cas 4421-09-4, Piperonylonitrile | Articles data

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Imidazole hydrochloride promoted synthesis of 3,5-disubstituted-1,2,4-oxadiazoles
Imidazole hydrochloride as an additive promotes the reaction of amidoximes and DMA derivatives to generated 3,5-disubstituted-1,2,4-oxadiazoles in low to excellent yields without the use of coupling reagents, oxidants, strong acids or bases and other additives.
Wang, Xuetong,Wang, Yin,Liu, Xiaoling,He, Tingshu,Li, Lingli,Wu, Huili,Zhou, Shangjun,Li, Dan,Liao, Siwei,Xu, Ping,Huang, Xing,Yuan, Jianyong
(2021/10/14)

Nickel-Catalyzed Reversible Functional Group Metathesis between Aryl Nitriles and Aryl Thioethers
We describe a new functional group metathesis between aryl nitriles and aryl thioethers. The catalytic system nickel/dcype is essential to achieve this fully reversible transformation in good to excellent yields. Furthermore, the cyanide- and thiol-free reaction shows high functional group tolerance and great efficiency for the late-stage derivatization of commercial molecules. Finally, synthetic applications demonstrate its versatility and utility in multistep synthesis.
Delcaillau, Tristan,Boehm, Philip,Morandi, Bill
supporting information
p. 3723 - 3728
(2021/04/07)

Revisiting the synthesis of aryl nitriles: a pivotal role of CAN
Facilitated by the dual role of Ceric Ammonium Nitrate (CAN), herein we report a cost-effective approach for the cyanation of aryl iodides/bromides with CAN-DMF as an addition to the existing pool of combined cyanation sources. In addition to being an oxidant, CAN acts as a source of nitrogen in our protocol. The reaction is catalyzed by a readily available Cu(ii) salt and the ability of CAN to generate ammonia in the reaction medium is utilized to eliminate the additional requirement of a nitrogen source, ligand, additive or toxic reagents. The mechanistic study suggests an evolution of CN?leading to the synthesis of a variety of aryl nitriles in moderate to good yields. The proposed mechanism is supported by a series of control reactions and labeling experiments.
Saikia, Rakhee,Park, Kwihwan,Masuda, Hayato,Itoh, Miki,Yamada, Tsuyoshi,Sajiki, Hironao,Mahanta, Sanjeev P.,Thakur, Ashim J.
p. 1344 - 1351
(2021/02/27)

CuO-catalyzed conversion of arylacetic acids into aromatic nitriles with K4Fe(CN)6 as the nitrogen source
Readily available CuO was demonstrated to be effective as the catalyst for the conversion of arylacetic acids to aromatic nitriles with non-toxic and inexpensive K4Fe(CN)6 as the nitrogen source via the complete cleavage of the C[tbnd]N triple bond. The present method allowed a series of arylacetic acids including phenylacetic acids, naphthaleneacetic acids, 2-thiopheneacetic acid and 2-furanacetic acid to be converted into the targeted products in low to high yields.
Ren, Yun-Lai,Shen, Zhenpeng,Tian, Xinzhe,Xing, Ai-Ping,Zhao, Zhe
(2020/10/26)

Cu2O-Catalyzed Conversion of Benzyl Alcohols Into Aromatic Nitriles via the Complete Cleavage of the C≡N Triple Bond in the Cyanide Anion
Nitrogen transfer from cyanide anion to an aldehyde is emerging as a promising method for the synthesis of aromatic nitriles. However, this method still suffers from a disadvantage that a use of stoichiometric Cu(II) or Cu(I) salts is required to enable the reaction. As we report herein, we overcame this drawback and developed a catalytic method for nitrogen transfer from cyanide anion to an alcohol via the complete cleavage of the C≡N triple bond using phen/Cu2O as the catalyst. The present condition allowed a series of benzyl alcohols to be smoothly converted into aromatic nitriles in moderate to high yields. In addition, the present method could be extended to the conversion of cinnamic alcohol to 3-phenylacrylonitrile.
Liu, Wenbo,Tang, Peichen,Zheng, Yi,Ren, Yun-Lai,Tian, Xinzhe,An, Wankai,Zheng, Xianfu,Guo, Yinggang,Shen, Zhenpeng
p. 3509 - 3513
(2021/10/04)

