- Reactions of 1,3-dehydroadamantane with inorganic oxygen-free acids
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A convenient and efficient procedure has been developed for the synthesis of 1-azidoadamantane, 1-adamantyl isocyanate, and 1-adamantyl isothiocyanate by reaction of 1,3-dehydroadamantane with hydrazoic, isocyanic, and isothiocyanic acids, respectively, under mild conditions. The reaction of 1,3-dehydroadamantane with hydrogen cyanide under analogous conditions gives adamantane-1-carbonitrile in a poor yield which may be improved using hexane as solvent.
- Butov,Mokhov,Burmistrov,Saad,Pitushkin
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Read Online
- Lewis Acid-Catalyzed Preparation of Bridge-head Adamantanoid Nitriles from their Corresponding Halides and Trimethylsilyl Cyanide
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Bridge-head adamantyl and diamantyl nitriles 2 have been prepared in good yields by refluxing the corresponding halides 1 with trimethylsilyl cyanide and tin(IV) chloride in dichloromethane.
- Olah, George A.,Farooq, Omar,Surya Prakash, G. K.
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Read Online
- Method for dehydrating primary amide into nitriles under catalysis of cobalt
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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.
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Paragraph 0123-0125
(2021/06/21)
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- Direct C(sp3)-H Cyanation Enabled by a Highly Active Decatungstate Photocatalyst
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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
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supporting information
p. 5501 - 5505
(2021/07/26)
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- Copper-Catalyzed Intermolecular Functionalization of Unactivated C(sp3)-H Bonds and Aliphatic Carboxylic Acids
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Intermolecular functionalization of C(sp3)-H bonds and aliphatic carboxylic acids enables the efficient synthesis of high value-added organic compounds from readily available starting materials. Although methods involving hydrogen atom transfer have been developed for such functionalization, these methods either work for only activated C(sp3)-H bonds or bring in a narrow set of functional groups. Here we describe a Cu-catalyzed process for the diverse functionalization of both unactivated C(sp3)-H bonds and aliphatic carboxylic acids. The process is enabled by the trapping of alkyl radicals generated through hydrogen atom abstraction by arylsulfonyl-based SOMO-philes, which introduces a large array of C, N, S, Se, and halide-based functional groups. The chemoselectivity can be switched from C-H functionalization to decarboxylative functionalization by matching the bond dissociation energy of the hydrogen atom transfer reagent with that of the target C-H or O-H bond.
- Mao, Runze,Bera, Srikrishna,Turla, Aurélya Christelle,Hu, Xile
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supporting information
p. 14667 - 14675
(2021/09/18)
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- Method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by Ru coordination compound
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The invention discloses a method for catalyzing receptor-free dehydrogenation of primary amine to generate nitrile by a Ru coordination compound. The method comprises: adding a Ru coordination compound, an alkali, a primary amine and an organic solvent into a reaction test tube according to a mol ratio of 1:100:(100-500):1000-3000, and carrying out a stirring reaction under the condition of 80 to120 DEG C; and when gas chromatography monitors that the raw materials completely disappear, stopping the reaction, collecting the reaction solution, centrifuging the reaction solution, taking the supernatant, extracting with dichloromethane, merging the organic phases, drying, filtering, evaporating the organic solvent under reduced pressure to obtain a filtrate, and carrying out column chromatography purification on the filtrate to obtain the target product nitrile. According to the invention, the catalyst is good in activity, single in catalytic system, good in product selectivity, simple in subsequent treatment and good in system universality after the reaction is finished, has a good catalytic effect on various aryl, alkyl and heteroaryl substituted primary amines, and also has a gooddehydrogenation performance on secondary amines.
