- Electrochemically promoted oxidative α-cyanation of tertiary and secondary amines using cheap AIBN
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The electrochemical α-cyanation of tertiary and secondary amines has been developed by using a cheap cyanide reagent, azobisisobutyronitrile (AIBN). The CN radical, generated throughn-Bu4NBr-meidated electrochemical oxidation, participates in a novel α-cyanation reaction under exogenous oxidant-free conditions.
- Cai, Tian-Cheng,Gui, Qing-Wen,Hu, Wenxia,Li, Qiang,Liu, Xiaoying,Teng, Fan,Wang, Xiaoli,Xiong, Zhi-Yuan,Yu, Jialing
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supporting information
p. 8254 - 8258
(2021/10/12)
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- A carbon dioxide-promoted three-component Strecker reaction
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A three-component Strecker reaction of aldehydes, amines and KCN has been performed for the first time in supercritical carbon dioxide. In the proposed procedure, non-toxic and non-flammable carbon dioxide acts not only as an environmentally benign reaction medium but also as a reaction promoter via in situ formation of carbonic acid which provides a gradual release of the true cyanating agent (HCN) from available KCN. The reaction conditions (pressure, temperature, and concentrations of reagents) were optimized, and various aromatic and aliphatic amines and aldehydes were transformed into valuable α-amino nitriles including prospective pharmacological substances. The equimolar amount of used cyanogen reagent, carrying out the process in a sealed autoclave in a 'green' solvent medium under mild conditions (90 bar, 35 °C) along with the high yields of products and the scalability of the developed procedure make it suitable for sustainable industrial applications. This journal is
- Fauziev, Ruslan V.,Ivanov, Roman E.,Kuchurov, Ilya V.,Zlotin, Sergei G.
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p. 10137 - 10144
(2021/12/24)
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- One-Pot Synthesis of α-Amino Nitrile Units through Alkylative Strecker Cyanation from Formamides
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In this work, we describe the one-pot synthesis of α-amino nitrile units by the concomitant addition of alkyl (or aryl) Grignard reagents and TMS cyanide through alkylative Strecker cyanation from readily available formamides. The reaction is broad in sco
- Yu, Bao,Bodinier, Florent,Saague-Tenefo, Maximiliene,Gerardo, Patrice,Ardisson, Janick,Lannou, Marie-Isabelle,Sorin, Geoffroy
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p. 3634 - 3640
(2021/07/22)
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- Strecker reactions with hexacyanoferrates as non-toxic cyanide sources
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The Strecker reaction is the most widely applied three-component reaction. Although highly useful for the preparation of α-amino nitriles, α-amino acids, hydantoins and numerous related compounds, the need for the application of toxic sources of HCN limits its application in both academic and industrial settings. Here, we present a facile protocol for Strecker reactions using a mixture of potassium ferri- and ferrocyanides as a non-toxic substitute.
- Grundke, Caroline,Opatz, Till
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supporting information
p. 2362 - 2366
(2019/05/17)
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- A unique combination of KI/ZnFe2O4 as a catalyst for oxidative Strecker reaction
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α-Aminonitriles as key intermediates for the preparation of α-amino acid derivatives, amides, diamines, peptides, proteins and heterocycles were synthesized through methylarene oxidation in the Strecker reaction using a unique combination of KI/ZnFe2O4 as the best catalyst and aqueous tert-butyl hydroperoxide as oxidant. A wide range of amines and methylarenes were converted to the corresponding products. Operational simplicity, short reaction time and recyclability of the catalyst are advantages of this protocol.