Selective oxidation of alcohols to nitriles with high-efficient Co-[Bmim]Br/C catalyst system
An efficient method for catalyzing the ammoxidation of aromatic alcohols to aromatic nitriles was developed, in which a new heterogeneous catalyst based on transition metal elements was employed, the new catalyst was named Co-[Bmim]Br/C-700 and then characterized by X-ray photo-electronic spectroscopy, transmission electron microscope and X-ray diffraction. The reaction was carried out by two consecutive dehydrogenations under the catalysis of Co-[Bmim]Br/C-700, which catalytically oxidized the alcohol to the aldehyde, and then the aldehyde was subjected to ammoxidation to the nitrile. The catalyst system was suitable for a wide range of substrates and nitriles obtained in high yields, especially, the conversion rate of benzyl alcohol, 4-methoxybenzyl alcohol, 4-chlorobenzyl alcohol and 4-nitrobenzyl alcohol reached 100%. The substitution of ammonia and oxygen for toxic cyanide to participate in the reaction accords with the theory of green chemistry.
Xia, Yu-Yan,Lv, Qing-Yang,Yuan, Hua,Wang, Jia-Yi
p. 3957 - 3964
(2021/04/09)

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.
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Paragraph 0034-0039; 0214-0219

(2020/09/16)

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)

Metal-free dehydrosulfurization of thioamides to nitriles under visible light
A visible light-mediated, metal-free dehydrosulfurization reaction of thioamides to nitriles is described. This reaction features high yields, mild reaction conditions, and the use of a cheap organic dye as the photoredox catalyst and air as the oxidant.
Xu, Tianxiao,Cao, Tianpeng,Feng, Qingyuan,Huang, Shenlin,Liao, Saihu
p. 5151 - 5153
(2020/05/26)

HCl·DMPU-assisted one-pot and metal-free conversion of aldehydes to nitriles
We report an efficient HCl·DMPU assisted one-pot conversion of aldehydes into nitriles. The use of HCl·DMPU as both an acidic source as well as a non-nucleophilic base constitutes an environmentally mild alternative for the preparation of nitriles. Our protocol proceeds smoothly without the use of toxic reagents and metal catalysts. Diverse functionalized aromatic, aliphatic and allylic aldehydes incorporating various functional groups were successfully converted to nitriles in excellent to quantitative yields. This protocol is characterized by a broad substrate scope, mild reaction conditions, and high scalability. This journal is
Hammond, Gerald B.,Mudshinge, Sagar R.,Potnis, Chinmay S.,Xu, Bo
supporting information
p. 4161 - 4164
(2020/07/14)

Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
Herein, a Grubbs-catalyzed route for the synthesis of nitriles via the aerobic oxidation of primary amines is reported. This reaction accommodates a variety of substrates, including simple primary amines, sterically hindered β,β-disubstituted amines, allylamine, benzylamines, and α-amino esters. Reaction compatibility with various functionalities is also noted, particularly with alkenes, alkynes, halogens, esters, silyl ethers, and free hydroxyl groups. The nitriles were also synthesized via the oxidation of imines generated from aldehydes and NH4OAc in situ. (Figure presented.).
Utsumi, Tatsuki,Noda, Kenta,Kawauchi, Daichi,Ueda, Hirofumi,Tokuyama, Hidetoshi
supporting information
p. 3583 - 3588
(2020/08/05)

Oxidation of aldehydes to nitriles with an oxoammonium salt: Preparation of piperonylonitrile
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Kaetzel, Nathaniel D.,Kelly, Christopher B.,Lambert, Kyle M.
p. 294 - 313
(2020/11/09)

Chlorotropylium Promoted Conversions of Oximes to Amides and Nitriles
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
p. 311 - 315
(2020/01/25)