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Paragraph 0034-0039; 0285-0290
(2020/09/16)
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- Nitrile Synthesis by Aerobic Oxidation of Primary Amines and in situ Generated Imines from Aldehydes and Ammonium Salt with Grubbs Catalyst
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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
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p. 3583 - 3588
(2020/08/05)
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- Acceptorless dehydrogenation of amines to nitriles catalyzed by N-heterocyclic carbene-nitrogen-phosphine chelated bimetallic ruthenium (II) complex
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We have developed a clean, atom-economical and environmentally friendly route for acceptorless dehydrogenation of amines to nitriles by combining a new dual N-heterocyclic carbene-nitrogen-phosphine ligand R(CNP)2 (R = o-xylyl) with a ruthenium precursor [RuCl2(η6-C6H6)]2. In this system, the electronic and steric factors of amines had a negligible influence on the reaction and a broad range of functional groups were well tolerated. All of the investigated amines could be converted to nitriles in good yield of up to 99% with excellent selectivity. The unprecedented catalytic performance of this system is attributed to the synergistic effect of two ruthenium centers chelated by R(CNP)2 and a plausible reaction mechanism is proposed according to the active species found via in situ NMR and HRMS.
- Chen, Hua,Fu, Haiyan,Ji, Li,Li, Ruixiang,Nie, Xufeng,Zheng, Yanling
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p. 378 - 385
(2020/10/02)
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- Method for preparing nitrile
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The invention provides a method for preparing nitrile. Aldoxime carboxylic ester is used as a reactant to prepare a nitrile compound. The aldoxime carboxylic ester can be completely converted into corresponding nitrile under common catalysis of ferric salt and phenol within a few minutes. The method for preparing the nitrile has the advantages of gentle reaction conditions, simple and easy-to-getused reagents, cheap and environment-friendly catalyst, wide substrate application range, simple operation, rapid reaction and the like.
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Paragraph 0015
(2019/06/13)
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- OXIDATIVE CONVERSION OF ALIPHATIC ALDEHYDES TO NITRILES USING OXOAMMONIUM SALT
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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
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Paragraph 0055-0063; 0136-0142
(2019/12/10)
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- Thiocyanate radical mediated dehydration of aldoximes with visible light and air
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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
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supporting information
p. 9701 - 9704
(2019/08/15)
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- Iron and Phenol Co-Catalysis for Rapid Synthesis of Nitriles under Mild Conditions
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A mild, scalable, high yielding, and rapid route to access diverse nitriles from aldehyde oxime esters enabled by iron(III) and phenol co-catalysis has been developed. The reaction was performed at room temperature to give nitriles in excellent yield within minutes. Mechanistic studies show that the reaction may proceed through a radical process in which benzoyl aldehyde oxime is not only a substrate, but also an ancillary ligand to support iron salt in the promotion of the transformation.
- Meng, Hong,Gao, Sen,Luo, Meiming,Zeng, Xiaoming
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p. 4617 - 4623
(2019/07/15)
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- Selective Phthalimido-N-oxyl (PINO)-Catalyzed C-H Cyanation of Adamantane Derivatives
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We present a new method for the selective C(sp 3)-H cyanation of adamantane derivatives with PINO as the hydrogen abstracting reagent. A cyano radical is thereby transferred from p - toluenesulfonyl cyanide, allowing the cyanation of adamantane derivatives in up to 71% yield. The protocol presents a novel way to orthogonally functionalized adamantanes that are otherwise difficult to prepare. Mechanistic studies support the hypothesis of a radical pathway.
- Berndt, Jan-Philipp,Erb, Frederik R.,Ochmann, Lukas,Beppler, Jaqueline,Schreiner, Peter R.
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p. 493 - 498
(2019/02/26)
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- Easy Ruthenium-Catalysed Oxidation of Primary Amines to Nitriles under Oxidant-Free Conditions
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A dehydrogenation of primary amine to give the corresponding nitrile under oxidant- and base-free conditions catalysed by simple [Ru(p-cym)Cl2]2 with no extra ligand is reported. The system is highly selective for alkyl amines, whereas benzylamine derivatives gave the nitrile product together with the imine in a ratio ranging from 14:1 to 4:1 depending on the substrate. Preliminary mechanistic investigations have been performed to identify the key factors that govern the selectivity.