- Ghandi, Leila,Kazemi Miraki, Maryam,Karimi, Meghdad,Radfar, Iman,Heydari, Akbar
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- Straightforward α-Amino Nitrile Synthesis Through Mo(CO)6-Catalyzed Reductive Functionalization of Carboxamides
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The selective reduction of amides into an intermediate hemiaminal catalyzed by Mo(CO)6 together with the inexpensive and easy to handle TMDS (1,1,3,3-tetramethyldisiloxane) as reducing agent, followed by subsequent trapping of the hemiaminal with a cyanide source, allows for the straightforward synthesis of α-amino nitriles. The methodology presented here, displays high levels of chemoselectivity allowing for the reduction of amides in the presence of functional groups such as ketones, imines, aldehydes, and acids, which affords a simple route for the synthesis of α-amino nitriles with a broad scope of functionalities in high yields. Furthermore, the applicability of this methodology is demonstrated by scale up experiments and by derivatization of the target compounds into synthetically interesting products. The selective cyanation is successfully applied in late stage functionalizations of amide containing drugs and prolinol derivatives.
- Trillo, Paz,Slagbrand, Tove,Adolfsson, Hans
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p. 12347 - 12351
(2018/09/10)
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- Magnetically separable g-C3N4 hybrid nanocomposite: Highly efficient and eco-friendly recyclable catalyst for one-pot synthesis of α-aminonitriles
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A magnetically separable graphitic carbon nitride nanocomposite (Fe3O4/g-C3N4) as a catalyst for the three-component condensation reactions of carbonyl compounds, amines and trimethylsilylcyanide was thoroughly investigated. The reaction of these three components was found to be efficient, economical and green and took place in the presence of a catalytic amount of the magnetically separable catalyst to yield the corresponding α-aminonitriles in good to excellent yields. The prepared nanocomposite was characterized using scanning electron microscopy and energy-dispersive X-ray and Fourier transform infrared spectroscopies. The nanocomposite was also found to be reusable could be recovered easily and reused several times without distinct deterioration in its catalytic activity.
- Azizi, Najmedin,Farhadi, Elham
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- Expeditious and efficient synthesis of Strecker's α-aminonitriles catalyzed by sulfated polyborate
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A straightforward, mild, efficient, and environmentally benign protocol for a three-component Strecker reaction of aldehydes or ketones, amines, and trimethylsilyl cyanide catalyzed by sulfated polyborate has been described to afford α-aminonitriles under solvent-free reaction conditions. The major advantages of the present method are excellent yields, shorter reaction time, simple experimental procedure, easy workup procedure, recyclability of the catalyst, solvent-free reaction conditions and ability to tolerate a variety of functional groups which gives economical as well as ecological rewards.
- Indalkar, Krishna S.,Khatri, Chetan K.,Chaturbhuj, Ganesh U.
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supporting information
p. 2144 - 2148
(2017/05/10)
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- Mechanochemical Strecker Reaction: Access to α-Aminonitriles and Tetrahydroisoquinolines under Ball-Milling Conditions
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A mechanochemical version of the Strecker reaction for the synthesis of α-aminonitriles was developed. The milling of aldehydes, amines, and potassium cyanide in the presence of SiO2gave the corresponding α-aminonitriles in good to high yields. The high efficiency of the mechanochemical Strecker-type multicomponent reaction allowed the one-pot synthesis of tetrahydroisoquinolines after a subsequent internal N-alkylation reaction.
- Hernández, José G.,Turberg, Mathias,Schiffers, Ingo,Bolm, Carsten
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supporting information
p. 14513 - 14517
(2016/10/03)
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- Propylphosphonic anhydride (T3P) catalyzed one-pot synthesis of α-aminonitriles
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Abstract The Strecker reaction was performed via a one-pot three component condensation of hetero aromatic/aromatic aldehydes, secondary amines and trimetylsilyl cyanide in the presence of propylphosphonic anhydride (T3P) to accomplish the corresponding α-aminonitriles. The main advantages of this method are very short reaction time and excellent yields.
- Reddy, Sirigireddy Sudharsan,Reddy, Bhoomireddy Rajendra Prasad,Reddy, Peddiahgari Vasu Govardhana
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p. 739 - 743
(2015/08/03)
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- Synergistic effect of a bis(proazaphosphatrane) in mild palladium-catalyzed direct α-arylations of nitriles with aryl chlorides
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The effect of a bis(proazaphosphatrane) ligand on the palladium-catalyzed direct α-arylation of nitriles with various aryl chlorides under mild conditions is reported. Comparisons of the catalytic properties of this ligand with those of three related mono(proazaphosphatrane)s under the same reaction conditions revealed that bis(proazaphosphatrane) displayed a synergistically enhanced activity. In the presence of the bis(proazaphosphatrane) ligand, ethyl cyanoacetate and primary as well as secondary nitriles were efficiently coupled with a wide variety of aryl chlorides that contained electron-rich, electron-poor, and electron-neutral groups.