Nickel-Catalyzed Transformation of Alkene-Tethered Oxime Ethers to Nitriles by a Traceless Directing Group Strategy
Nickel-catalyzed transformation of alkene-tethered oxime ethers to nitriles using a traceless directing group strategy has been developed. A series of alkene-tethered oxime ethers derived from benzaldehyde and cinnamyl aldehyde derivatives were converted into the corresponding benzonitriles and cinnamonitriles in 46-98% yields using the nickel catalyst system. Control experiments showed that the alkene group tethered to an oxygen atom on the oximes via one methylene unit plays a key role as a traceless directing group during the catalysis.
Takahashi, Yoshiyuki,Tsuji, Hiroaki,Kawatsura, Motoi
p. 2654 - 2665
(2020/02/04)

SO2F2-Mediated one-pot cascade process for transformation of aldehydes (RCHO) to cyanamides (RNHCN)
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
p. 17288 - 17292
(2020/05/18)

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
(2020/08/19)

Nickel-Catalyzed Cyanation of Aryl Halides and Hydrocyanation of Alkynes via C-CN Bond Cleavage and Cyano Transfer
We report nickel-catalyzed cyanation and hydrocyanation methods to prepare aryl nitriles and vinyl nitriles from aryl halides and alkynes, respectively. Using inexpensive and nontoxic 4-cyanopyridine N-oxide as the cyano shuttle, the methods provide an efficient approach to prepare aryl cyanides and vinyl nitriles under mild and operationally simple reaction conditions with a broad range of functional group tolerances. In hydrocyanation of alkynes, the method demonstrated good regioselectivity, producing predominantly E- or Z-alkenyl nitriles in a controlled manner and exclusively Markovnikov vinyl nitriles when internal diaryl alkynes and terminal alkynes were applied as the substrates, respectively. The preliminary mechanistic investigation indicated that the C-CN bond cleavage process is promoted by oxidative addition to the nickel(I) complex in the cyanation of aryl halides, and further studies via a series of deuterium exchange experiments indicated that water serves as the hydrogen source for the hydrocyanation of alkynes.
Chen, Hui,Sun, Shuhao,Liu, Yahu A.,Liao, Xuebin
p. 1397 - 1405
(2020/02/04)

Atomically Dispersed Ru on Manganese Oxide Catalyst Boosts Oxidative Cyanation
There is a strong incentive for environmentally benign and sustainable production of organic nitriles to avoid the use of toxic cyanides. Here we report that manganese oxide nanorod-supported single-site Ru catalysts are active, selective, and stable for oxidative cyanation of various alcohols to give the corresponding nitriles with molecular oxygen and ammonia as the reactants. The very low amount of Ru (0.1 wt %) with atomic dispersion boosts the catalytic performance of manganese oxides. Experimental and theoretical results show how the Ru sites enhance the ammonia resistance of the catalyst, bolstering its performance in alcohol dehydrogenation and oxygen activation, the key steps in the oxidative cyanation. This investigation demonstrates the high efficiency of a single-site Ru catalyst for nitrile production.
Gates, Bruce C.,Guan, Erjia,Meng, Xiangju,Wang, Chengtao,Wang, Hai,Wang, Liang,Wang, Sai,Xiao, Feng-Shou,Xu, Dongyang,Xu, Hua,Yang, Bo,Zhang, Jian
p. 6299 - 6308
(2020/07/21)

Visible-light-driven catalytic oxidation of aldehydes and alcohols to nitriles by 4-acetamido-tempo using ammonium carbamate as a nitrogen source
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.
supporting information
p. 9182 - 9186
(2019/11/05)

A Transition-Metal-Free One-Pot Cascade Process for Transformation of Primary Alcohols (RCH2OH) to Nitriles (RCN) Mediated by SO2F2
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
p. 3190 - 3194
(2019/05/21)

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)

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)