- Achard, Thierry,Egly, Julien,Sigrist, Michel,Maisse-Fran?ois, Aline,Bellemin-Laponnaz, Stéphane
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supporting information
p. 13271 - 13274
(2019/10/21)
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- Development and Utilization of a Palladium-Catalyzed Dehydration of Primary Amides to Form Nitriles
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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.
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supporting information
p. 6046 - 6050
(2018/09/27)
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- Mechanistic Insight Facilitates Discovery of a Mild and Efficient Copper-Catalyzed Dehydration of Primary Amides to Nitriles Using Hydrosilanes
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Metal-catalyzed silylative dehydration of primary amides is an economical approach to the synthesis of nitriles. We report a copper-hydride(CuH)-catalyzed process that avoids a typically challenging 1,2-siloxane elimination step, thereby dramatically increasing the rate of the overall transformation relative to alternative metal-catalyzed systems. This new reaction proceeds at ambient temperature, tolerates a variety of metal-, acid-, or base-sensitive functional groups, and can be performed using a simple ligand, inexpensive siloxanes, and low catalyst loading.
- Liu, Richard Y.,Bae, Minwoo,Buchwald, Stephen L.
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supporting information
p. 1627 - 1631
(2018/02/17)
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- Dehydration of Amides to Nitriles under Conditions of a Catalytic Appel Reaction
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A highly expedient protocol for a catalytic Appel-type dehydration of amides to nitriles has been developed that employs oxalyl chloride and triethylamine along with triphenylphosphine oxide as a catalyst. The reactions are usually complete in less than 10 min with only a 1 mol % catalyst loading. The reaction scope includes aromatic, heteroaromatic, and aliphatic amides, including derivatives of α-hydroxy and α-amino acids.
- Shipilovskikh, Sergei A.,Vaganov, Vladimir Yu.,Denisova, Elena I.,Rubtsov, Aleksandr E.,Malkov, Andrei V.
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supporting information
p. 728 - 731
(2018/02/09)
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- A metal-free direct C (sp3)-H cyanation reaction with cyanobenziodoxolones
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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
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supporting information
p. 1971 - 1975
(2018/03/23)
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- A practical iodine-catalyzed oxidative conversion of aldehydes to nitriles
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A simple and efficient method for the direct synthesis of nitriles from aldehydes using ammonium acetate as the nitrogen source has been developed. The reactions were performed with iodine as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.
- Fang, Chaojie,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
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p. 1484 - 1489
(2017/01/21)
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- Catalytic and oxidizing synthetic method of nitriles compound
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The invention discloses a catalytic and oxidizing synthetic method of a nitriles compound. The catalytic and oxidizing synthetic method comprises the following steps: adding reaction substrate aldehyde, NH4OAc, alkaline additives, I2 and TBHP (tert-butyl hydroperoxide) into an ethanol solvent, facilitating the reaction for 3 to 17 h at 40 to 60 DEG C, adding a sodium thiosulfate solution into a reaction solution, stirring, extracting with diethyl ether, separating to obtain an organic layer, decompressing and steaming to remove the solvent, performing the column chromatography isolation, adopting a mixed solution of ethyl acetate/petroleum ether in a volume ratio of 1: 100 as an eluent, collecting an elution solution containing a target compound, and steaming to remove the solvent, thus obtaining the product nitriles, wherein a weight ratio of the reaction substrate aldehyde to the alkaline additives to NH4OAc to I2 to TBHP is 100: (100 to 120): (120 to 160): (2 to 3): (100 to 120). The synthetic method has the beneficial effects that the operation is simple and safe, and the reaction condition is relatively moderate; and the reaction substrate is wide in application range.
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Paragraph 0053
(2017/07/23)
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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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- 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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p. 5156 - 5159
(2016/04/09)
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- A Mild TEMPO-Catalyzed Aerobic Oxidative Conversion of Aldehydes into Nitriles
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An efficient method to prepare nitriles from aldehydes using hexamethyldisilazane (HMDS) as the nitrogen source has been developed. The reactions were performed with 2,2,6,6-tetramethylpiperidine l-oxyl (TEMPO) as the catalyst, NaNO2 or TBN as the co-catalyst, and molecular oxygen as the terminal oxidant under mild conditions. A variety of aromatic, heteroaromatic, aliphatic and allylic aldehydes could be converted into their corresponding nitriles in good to excellent yields.