- Han Kim, So,Jang, Wonseok,Kim, Min,Verkade, John G.,Kim, Youngjo
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p. 6025 - 6029
(2015/03/30)
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- Zn(OAc)2·2H2O-catalyzed one-pot efficient synthesis of α-amino nitriles
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A mild, efficient one-pot three component strecker reaction involving electronically and structurally divergent aldehydes, amines and trimethly silyl cyanide in chloroform as solvent at room temperature was accomplished in moderate to excellent yields using an inexpensive and readily available catalyst, Zn(OAc)2.2H2O.
- Reddy, V. Venkata Rami,Saritha,Ramu,Varala, Ravi,Jayashree
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p. 7439 - 7442
(2015/04/22)
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- Redox-neutral α-cyanation of amines
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α-Aminonitriles inaccessible by traditional Strecker chemistry are obtained in redox-neutral fashion by direct amine α-cyanation/N-alkylation or alternatively, α-aminonitrile isomerization. These unprecedented transformations are catalyzed by simple carboxylic acids.
- Ma, Longle,Chen, Weijie,Seidel, Daniel
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p. 15305 - 15308
(2012/10/29)
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- Sulfated tungstate: A green catalyst for Strecker reaction
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A straightforward, mild, efficient, and general method has been developed for the synthesis of α-aminonitriles via Strecker reaction starting from aldehydes or ketones, amines, and trimethylsilyl cyanide in the presence of sulfated tungstate as a heterogeneous mild solid acid catalyst at room temperature and solvent free condition. The developed method has been successfully applied for the synthesis of a wide range of α-aminonitriles with variable functionality.
- Pathare, Sagar P.,Akamanchi, Krishnacharya G.
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experimental part
p. 871 - 875
(2012/03/08)
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- Catalyst-free Strecker reaction in water: A simple and efficient protocol using acetone cyanohydrin as cyanide source
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A simple, convenient, and practical method for the synthesis of α-amino nitriles through a one-pot, three-component Strecker reaction of a carbonyl compound, amine, and acetone cyanohydrin in water has been developed. Reactions proceed very efficiently without any catalyst at room temperature with high chemoselectivity and give, in some cases, the expected α-amino nitrile pure after direct separation from water. The protocol is particularly efficient for both aliphatic and aromatic aldehydes, and cyclic ketones, in combination with primary and secondary amines. An unusual application of the Strecker reaction to 1,2-diamines to obtain 1,2-diamino nitriles, and to cyclic secondary amines is reported. Copyright
- Galletti, Paola,Pori, Matteo,Giacomini, Daria
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experimental part
p. 3896 - 3903
(2011/09/12)
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- Heterogeneously catalysed Strecker-type reactions using supported Co(ii) catalysts: Microwave vs. conventional heating
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A range of α-aminonitriles could be efficiently prepared from various aldehydes/ketones and primary or secondary amines using a highly active and stable Co(ii) complex supported on different mesoporous supports at both room temperature and low temperature microwave irradiation under solventless conditions. Catalysts were also highly reusable under the investigated reaction conditions and could be reused at least 10 times without loss of catalytic activity. The Royal Society of Chemistry.
- Rajabi, Fatemeh,Nourian, Saghar,Ghiassian, Sara,Balu, Alina M.,Saidi, Mohammad Reza,Serrano-Ruiz, Juan Carlos,Luque, Rafael
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supporting information; experimental part
p. 3282 - 3289
(2011/12/15)
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- Ga-TUD-1: A new heterogeneous mesoporous catalyst for the solventless expeditious synthesis of α-aminonitriles
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The high surface area three-dimensional porous catalyst has been prepared and characterized by TEM, BET S.A, low angle XRD, 29Si MAS NMR, NH3 TPD techniques. A simple, efficient and rapid method for the green synthesis of α-aminonitriles has been demonstrated over a new mesoporous gallosilicate catalyst Ga-TUD-1. The solventless technique has been applied for the synthesis of a range of compounds with variable functionality with excellent yield and selectivity. The catalyst has been recycled four times with reproducible yield.
