao, Hsuan-Hung,Lee, Shao-Chi,Rueping, Magnus
supporting information
p. 4255 - 4258
(2017/08/23)

Green and Practical Oxidative Deoximation of Oximes to Ketones or Aldehydes with Hydrogen Peroxide/Air by Organoselenium Catalysis
Organoselenium-catalyzed oxidative deoximations afforded ketones and aldehydes under mild conditions. The reactions employ hydrogen peroxide and air as clean oxidants and lead to a waste-free and metal-free deprotection protocol for carbonyl protection strategies as well as the green synthesis of ketones and aldehydes. The mechanisms of this interesting organoselenium-catalyzed reaction have been investigated by control experiments as well as the selenium 77 nuclear magnetic resonance (77Se NMR) tests. This novel reaction largely expands the application scope of organoselenium catalysis. (Figure presented.).
Jing, Xiaobi,Yuan, Dandan,Yu, Lei
p. 1194 - 1201
(2017/04/13)

Direct C-H Cyanation of Arenes via Organic Photoredox Catalysis
Methods for the direct C-H functionalization of aromatic compounds are in demand for a variety of applications, including the synthesis of agrochemicals, pharmaceuticals, and materials. Herein, we disclose the construction of aromatic nitriles via direct C-H functionalization using an acridinium photoredox catalyst and trimethylsilyl cyanide under an aerobic atmosphere. The reaction proceeds at room temperature under mild conditions and has proven to be compatible with a variety of electron-donating and -withdrawing groups, halogens, and nitrogen- and oxygen-containing heterocycles, as well as aromatic-containing pharmaceutical agents.
McManus, Joshua B.,Nicewicz, David A.
supporting information
p. 2880 - 2883
(2017/03/11)

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)

Oxoammonium salt-mediated oxidative nitriles synthesis from aldehydes with ammonium acetate
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
supporting information
p. 4695 - 4698
(2017/11/17)

Direct synthesis of nitriles from cleavage of C=C double bond with nitrite as the nitrogen source and oxidant
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
supporting information
p. 2620 - 2623
(2016/06/01)

Facile one-pot transformation of arenes into aromatic nitriles under metal-cyanide-free conditions
Electron-rich arenes bearing methyl or methoxy groups on the aromatic ring were treated with dichloromethyl methyl ether and ZnBr2, and then with molecular iodine and aq. ammonia to give the corresponding aromatic nitriles in good yields. Using this method, febuxostat was efficiently prepared from 4-bromophenol in four steps. The method can be used for the preparation of aromatic nitriles from arenes in one pot under metal-cyanide-free conditions. Various electron-rich arenes could be effectively converted into the corresponding aromatic nitriles in good yields, by treatment with ZnBr2 and dichloromethyl methyl ether, followed by reaction with molecular iodine and aq. ammonia.
Tamura, Toshiyuki,Moriyama, Katsuhiko,Togo, Hideo
p. 2023 - 2029
(2015/03/18)

METHOD FOR PRODUCING NITRILE COMPOUND
PROBLEM TO BE SOLVED: To provide a method for producing a nitrile compound capable of obtaining a nitrile compound in a short time and at a low temperature, while maintaining a high yield. SOLUTION: There is provided a method for producing a nitrile compound using a compound having a hydroxymethylene group as a raw material. The nitrile compound is obtained by mixing and reacting an aliphatic compound or an aromatic compound having a hydroxymethylene group with a N-nitrosyl compound, an oxidant, an iodinating agent and ammonia water. COPYRIGHT: (C)2015,JPO&INPIT
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Paragraph 0041-0044; 0046; 0047

(2016/11/17)

Electroorganic synthesis of nitriles via a halogen-free domino oxidation-reduction sequence
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.
supporting information
p. 16346 - 16348
(2015/11/16)

Dehydration of Aldoximes Using PhSe(O)OH as the Pre-Catalyst in Air
PhSe(O)OH was found to be a good pre-catalyst for aldoxime dehydrations in open air. Compared with the previously reported (PhSe)2-H2O2 system, it is more stable and milder, affording broader application scopes due to a higher functional group tolerance. The control experiments for mechanism study disclosed that air was the key factor for the reaction to maintain enough concentration of PhSeOH, which should be the real catalytic species.
Zhang, Xu,Sun, Jingjing,Ding, Yuanhua,Yu, Lei
supporting information
p. 5840 - 5842
(2015/12/11)

Copper-catalyzed aerobic radical C-C bond cleavage of N-H ketimines
We report herein studies on copper-catalyzed aerobic radical C-C bond cleavage of N-H ketimines. Treatment of N-H ketimines having an α-sp3 hybridized carbon under Cu-catalyzed aerobic reaction conditions resulted in a radical fragmentation with C-C bond cleavage to give the corresponding carbonitrile and carbon radical intermediate. This radical process has been applied for the construction of oxaspirocyclohexadienones as well as in the electrophilic cyanation of Grignard reagents with pivalonitrile as a CN source.
Tnay, Ya Lin,Ang, Gim Yean,Chiba, Shunsuke
supporting information
p. 1933 - 1943
(2016/04/19)