- Fang, Chaojie,Li, Meichao,Hu, Xinquan,Mo, Weimin,Hu, Baoxiang,Sun, Nan,Jin, Liqun,Shen, Zhenlu
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p. 1157 - 1163
(2016/04/19)
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- Nitrilation of carboxylic acids with acetonitrile catalyzed by molybdenum and vanadium complexes
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Various carbonitriles were synthesized by reaction of the corresponding carboxylic acids with acetonitrile in carbon tetrachloride in the presence of VO(acac)2and Mo(CO)6in 6 h at 150–170°C.
- Khusnutdinov,Shchadneva,Bayguzina,Mayakova, Yu. Yu.
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p. 1282 - 1286
(2016/10/26)
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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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- 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 0028; 0029
(2016/10/17)
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- Electrochemical synthesis of nitriles from aldehydes using TEMPO as a mediator
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A novel electrochemical route to generate nitriles from aldehydes under mild conditions using a catalytic amount of TEMPO (2,2,6,6-tetramethylpiperidinyl-l-oxy) as the mediator and hexamethyldisilazane as the nitrogen source in the presence of acetic acid has been developed. A variety of aromatic, heteroaromatic and aliphatic aldehydes have been converted to their corresponding nitriles in good to excellent yields. A plausible reaction mechanism is proposed based on the cyclic voltammetry, in situ FTIR and the identification of intermediates.
- Chen, Qiguo,Fang, Chaojie,Shen, Zhenlu,Li, Meichao
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- 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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- Access to nitriles from aldehydes mediated by an oxoammonium salt
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A scalable, high yielding, rapid route to access an array of nitriles from aldehydes mediated by an oxoammonium salt (4-acetylamino-2,2,6,6-tetramethylpiperidine-1-oxoammonium tetrafluoroborate) and hexamethyldisilazane (HMDS) as an ammonia surrogate has been developed. The reaction likely involves two distinct chemical transformations: reversible silyl-imine formation between HMDS and an aldehyde, followed by oxidation mediated by the oxoammonium salt and desilylation to furnish a nitrile. The spent oxidant can be easily recovered and used to regenerate the oxoammonium salt oxidant.
- Kelly, Christopher B.,Lambert, Kyle M.,Mercadante, Michael A.,Ovian, John M.,Bailey, William F.,Leadbeater, Nicholas E.
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p. 4241 - 4245
(2015/04/14)
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- Versatile and chemoselective transformation of aliphatic and aromatic secondary amides to nitriles
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Triflic anhydride in combination with 2-fluoropyridine effectively dehydrates secondary amides to afford nitriles under mild reaction conditions. The reaction is general in scope and compatible with the use of aliphatic, α,β-unsaturated, aromatic, and heteroaromatic amides bearing either secondary, tertiary, or benzylic N-alkyl groups. The reaction also shows good to excellent chemoselectivity for the secondary amide and tolerates several labile functional groups.
- Geng, Hui,Huang, Pei-Qiang
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p. 3795 - 3801
(2015/06/02)
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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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- One-pot oxidative conversion of alcohols into nitriles by using a TEMPO/PhI(OAc)2/NH4OAc system
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A direct conversion of alcohols into nitriles with 2,2,6,6- tetramethylpiperidine-1-oxyl (TEMPO), iodosobenzene diacetate, and ammonium acetate as a nitrogen source is reported. This transformation, which proceeds through an oxidation-imination-aldimine oxidation sequence in situ, has been applied to a range of aliphatic, benzylic, heteroaromatic, allylic, and propargyl alcohols. Highly chemoselective ammoxidation of primary alcohols in the presence of secondary alcohols was also achieved. Georg Thieme Verlag Stuttgart New York.