- Karmakar, Bikash,Sinhamahapatra, Apurba,Panda, Asit Baran,Banerji, Julie,Chowdhury, Biswajit
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experimental part
p. 111 - 117
(2011/10/13)
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- Efficient Co(ii) heterogeneously catalysed synthesis of α-aminonitriles at room temperature via Strecker-type reactions
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An environmentally friendly and highly active mesoporous Co(ii) complex on mesoporous SBA-15 material could be used as an easily recoverable catalyst for the synthesis of α-aminonitriles from a wide range of aldehydes/ketones and primary or secondary amines with good to excellent conversions yields at room temperature under solventless conditions. The catalyst can be recovered by simple filtration and could be reused at least 10 times without loss of catalytic activity.
- Rajabi, Fatemeh,Ghiassian, Sara,Saidi, Mohammad Reza
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supporting information; experimental part
p. 1349 - 1352
(2010/09/15)
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- K2PdCl4 catalyzed efficient multicomponent synthesis of α-aminonitriles in aqueous media
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An efficient, mild and environmentally friendly method has been developed for the Strecker reaction to synthesize α-aminonitriles in the presence of K2PdCl4 as a catalyst. The three-component one-pot condensation of an aldehyde, amine and trimethylsilyl cyanide proceeded smoothly in water to afford the corresponding product in high yield with short reaction times. Crown Copyright
- Karmakar, Bikash,Banerji, Julie
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scheme or table
p. 2748 - 2750
(2010/07/06)
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- Superparamagnetic iron oxide as an efficient catalyst for the one-pot, solvent-free synthesis of α-aminonitriles
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Superparamagnetic Fe3O4 is shown to act as a very efficient catalyst for the one-pot, three-component synthesis of α-aminonitriles from aldehydes, amines, and TMSCN. The catalyst is easily recovered by the use of an external magnet and reused in several reactions without any noticeable loss of activity. The products are obtained rapidly at room temperature in good purity upon separation of the catalyst and evaporation of the volatiles of the reaction mixture.
- Mojtahedi, Mohammad M.,Saeed Abaee,Alishiri, Tooba
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experimental part
p. 2322 - 2325
(2009/09/06)
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- Sulfamic acid catalyzed direct condensation of aldehydes, amines, and TMSCN to α-aminonitriles at ambient temperature
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A simple and efficient method has been developed for the synthesis of α-aminonitriles by a one-pot three-component condensation of aldehydes, amines, and trimethylsilyl cyanide in the presence of a catalytic amount of sulfamic acid at room temperature. Georg Thieme Verlag Stuttgart.
- Li, Zhenjiang,Sun, Yingjie,Ren, Xinghua,Wei, Ping,Shi, Yuhu,Ouyang, Pingkai
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p. 803 - 805
(2007/12/25)
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- Preparation of non-racemic single-stereocentre α-aminonitriles and a study of their fate in Bruylants reactions
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A number of chiral carboxamide dehydration methods were investigated for the preparation of four representative enantiomerically enriched α-aminonitriles possessing only one stereogenic centre; best results were observed using Burgess' salt (yield up to 87%, er up to 92/8) or the trifluoroacetic anhydride-triethylamine combination (yield up to 98%, er up to 86/14). Two of the aminonitriles thus obtained were subjected to Bruylants reactions with a methyl Grignard reagent to furnish the corresponding tertiary amines; these products, along with any unreacted starting materials, were obtained essentially in racemic form. In accord with the accepted mechanism for this reaction, a magnesium species is implicated in the formation of an iminium, the common intermediate for both chemical transformation and racemization processes.