Preparing method of aromatic nitrile or alkenyl nitrile compound
The invention discloses a preparing method of an aromatic nitrile or alkenyl nitrile compound. The preparing method comprises the following step that under protection of inert gas, an aryl or heteroaryl sulphonate compound shown in a formula II or an alkenyl sulphonate compound shown in a formula IV and a cyanation reagent are subjected to a cross-coupling reaction as is shown below in a solvent under the condition of the presence of a nickel complex, metal zinc and an additive to obtain the aromatic nitrile or alkenyl nitrile compound, wherein 4-dimethylamiopryidine (DMAP) is adopted as the additive, and zinc cyanide is adopted as the cyanation reagent. By means of the preparing method, cyanation of aryl sulphonate, heteroaryl sulphonate or alkenyl sulphonate can be simply and efficientlyachieved with a cheap catalysis system; moreover, the functional group compatibility and substrate universality are good, and a better application prospect and higher using value are provided for achieving industrial synthesis of the aromatic nitrile or alkenyl nitrile compound.
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Paragraph 0130-0132; 0148-0150; 0232-0233

(2019/10/01)

Thiocyanate radical mediated dehydration of aldoximes with visible light and air
We developed a new means of activating aldoximes by an in situ generated thiocyanate radical from ammonium thiocyanate and molecular oxygen at room temperature. With a catalytic amount of organic dye aizenuranine as the photocatalyst, the dehydration of aldoximes proceeds smoothly under visible light irradiation, providing a simple to handle, excellent functional group tolerance, and metal-free protocol for a wide range of nitriles.
Ban, Yong-Liang,Dai, Jian-Ling,Jin, Xiao-Ling,Zhang, Qing-Bao,Liu, Qiang
supporting information
p. 9701 - 9704
(2019/08/15)

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)

NOVEL IMIDAZOLE DERIVATIVE HAVING JNK INHIBITORY ACTIVITY AND USE THEREOF
The present invention relates to a novel imidazole derivative having a C-Jun N-terminal kinase (JNK) inhibitory activity and a use thereof. A novel imidazole derivative or a pharmaceutically acceptable salt thereof according to the present invention exhibits an excellent inhibitory activity against C-Jun N-terminal kinase (JNK), and thus it is anticipated that a more fundamental approach and target treatment will be possible in the prevention or treatment of degenerative brain nervous system diseases.
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Paragraph 0059

(2018/12/13)

Direct Conversion of Benzyl Ethers into Aryl Nitriles
A direct method was developed for the conversion of benzyl ethers into aryl nitriles by using NH 4 OAc as the nitrogen source and oxygen as the terminal oxidant with catalysis by TEMPO/HNO 3; the method is valuable for both the synthesis of aromatic nitriles and for the deprotection of ether-protected hydroxy groups to form nitrile groups in multistep organic syntheses.
Tian, Xinzhe,Ren, Yun-Lai,Ren, Fangping,Cheng, Xinqiang,Zhao, Shuang,Wang, Jianji
p. 2444 - 2448
(2018/11/23)

Nickel-Catalyzed Cyanation of Phenol Derivatives with Zn(CN)2 Involving C-O Bond Cleavage
An efficient nickel-catalyzed cyanation of aryl sulfonates, fluorosulfonates, and sulfamates with Zn(CN)2 was developed, which provides a facile access to the nitrile products in generally good to excellent yields. The reaction is accomplished by using NiII complex as the precatalyst and DMAP as the additive. The method also displays wide functional group compatibility; for example, keto, methoxy, N,N-dimethylamino, cyano, ester, and pyridyl groups are well-tolerated during the reaction process.
Gan, Yi,Wang, Gaonan,Xie, Xin,Liu, Yuanhong
p. 14036 - 14048
(2018/11/03)

Nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine
A nickel-catalyzed cyanation of phenol derivatives activated by 2,4,6-trichloro-1,3,5-triazine (TCT) using aminoacetonitrile as the cyanating agent is described. This catalytic system delivered the desired products in moderate to good yields with good substrate compatibility. The readily available starting materials, cost-effective nickel catalyst and metal-free cyanating agent are the major features of the present method.
Wang, Liang,Wang, Yaoyao,Shen, Jun,Chen, Qun,He, Ming-Yang
supporting information
p. 4816 - 4820
(2018/07/13)