- Vatèle, Jean-Michel
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p. 1275 - 1278
(2014/06/10)
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- 3-(1-Adamantyl)furazans
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The reactivity of 3-(1-adamantyl)-4-aminofurazan was studied. Upon treatment with oxidizing reagents the amino group is oxidized to azo, azoxy, and nitro groups. The nitration of 3-(1-adamantyl)-4-aminofurazan with nitric acid provided the corresponding n
- Sheremetev,Kozeev,Aleksandrova,Struchkova,Suponitsky
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p. 1358 - 1369
(2014/01/17)
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- Photoinduced direct cyanation of C(sp3)-H bonds
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A general and practical synthetic protocol for the direct transformation of unreactive C(sp3)-H bonds to C(sp3)-CN bonds has been developed. The homolytic cleavage of the C-H bond is initiated by photo-excited benzophenone, and the resulting carbon radical subsequently reacts with tosyl cyanide to afford the corresponding nitrile in a highly efficient manner. The present methodology is widely applicable to various starting materials including ethers, alcohols, amine derivatives, alkanes, and alkylbenzenes. This newly developed C-H cyanation protocol provides a powerful tool for selective one-carbon elongation for the construction of architecturally complex molecules. Georg Thieme Verlag Stuttgart - New York.
- Hoshikawa, Tamaki,Yoshioka, Shun,Kamijo, Shin,Inoue, Masayuki
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p. 874 - 887
(2013/05/09)
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- One-pot transformation of carboxylic acids into nitriles
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A variety of aromatic and aliphatic carboxylic acids were smoothly converted into the corresponding nitriles in good yields in a one-pot procedure by treatment with ethyl iodide/K2CO3/18-crown-6, followed by sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), and finally treatment with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH), and aqueous ammonia. This method is useful for the conversion of various aromatic and aliphatic carboxylic acids into the corresponding nitriles in a one-pot procedure. A variety of aromatic and aliphatic carboxylic acids were smoothly converted into the corresponding nitriles in good yields in a one-pot procedure by treatment with ethyl iodide/K2CO3/18-crown-6, followed by sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), and finally treatment with molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH), and aqueous ammonia. Copyright
- Miyagi, Kotaro,Moriyama, Katsuhiko,Togo, Hideo
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p. 5886 - 5892
(2013/09/23)
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- An efficient zinc-catalyzed dehydration of primary amides to nitriles
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In the present study, the zinc-catalyzed dehydration of a variety of amides with N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) as a dehydration reagent into the corresponding nitriles has been examined in detail. With the straightforward and commercially available zinc(II)triflate as the precatalyst and MSTFA, an excellent system has been established to afford nitriles in excellent yields and chemoselectivities. After investigation of reaction conditions and the scope and limitations, several efforts were carried out to understand the reaction mechanism.
- Enthaler, Stephan,Inoue, Shigeyoshi
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experimental part
p. 169 - 175
(2012/03/26)
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- First synthesis of α-(3-R-1-adamantyl)sulfoacetic acids and their derivatives
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By sulfonation of 3-R-1-adamantylacetic acids 1 with H2SO 4 in trifluoroacetic anhydride (TFAA), the previously unknown α-(3-R-adamantyl)sulfoacetic acids 2 were obtained. In the case of 1-adamantylacetic acid 1a, the use of ~1 equiv of H2SO 4 led to only 1-adamantylacetic acid 2a, while with an excess of the reactant the hydroxylation of the adamantane tertiary C-H bond also occurred. It is assumed that the bis(trifluoroacetyl)sulfate generated in situ from H 2SO4 and TFAA is responsible both for sulfonation and oxidation steps. The adamantylated sulfoacetic acids were used for the preparation of a series of derivatives by modifications of carboxylic, sulfonic acid, and tertiary adamantane OH-groups. Due to the use of TFAA as a medium, a series of derivatives of sulfoacetic acids was obtained directly from acids 1 within one-pot procedures. Some of the synthesized compounds possess anti-HSV activity.