- Beaufort-Droal, Virginie,Pereira, Elisabeth,Théry, Vincent,Aitken, David J.
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p. 11948 - 11954
(2007/10/03)
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- [HP(HNCH2CH2)3N]NO3: An efficient homogeneous and solid-supported promoter for aza and thia-Michael reactions and for Strecker reactions
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In the presence of a catalytic amount of an azaphosphatrane nitrate salt, amines and thiols react readily with Michael acceptors. The salt is also an efficient promoter for the one pot synthesis of α-amino and α-amidonitriles. By anchoring the salt to Merrifield Resin, a reusable heterogeneous catalyst is obtained for these reactions. Evidence is presented for catalysis being attributable solely to the NO3- ion.
- Fetterly, Brandon M.,Jana, Nirmal K.,Verkade, John G.
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p. 440 - 456
(2007/10/03)
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- One-pot, solvent-free synthesis of α-aminonitriles under catalysis by magnesium bromide ethyl etherate
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A three-component, efficient, and facile procedure has been developed for the synthesis of α-aminonitriles from aldehydes, amines, and trimethylsilyl cyanide using a catalytic amount of magnesium bromide ethyl etherate in the absence of solvent. Rapid formation of products is observed at room temperature in a one-pot procedure under very mild conditions giving excellent yields of the title compounds.
- Mojtahedi, Mohammad M.,Abaee, M. Saeed,Abbasi, Hasean
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p. 429 - 432
(2007/10/03)
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- Aromatic organozinc reagents as nucleophiles in the α-arylation of piperidine and tetrahydropyran
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The arylation at the α-position of piperidine derivatives is achieved in good yield using aromatic organozinc reagents and either 2-methoxylated or α-cyanated piperidine. Oxygen-containing heterocycles such as 2-methoxy-tetrahydropyran reacts in a same manner to yield efficiently 2-arylated tetrahydropyran.
- Le Gall, Erwan,Gosmini, Corinne,Troupel, Michel
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p. 455 - 458
(2007/10/03)
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- Silica sulfuric acid catalyzed one-pot synthesis of α-aminonitriles
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A simple and efficient method has been developed for the synthesis of α-aminonitriles by a one-pot three-component condensation of aldehydes, amines, and trimethylsilyl cyanide in the presence of a catalytic amount of silica sulfuric acid at room temperature. The silica sulfuric acid is reusable and could be applied in subsequent reactions with comparable activity. Georg Thieme Verlag Stuttgart.
- Chen, Wei-Yi,Lu, Jun
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p. 2293 - 2296
(2007/10/03)
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- Synthesis α-Aminonitrile through Anodic Cyanation of N-Benzylpiperidine
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Six-membered cyclic α-aminonitrile has been prepared from anodic cyanation of N-benzylpiperidine. Good yields of α-aminonitriles could be obtained through potentiostatic electrolysis under different conditions. The results also explain why high yield α-aminonitriles could not be obtained under constant current electrolysis.
- Zhao, Ping,Yin, Ying-Wu
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p. 157 - 160
(2007/10/03)
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- Lithium Perchlorate Mediated Three-Component Preparation of α-Aminonitriles under Solvent-Free Conditions
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A three-component reaction between aliphatic or aromatic aldehyde, an amine and trimethylsilyl cyanide mediated by solid LiClO4, gave amino nitriles in good to excellent yields. The reaction proceeded smoothly under solvent-free conditions without any side products.
- Azizi, Najmedin,Saidi, Mohammad R.
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p. 1207 - 1214
(2007/10/03)
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- La(O-i-Pr)3 catalyzed three-component condensation reaction: A convenient synthesis of N,N-dialkyl-α-cyanoamines
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In the presence of 10 mol% of La(O-i-Pr)3, a three-component condensation reaction of aldehyde, secondary amine and trimethylsilylcyanide proceeded smoothly to afford N,N-dialkyl-α-cyanoamine in good yield.