Transnitrilation from Dimethylmalononitrile to Aryl Grignard and Lithium Reagents: A Practical Method for Aryl Nitrile Synthesis
An electrophilic cyanation of aryl Grignard or lithium reagents, generated in situ from the corresponding aryl bromides or iodides, by a transnitrilation with dimethylmalononitrile (DMMN) was developed. DMMN is a commercially available, bench-stable solid. The transnitrilation with DMMN avoids the use of toxic reagents and transition metals and occurs under mild reaction conditions, even for extremely sterically hindered substrates. The transnitrilation of aryllithium species generated by directed ortho-lithiation enabled a net C-H cyanation. The intermediacy of a Thorpe-type imine adduct in the reaction was supported by isolation of the corresponding ketone from the quenched reaction. Computational studies supported the energetic favorability of retro-Thorpe fragmentation of the imine adduct. (Chemical Equation Presented).
Reeves, Jonathan T.,Malapit, Christian A.,Buono, Frederic G.,Sidhu, Kanwar P.,Marsini, Maurice A.,Sader, C. Avery,Fandrick, Keith R.,Busacca, Carl A.,Senanayake, Chris H.
supporting information
p. 9481 - 9488
(2015/08/11)

Phosphinoferrocene ureas: Synthesis, structural characterization, and catalytic use in palladium-catalyzed cyanation of aryl bromides
Phosphinoferrocene ureas Ph2PfcCH2NHCONR2, where NR2 = NH2 (1a), NHMe (1b), NMe2 (1c), NHCy (1d), and NHPh (1e); the analogous thiourea Ph2PfcCH2NHCSNHPh (1f); and the acetamido derivative Ph2PfcCH2NHCOMe (1g) (Cy = cyclohexyl, fc = ferrocene-1,1′-diyl) were prepared via three different approaches starting from Ph2PfcCH2NH2·HCl (3·HCl) or Ph2PfcCHO (4). The reactions of the representative ligand 1e with [PdCl2(cod)] (cod = cycloocta-1,5-diene) afforded [PdCl(μ-Cl)(1e-κP)2]2 or [PdCl2(1e-κP)2]2 depending on the metal-to-ligand stoichiometry, whereas those with [PdCl(η3-C3H5)]2 and [PdCl(LNC)]2 produced the respective bridge cleavage products, [PdCl(η3-C3H5)(1e-κP)] and [PdCl(LNC)(1e-κP)] (LNC = [(2-dimethylamino-κN)methyl]phenyl-κC1). Attempts to involve the polar pendant in coordination to the Pd(II) center were unsuccessful, indicating that the phosphinoferrocene ureas 1 bind Pd(II) preferentially as modified phosphines rather than bifunctional donors. When combined with palladium(II) acetate, the ligands give rise to active catalysts for Pd-catalyzed cyanation of aryl bromides with potassium hexacyanoferrate(II). Optimization experiments revealed that the best results are obtained in 50% aqueous dioxane with a catalyst generated from 1 mol % of palladium(II) acetate and 2 mol % of 1e in the presence of 1 equiv of Na2CO3 as the base and half molar equivalent of K4[Fe(CN)6]·3H2O. Under such optimized conditions, bromobenzenes bearing electron-donating substituents are cyanated cleanly and rapidly, affording the nitriles in very good to excellent yields. In the case of substrates bearing electron-withdrawing groups, however, the cyanation is complicated by the hydrolysis of the formed nitriles to the respective amides, which reduces the yield of the desired primary product. Amine- and nitro-substituted substrates are cyanated only to a negligible extent, the former due to their metal-scavenging ability.
?koch, Karel,Císa?ová, Ivana,?těpni?ka, Petr
p. 1942 - 1956
(2015/06/08)

Copper-catalyzed aerobic conversion of the C=O bond of ketones to a C≡N bond using ammonium salts as the nitrogen source
The conversion of the C=O bond of ketones to a C≡N bond is described. This conversion is catalyzed by copper salts with ammonium salts as the nitrogen source in the presence of molecular oxygen. A wide variety of ketones can be converted into the corresponding compounds containing a C≡N bond. Based on the preliminary experiments, a plausible mechanism of this transformation is disclosed.
Xu, Bin,Jiang, Qing,Zhao, An,Jia, Jing,Liu, Qiang,Luo, Weiping,Guo, Cancheng
supporting information
p. 11264 - 11267
(2015/07/08)

"Nanorust"-catalyzed benign oxidation of amines for selective synthesis of nitriles
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
p. 92 - 96
(2015/02/19)