- Shmailov, Alexander,Alimbarova, Ludmila,Vatsouro, Ivan,Tafeenko, Viktor,Shokova, Elvira,Kovalev, Vladimir
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experimental part
p. 4765 - 4772
(2012/07/30)
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- Straightforward uranium-catalyzed dehydration of primary amides to nitriles
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Easy for U! The efficient uranium-catalyzed dehydration of a variety of primary amides, using N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) as a dehydration reagent, to the corresponding nitriles has been investigated. With this catalyst system, extraordinary catalyst activities and selectivities were feasible (see scheme; DME=dimethoxyethane). Copyright
- Enthaler, Stephan
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supporting information; experimental part
p. 9316 - 9319
(2011/09/16)
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- Copper-catalyzed dehydration of primary amides to nitriles
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In the present study we introduce a copper-catalyzed protocol for the dehydration of primary amides to their corresponding nitriles applying N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA) as silylation reagent. For that purpose investigations of various reaction parameters (copper source, solvent, temperature, MSTFA and copper loading) have been carried out to find suitable reaction conditions. Simple copper(I) chloride (2.5 mol%) and MSTFA (2.0 equiv) in toluene allow for the straightforward synthesis of a variety of nitriles (15 examples).
- Enthaler, Stephan,Weidauer, Maik
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experimental part
p. 1079 - 1085
(2012/06/18)
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- Photochemically induced radical transformation of C(sp3)-H bonds to C(sp3)-CN bonds
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A general protocol for direct transformation of unreactive C(sp 3)-H bonds to C(sp3)-CN bonds has been developed. The C-H activation was effected by photoexcited benzophenone, and the generated carbon radical was subsequently trapped with tosyl cyanide to afford the corresponding nitrile in a highly efficient manner. The present methodology is widely applicable to versatile starting materials and, thus, serves as a powerful tool for selective one-carbon elongation for construction of architecturally complex molecules.
- Kamijo, Shin,Hoshikawa, Tamaki,Inoue, Masayuki
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supporting information; experimental part
p. 5928 - 5931
(2011/12/21)
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- Facile transformation of esters to nitriles
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Various esters were efficiently converted into the corresponding nitriles in good yields by the treatment with sodium diisobutyl-tert-butoxyaluminium hydride (SDBBA-H), followed by treatment with molecular iodine in aq ammonia. The present one-pot method is very efficient and practical for the conversion of various aromatic and aliphatic esters into the corresponding nitriles.
- Suzuki, Yusuke,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 7956 - 7962
(2011/11/07)
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- Direct transformation of N,N-disubstituted amides and isopropyl esters to nitriles
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Various N,N-dimethyl amides, N-methoxy-N-methyl amides, and isopropyl esters were smoothly transformed into the corresponding nitriles in good to moderate yields by the treatment with diisobutylaluminium hydride, followed by treatment with molecular iodine in aq ammonia. The present reactions are novel one-pot and practical methods for the transformation of N,N-disubstituted amides and isopropyl esters into nitriles, through the formation of hemiaminal O-AlBu2 and hemiacetal O-AlBu2, respectively.
- Suzuki, Yusuke,Yoshino, Takumi,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 3809 - 3814
(2011/06/25)
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- Transformation of aromatic bromides into aromatic nitriles via formations of grignard reagents and their DMF adducts
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Various aromatic bromides were efficiently transformed into the corresponding aromatic nitriles in good yields via the formations of Grignard reagents and subsequently N,N-dimethyl formamide (DMF) adducts, followed by treatment with molecular iodine (I2) in aq NH3 at room temperature. The present reaction is an easy and practical method for the preparation of aromatic nitriles from aromatic bromides with less toxic reagents, such as Mg, DMF, I2, and aq NH3.
- Ishii, Genki,Moriyama, Katsuhiko,Togo, Hideo
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experimental part
p. 2404 - 2406
(2011/05/16)
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- Supported monomeric vanadium catalyst for dehydration of amides to form nitriles
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Monomeric vanadium oxide species is created on the surface of hydrotalcite (V/HT), which acts as a reusable solid catalyst for the highly efficient dehydration of amides into the corresponding nitriles.