- Sun, Peipei,Qian, Changtao,Wang, Limin,Chen, Ruifang
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p. 2973 - 2978
(2007/10/03)
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- Application of Electro-Oxidative α-Cyanation of Aza-Rings to the Synthesis of Gephyrotoxin 223AB
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Six and five-membered cyclic α-cyanoamines have been prepared efficiently from N-benzylpiperidine and N-benzylpyrrolidine.These α-cyanoamines were successfully used in the synthesis of gephyrotoxin 223AB.
- Yang, Teng-Kuei,Yeh, Shun-Tsai,Lay, Yen-Yuan
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p. 1711 - 1716
(2007/10/02)
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- Steric Inhibition of Synergistic Radical Stabilizing Effects
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Equilibrium acidities in Me2SO for 14 α-N-morpholinyl-, 6 α-N-piperidinyl-, and 7 α-cyclohexylarylacetonitriles and the oxidation potentials of their conjugate bases have been determined.The increased pKHA values by about 2 units observed in these systems, relative to the corresponding arylacetonitriles, is ascribed to the presence of increased steric constraints in the anions.Hammett plots revealed larger ρ values than for arylacetonitriles (6-7 versus 5.5), pointing to an increased negative charge density on the benzylic carbon atoms in the anions.A plot of anion oxidation potentials, Eox(A-), versus pKHA for the α-N-morpholinylarylacetonitriles was linear with a slope near unity, showing that remote substituents for the most part have very little effect on radical stabilities.A 5 and 6 kcal/mol lowering of the BDE of the acidic C-H bond caused by replacing the cyclohexyl group in α-cyclohexylphenylacetonitrile by α-N-morpholinyl or N-piperidinyl groups, respectively, is attributed to the strong donor properties of these amino functions.The effects are only about one-third as large, however, as similar effects in R2NCH2COPh, where the steric effect of Ph is absent and a synergistic effect is believed to be operative.
- Bordwell, F. G.,Bausch, Mark J.,Cheng, Jin-Pei,Cripe, Thomas H.,Lynch, Tsuei-Yun,Mueller, Mark E.
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- REGIOSPECIFIC FUNCTIONALISATION OF CARBON ATOMS α TO HETEROCYCLIC NITROGEN
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Previously, methods have been devised to functionalise the two endocyclic C atoms α to the piperidine N.In the present study we show that a nitrile substituent can be introduced also to the exocyclic α-C, making the centre either nucleo- or electrophilic in subsequent transformations.NMR studies have been used to gain knowledge of the mechanistic aspects leading to the observed regiospecificity.The generality of the method, along with the ease of operation, high yields and regiospecificity, make it highly versatile for synthetic purposes.
- Koskinen, Ari,Lounasmaa, Mauri
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p. 1627 - 1634
(2007/10/02)
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- Orthoamides, XXXIII.-Contributions to the Chemistry of Bis(dialkylamino)acetonitriles
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Bis(dialkylamino)acetonitriles 2a-d react with acetyl chloride and antimony pentachloride to give N,N,N',N'-tetraalkylformamidinium hexachloroantimonates 5a-d.Reaction of p-nitrophenol with 2a,b affords N,N,N',N'-tetraalkylformamidinium salts 8a,b, while reaction of aromatic aldehydes 11 with compounds 2 gives aryl(dialkylamino)acetonitriles 12.Phenyl isothiocyanate reacts with the nitriles 2a-c to give 1:1 adducts for which the structure of N,N,N',N'-tetraalkylformamidinium cyano-N-(phenyl)thioformamidates 19 is proposed.N,N,N',N'-Tetraalkylformamidinium p-toluenesulfonates 30a,b have been prepared from nitriles 2a,b and methyl p-toluoenesulfonate (28).Alkylation of 2c with 28 at higher temperatures affords 1,1-dimethylpiperidinium p-toluoenesulfonate (34) and a small amount (1-piperidinyl)malonodinitrile (33).The nitrile 2a reacts with CH acidic compounds such as ethyl cyanoacetate, malonodinitrile and benzyl cyanide to form the enamines 38.
- Kantlehner, Willi,Baur, Richard,Bredereck, Hellmut
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p. 358 - 371
(2007/10/02)
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