Nickel-Catalyzed Deoxycyanation of Activated Phenols via Cyanurate Intermediates with Zn(CN)2: A Route to Aryl Nitriles
A novel, and efficient nickel-catalyzed deoxycyanation of phenolic compounds using relatively nontoxic Zn(CN)2 as the cyanide source was developed. The reaction of C-O bond activated phenolic compounds by 2,4,6-trichloro-1,3,5-triazine with Zn(CN)2 in the presence of a nickel precatalyst afforded the aromatic nitriles in good to excellent yields.
Heravi, Majid M.,Panahi, Farhad,Iranpoor, Nasser
supporting information
p. 2753 - 2756
(2018/05/22)

Palladium-Catalyzed Synthesis of Aryl Nitriles: Using α-Iminonitrile as Cyano Source for Aryl Halide Cyanations
An efficient and ligand-free palladium-catalyzed exchange reaction to synthesize aryl nitriles by using α-iminonitrile as a starting reagent has been developed. This methodology provides an optional method for the synthesis of aryl nitriles with moderate to good yields. At the same time, this approach is adaptable for many substrates.
Shi, Yu-Long,Yuan, Qing,Chen, Zhen-Bang,Zhang, Fang-Ling,Liu, Kui,Zhu, Yong-Ming
supporting information
p. 359 - 363
(2017/11/15)

Pd-Catalyzed Cyanation of (Hetero)Aryl Halides by Using Biphosphine Ligands
Tetraadamantylbiphosphine (TABP; L1), which showed superior activity in the palladium-catalyzed cyanation of 4-chloroanisole compared to standard phosphines, was synthesized as a new ligand. The generality of the new catalytic system was shown by the cyanation reaction of approximately 30 (hetero)aryl halides including hindered, electron-rich, and electron-poor aryl chlorides. These reactions constitute the first examples of using biphosphine ligands in Pd-catalyzed coupling reactions.
Zhang, Shaoke,Neumann, Helfried,Beller, Matthias
supporting information
p. 67 - 70
(2017/11/27)

Practical CuCl/DABCO/4-HO-TEMPO-catalyzed oxidative synthesis of nitriles from alcohols with air as oxidant
A mild and efficient methodology for the direct oxidative synthesis of nitriles from easily available alcohols and aqueous ammonia by employing CuCl/DABCO/4-HO-TEMPO as the catalysts is described. This protocol uses the air as a green oxidant and aqueous ammonia as the nitrogen source at room temperature. A variety of aryl, heterocyclic and allylic alcohols are smoothly converted into the corresponding nitriles in good to excellent yields.
Hu, Yongke,Chen, Lei,Li, Bindong
supporting information
p. 464 - 466
(2017/11/13)

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; 0114

(2017/11/08)

Catalyst-free, efficient and one pot protocol for synthesis of nitriles from aldehydes using glycerol as green solvent
We described herein the novel, efficient and one-pot catalyst free protocol for the synthesis of nitriles from aldehydes by using hydroxyl amine hydrochlorides in glycerol as a green solvent. This protocol was efficiently used for transformation of aromatic aldehydes bearing electron-withdrawing and electron-donating groups into a aryl nitriles in good to excellent yields. The methodology offers a very simple, efficient and environmentally benign procedure.
Ingale, Ajit P.,Patil, Shripad M.,Shinde, Sandeep V.
p. 4845 - 4848
(2017/11/30)

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)

Nickel-Catalyzed Cyanation of Aryl Chlorides and Triflates Using Butyronitrile: Merging Retro-hydrocyanation with Cross-Coupling
We describe a nickel-catalyzed cyanation reaction of aryl (pseudo)halides that employs butyronitrile as a cyanating reagent instead of highly toxic cyanide salts. A dual catalytic cycle merging retro-hydrocyanation and cross-coupling enables the conversion of a broad array of aryl chlorides and aryl/vinyl triflates into their corresponding nitriles. This new reaction provides a strategically distinct approach to the safe preparation of aryl cyanides, which are essential compounds in agrochemistry and medicinal chemistry.
Yu, Peng,Morandi, Bill
supporting information
p. 15693 - 15697
(2017/12/02)