- Sueoka, Shoichiro,Mitsudome, Takato,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
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supporting information; experimental part
p. 8243 - 8245
(2010/12/25)
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- Metal-free one-pot oxidative conversion of benzylic alcohols and benzylic halides into aromatic amides with molecular iodine in aq ammonia, and hydrogen peroxide
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Various primary alcohols, particularly benzylic alcohols, could be converted into the corresponding aromatic amides in good yields in a one-pot manner by treatment with molecular iodine in aq. NH3, followed by reaction with ~30% aq H2O2. Similarly, various benzylic halides could be also converted into the corresponding aromatic amides in good yields in a one-pot manner by treatment with molecular iodine in aq NH3, followed by reaction with ~30% aq H2O 2. The present reactions involve the metal-free one-pot oxidative conversion of benzylic alcohols and benzylic halides into the corresponding aromatic amides, respectively.
- Ohmura, Ryosuke,Takahata, Misato,Togo, Hideo
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experimental part
p. 4378 - 4381
(2010/09/12)
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- Generation of iminyl copper species from α-azido carbonyl compounds and their catalytic C-C bond cleavage under an oxygen atmosphere
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Figure presented A copper-catalyzed reaction of α-azidocarbonyl compounds under an oxygen atmosphere is reported where nitriles are formed via C-C bond cleavage of a transient iminyl copper intermediate. The transformation is carried out by a sequence of denitrogenative formation of iminyl copper species from α-azidocarbonyl compounds and their C-C bond cleavage, where molecular oxygen (1 atm) is a prerequisite to achieve the catalytic process and one of the oxygen atoms of O2 was found to be incorporated into the β-carbon fragment as a carboxylic acid.
- Chiba, Shunsuke,Zhang, Line,Ang, Gim Yean,Hui, Benjamin Wei-Qiang
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supporting information; experimental part
p. 2052 - 2055
(2010/07/04)
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- New catalytic properties of iron complexes: Dehydration of amides to nitriles
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Various iron carbonyl clusters such as Fe2(CO)9 or [Et3NH][HFe3(CO)11] are shown to catalyze the dehydration of amides into the corresponding nitriles in the presence of silanes in high yields; this novel protocol showed good functional group tolerance and wide substrate scope.
- Zhou, Shaolin,Addis, Daniele,Das, Shoubhik,Junge, Kathrin,Beller, Matthias
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supporting information; experimental part
p. 4883 - 4885
(2009/12/08)
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- Radical cyanation of alkyl iodides with diethylphosphoryl cyanide
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The β-elimination of an organophosphoryl group from an iminyl radical is observed for the first time. On the basis of this finding, radical cyanation of alkyl iodides is achieved by using diethylphosphoryl cyanide. Georg Thieme Verlag Stuttgart.
- Chang, Ho Cho,Jin, Young Lee,Kim, Sunggak
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experimental part
p. 81 - 84
(2009/05/30)
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- Iminyl radicals from α-azido o-iodoanilides via 1,5-H transfer reactions of aryl radicals: New transformation of α-azido acids to decarboxylated nitriles
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(Chemical Equation Presented) The radical reaction of tributyltin hydride with o-iodo-N-methylanilides derived from α-azido acids provides an excellent access to α-(aminocarbonyl)iminyl radicals through 1,5-hydrogen transfer reaction of initially formed aryl radicals followed by β-elimination of dinitrogen from ensuing α-azido-α- (aminocarbonyl)alkyl radicals. The outcoming iminyls display a peculiar tendency to form corresponding nitriles by β-elimination of aminocarbonyl radicals.
- Bencivenni, Giorgio,Lanza, Tommaso,Leardini, Rino,Minozzi, Matteo,Nanni, Daniele,Spagnolo, Piero,Zanardi, Giuseppe
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p. 4721 - 4724
(2008/09/21)
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