A highly efficient electrochemical route for the conversion of aldehydes to nitriles
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
p. 747 - 750
(2015/04/14)

Cu-mediated nitrogen atom transfer via C≡N bond cleavage
A nitrogen atom transfer to organic molecules via Cu-mediated C-N triple bond cleavage is firstly developed, which provides a variety of functionalized aryl nitriles from the readily accessible acetonitrile and aryl aldehydes.
Liu, Lixin,Dong, Jianyu,Zhang, Yaxing,Zhou, Yongbo,Yin, Shuang-Feng
supporting information
p. 9948 - 9952
(2015/10/12)

Aerobic Oxidative Conversion of Aromatic Aldehydes to Nitriles Using a Nitroxyl/NOx Catalyst System
The first transition-metal-free aerobic oxidative conversion of aldehyde catalyzed by a nitroxyl radical/NOx system is presented for the synthesis of nitrile. In the presence of a catalytic amount of 4-AcNH-TEMPO (4-acetamido-2,2,6,6-tetramethylpiperidine-N-oxyl), NaNO2, and HNO3, benzaldehydes bearing a variety of functional groups underwent condensation with NH4OAc and following aerobic oxidation to produce nitriles selectively under an O2 balloon. Aerobic oxidative conversion of a primary alcohol instead of aldehyde is also achieved by a one-pot sequential strategy.
Noh, Ji-Hyun,Kim, Jinho
p. 11624 - 11628
(2015/12/01)

Copper iodide nanoparticles-catalysed cyanation of aryl halides using non-toxic K4[Fe(CN)6] in the presence of 1,2-bis(5-tetrazolyl)benzene as an efficient ligand
Cyanation of aryl bromides were carried out with K4[Fe(CN) 6] in the presence of catalytic amounts of a copper salt and 1,2-bis(5-tetrazolyl)benzene as a ligand under thermal conditions. This method has the advantages of high yields, simple methodology and easy work up.
Maham, Mehdi,Bahari, Siavash
p. 291 - 294
(2014/06/09)

Iron(II)-catalyzed direct cyanation of arenes with aryl(cyano)iodonium triflates
A direct oxidative cyanation of arenes under FeII catalysis with 3,5-di(trifluoromethyl)phenyl(cyano)iodonium triflate (DFCT) as the cyanating agent has been developed. The reaction is applicable to wide range of aromatic substrates, including polycyclic structures and heteroaromatic compounds. Copyright
Shu, Zhibin,Ji, Wenzhi,Wang, Xi,Zhou, Yujing,Zhang, Yan,Wang, Jianbo
supporting information
p. 2186 - 2189
(2014/03/21)

Phenyliodonium diacetate mediated direct synthesis of benzonitriles from styrenes through oxidative cleavage of C=C bonds
A metal-free PhI(OAc)2 mediated nitrogenation of alkenes through C=C bond cleavage using inorganic ammonia salt as nitrogen source under mild conditions was developed, affording nitriles in moderate to good yields. The advantages of this reaction are mild reaction conditions, operational simplicity, and use of an ammonium salt as nitrogen source. Based upon experimental observations, a plausible reaction mechanism is proposed.
Xu, Jin-Hui,Jiang, Qing,Guo, Can-Cheng
p. 11881 - 11886
(2014/01/06)

Cu2O-mediated room temperature cyanation of aryl boronic acids/esters and TMSCN
A method for the efficient and reliable synthesis of aryl nitriles via the Cu2O-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. A broad range of substrates decorated by electron-rich and deficient, sterically very congested, and labile functionalities were tolerated. Moreover, the reaction can proceed under mild conditions at room temperature. These advantages paired with the use of cheap, readily available, and halogen-free Cu2O as catalysts make the protocol an appealing option for aryl cyanations. A method for the efficient and reliable synthesis of aryl nitriles via the Cu2O-catalyed cross-coupling of aryl boronic acids or esters and TMSCN is presented. The room temperature operation paired with the use of cheap, readily available, and halogen-free Cu2O as catalysts makes the protocol an appealing option for aryl cyanations. Copyright
Ye, Yong,Wang, Yanhua,Liu, Pengtang,Han, Fushe
supporting information
p. 27 - 30
(2013/08/24)