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)

A room temperature cyanation of (hetero)aromatic chlorides by an air stable nickel(II) XantPhos precatalyst and Zn(CN)2
A methodology for the synthesis of (hetero)aromatic nitriles from aryl chlorides at room temperature has been developed. This methodology uses an air and moisture stable nickel(ii) XantPhos precatalyst and Zn(CN)2 as the cyanide (CN-) source.
Beattie, D. Dawson,Schareina, Thomas,Beller, Matthias
supporting information
p. 4291 - 4294
(2017/07/10)

Decarbonylative Cyanation of Amides by Palladium Catalysis
Transition-metal-catalyzed cyanation of aryl halides is a process of significant importance in the preparation pharmaceuticals, organic materials and agrochemicals. Here, we demonstrate a palladium-catalyzed decarbonylative cyanation of amides by highly selective carbon-nitrogen bond cleavage for the synthesis of a wide range of aryl nitriles. The utility of this technology is demonstrated by the synthesis of isotopically labeled aryl nitriles and orthogonal cross-coupling reactions of bench-stable amides to establish cross-coupling synthons with opposite polarity.
Shi, Shicheng,Szostak, Michal
supporting information
p. 3095 - 3098
(2017/06/23)

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)

Synthesis of nitriles from amines using nanoscale Co3O4-based catalysts via sustainable aerobic oxidation
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
supporting information
p. 3356 - 3359
(2016/04/09)

Metal-Free Oxidation of Primary Amines to Nitriles through Coupled Catalytic Cycles
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.
supporting information
p. 5156 - 5159
(2016/04/09)

Direct synthesis of nitriles from aldehydes with hydroxylamine-O-sulfonic acid in acidic water
Herein is reported the selective transformation of aldehydes to nitriles in the presence of hydroxylamine-O-sulfonic acid (NH2OSO3H) as a source of the N atom and acidic water. The reaction works with high yields for a large array of aromatic and aliphatic aldehydes, as well as hindered aldehydes and conjugated aldehydes without purification. The reaction conditions are very mild and tolerate a wide array of functional groups. In principle, the reaction can be completed in vinegar.
Quinn, Dylan J.,Haun, Graham J.,Moura-Letts, Gustavo
supporting information
p. 3844 - 3847
(2016/08/02)

Improved schmidt conversion of aldehydes to nitriles using azidotrimethylsilane in 1,1,1,3,3,3-Hexafluoro-2-Propanol
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
(2016/02/05)

Erratum: Copper-mediated cyanation of indoles and electron-rich arenes using DMF as a single surrogate (Org. Biomol. Chem. (2015) 13 (8322-8329))
Correction for 'Copper-mediated cyanation of indoles and electron-rich arenes using DMF as a single surrogate' by Lianpeng Zhang et al., Org. Biomol. Chem., 2015, 13, 8322-8329.
Zhang, Lianpeng,Lu, Ping,Wang, Yanguang
p. 1840 - 1840
(2016/02/09)

Radical Beckmann Rearrangement and Its Application in the Formal Total Synthesis of Antimalarial Natural Product Isocryptolepine via C-H Activation
The Beckmann rearrangement of ketoximes, mediated by ammonium persulfate-dimethyl sulfoxide as a reagent, has been achieved under neutral conditions. Based on the radical trapping and 18O-labeling experiments, the transformation follows a mechanism involving a radical pathway. The scope and generality of the developed protocol has been demonstrated by 19 examples. The developed protocol and Pd-catalyzed intramolecular double C-H activation were used as key steps in the formal total synthesis of antimalarial natural product isocryptolepine.
Mahajan, Pankaj S.,Humne, Vivek T.,Tanpure, Subhash D.,Mhaske, Santosh B.
supporting information
p. 3450 - 3453
(2016/07/26)

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)

"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)