Practical one-pot conversion of aryl bromides and β-bromostyrenes into aromatic nitriles and cinnamonitriles
Various aryl bromides were efficiently converted into the corresponding aromatic nitriles in good yields by the treatment with Mg turnings and subsequently DMF, followed by treatment with molecular iodine and aq NH 3. The same treatment of aryl bromides, which are weakly reactive to Mg turnings, with iPrMgCl·LiCl and subsequently DMF, followed by the treatment with molecular iodine and aq NH3 also afforded the corresponding aromatic nitriles in good yields. On the other hand, when N-formylpiperidine was used instead of DMF, p-substituted β-bromostyrenes were converted into the corresponding p-substituted cinnamonitriles, i.e., α,β-unsaturated nitriles, in good to moderate yields by the same procedure. The reactions were carried out by means of a simple experimental procedure and did not require any toxic metal cyanides or expensive rare metals. Therefore, the present reactions are practical and environmentally benign one-pot methods for the preparation of aromatic nitriles, cinnamonitriles, and aliphatic nitriles from aryl bromides, β-bromostyrenes, and alkyl bromides, respectively, through the formation of Grignard reagents and their DMF or N-formylpiperidine adducts.
Ishii, Genki,Harigae, Ryo,Moriyama, Katsuhiko,Togo, Hideo
p. 1462 - 1469
(2013/02/25)

Simple one-pot conversion of alcohols into nitriles
Various benzylic and primary alcohols were efficiently converted into the corresponding nitriles in good yields at room temperature by treatment with tert-butyl hypochlorite, diiodine, or 1,3-diiodo-5,5-dimethylhydantoin in the presence of (2,2,6,6-tetramethylpiperidin-1-yl)oxidanyl (TEMPO), followed by treatment with diiodine and aqueous ammonia. The nitriles were obtained in good yields and high purities simply by extraction of the reaction mixture with chloroform and subsequent removal of the solvent.
Shimojo, Hiroyuki,Moriyama, Katsuhiko,Togo, Hideo
p. 2155 - 2164
(2013/08/23)

Copper-catalyzed oxidative cyanation of aryl halides with nitriles involving carbon-carbon cleavage
A novel, general route for the synthesis of aromatic nitriles is presented that proceeds through Cu(OAc)catalyzed oxidative cyanation of aryl halides using commercially available nitriles as the cyanide sources and Ag/air as the oxidizing agent. It is noteworthy that this work provides a new example of using acetonitrile as the cyanide source for aromatic nitrile synthesis through a Cu-catalyzed oxidative C-C bond cleavage and cyanation process.
Song, Ren-Jie,Wu, Ji-Cheng,Liu, Yu,Deng, Guo-Bo,Wu, Cui-Yan,Wei, Wen-Ting,Li, Jin-Heng
supporting information
p. 2491 - 2496,6
(2012/12/11)

Practical one-pot transformation of electron-rich aromatics into aromatic nitriles with molecular iodine and aq NH3 using Vilsmeier-Haack reaction
Various electron-rich aromatics could be efficiently transformed into the corresponding aromatic nitriles in good to moderate yields by treatment with DMF and POCl3, followed by the reaction with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH) in aq NH3. Some of less reactive aromatics, such as anisole, 1,2-dimethoxybenzene, 1,4-dimethoxybenzene, and mesityrene, could be also transformed into the corresponding aromatic nitriles in good to moderate yields using N-methylformanilide and O(POCl 2)2, followed by the reaction with molecular iodine in aq NH3. Moreover, propiophenone derivatives could be successfully transformed into the corresponding β-chlorocinnamonitriles by the reaction with DMF and POCl3, followed by the reaction with molecular iodine and aq NH3. These reactions are novel metal-free one-pot methods for the preparation of aromatic nitriles from electron-rich aromatics and β-chlorocinnamonitriles from propiophenones.
Ushijima, Sousuke,Moriyama, Katsuhiko,Togo, Hideo
experimental part
p. 4588 - 4595
(2012/07/27)

Straightforward zinc-catalyzed transformation of aldehydes and hydroxylamine hydrochloride to nitriles
In the present study, the zinc-catalyzed dehydration of a range of in situ generated aldoximes, available by the reaction of aldehydes and hydroxylamine hydrochloride, has been explored. After investigating various reaction parameters, with Zn(OTf)2 an excellent and easily accessible pre-catalyst was obtained. The system was highly active and dehydrated a broad range of aldoximes selectively to the corresponding nitriles under mild reaction conditions.
Enthaler, Stephan,Weidauer, Maik,Schr?der, Fanny
experimental part
p. 882 - 885
(2012/03/26)

A novel and convenient synthesis of benzonitriles: Electrophilic cyanation of aryl and heteroaryl bromides
N-Cyano-N-phenyl-p-methylbenzenesulfonamide has been used as a more benign electrophilic cyanation reagent for the synthesis of various benzonitriles from (hetero)aryl bromides via formation of Grignard reagents. Electronically different and sterically demanding aryl bromides including functionalized substrates and heteroaryl bromides are successfully cyanated in good to excellent yields. The efficiency of the present methodology is shown by the expeditious syntheses of interesting pharmaceutical intermediates. Notably, chemoselective monocyanation of dibromoarenes is also achieved. Copyright
Anbarasan, Pazhamalai,Neumann, Helfried,Beller, Matthias
supporting information; experimental part
p. 4217 - 4222
(2011/05/06)