- Iron-Catalyzed α-C-H Cyanation of Simple and Complex Tertiary Amines
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This manuscript details the development of a general and mild protocol for the α-C-H cyanation of tertiary amines and its application in late-stage functionalization. Suitable substrates include tertiary aliphatic, benzylic, and aniline-type substrates and complex substrates. Functional groups tolerated under the reaction conditions include various heterocycles and ketones, amides, olefins, and alkynes. This broad substrate scope is remarkable, as comparable reaction protocols for α-C-H cyanation frequently occur via free radical mechanisms and are thus fundamentally limited in their functional group tolerance. In contrast, the presented catalyst system tolerates functional groups that typically react with free radicals, suggesting an alternative reaction pathway. All components of the described catalyst system are readily available, allowing implementation of the presented methodology without the need for lengthy catalyst synthesis.
- Yilmaz, Ozgur,Dengiz, Cagatay,Emmert, Marion H.
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supporting information
p. 2489 - 2498
(2021/02/06)
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- Iron-catalyzed reductive strecker reaction
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Strecker reaction is widely applied for the synthesis of amino acids from aldehydes, amines and cyanides. Herein, we report the FeI2-catalyzed reductive Strecker type reaction of formamides instead of aldehydes to produce amino acetonitriles. The challenging capture of carbinolamine intermediates by CN? was achieved via Fe catalysis. This approach afforded better yields than the use of Ir- or Rh-catalysts. The application ability of this methodology is demonstrated by 1) one-pot construction of (13C labeled) complex molecules from CO2 via amino acetonitrile intermediates and 2) convenient production of homologated carboxylic acids from aldehydes.
- Yan, Fachao,Huang, Zijun,Du, Chen-Xia,Bai, Jian-Fei,Li, Yuehui
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p. 188 - 194
(2021/02/03)
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- Method for preparing alpha-aminonitrile and product and application thereof
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The invention discloses a method for preparing alpha-aminonitrile, which comprises the following steps: by using tertiary amine and benzoyl cyanide as reactants, carrying out visible light irradiationin an organic solvent under the condition of oxygen or
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Paragraph 0061-0065
(2021/02/24)
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- Nano cobalt-copper ferrite catalyzed regioselective α-C(sp3)–H cyanation of amines: Secondary, tertiary, and drug molecules
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Oxidative cyanation of sp3C–H bonds at the α position of amines was achieved using CoCuFe2O4 as a catalyst and NaCN as an inexpensive cyanide source at room temperature. CoCuFe2O4 was found to be an active catalyst for Csp [3]-Csp coupling, efficiently delivering valuable α-aminonitriles from tertiary/secondary amines in good yields. The corresponding products were obtained with high selectivity toward α position. In addition, functional group tolerance offered the opportunity for application in late-stage functionalization of biologically active molecules. This transformation proceeds convenient on a gram-scale, and the catalyst can be reused for several runs with consistent catalytic activity.
- Heidarian, Mahdi,Moghaddam, Firouz Matloubi,Pourkaveh, Raheleh
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- Electron Donor-Acceptor Complex-Initiated Photochemical Cyanation for the Preparation of α-Amino Nitriles
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An electron donor-acceptor complex-initiated α-cyanation of tertiary amines has been described. The reaction protocol provides a novel method to synthesize various α-amino nitriles under mild conditions. The reaction can proceed smoothly without the presence of photocatalysts and transition metal catalysts, and either oxidants are unnecessary or O2 is the only oxidant. The practicality of this method is showcased not only by the late-stage functionalization of natural alkaloid derivatives and pharmaceutical intermediate, but also by the applicability of a stop-flow microtubing reactor.
- Xia, Qing,Li, Yufei,Cheng, Lan,Liang, Xin,Cao, Chenlin,Dai, Peng,Deng, Hongping,Zhang, Weihua,Wang, Qingmin
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supporting information
p. 9638 - 9643
(2020/12/21)
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- Covalently hooked EOSIN-Y in a Zr(IV) framework as visible-light mediated, heterogeneous photocatalyst for efficient C–H functionalization of tertiary amines
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Herein, we report the synthesis of a novel heterogeneous photo-catalyst by utilizing post-synthetic modification of an amine functionalized Zr(IV) metal-organic framework (UiO-66-NH2) through covalent hooking of EOSIN-Y via dehydrating coupling. The characterization of the catalyst was accomplished by FT-IR, XRD, BET surface analysis, TGA, as well as TEM, SEM, XPS, DRS-UV–visible, and NMR spectroscopy, confirming successful covalent linking of EOSIN-Y with the pendent –NH2 functionality in the framework. That post-modified EY@UiO-66-NH2 acts as simple and green visible light mediated photo-catalyst for the C–H activation of tertiary amines with excellent yields. Importantly, the activity of dye incorporated heterogeneous photo-catalyst is found superior to that for the homogeneous photo-catalyst EOSIN-Y. Thus, separation difficulty of homogeneous catalysis, as well as the environmental adverse effects of toxic EOSIN-Y can be excluded by developing such photo-catalyst. Moreover, EY@UiO-66-NH2 catalyst could be consistently recycled up to 10 cycles, without any significant loss in activity. Based on literature report and experimental findings, we also propose a plausible mechanism for the reaction.
- Kumar, Gaurav,Solanki, Pratik,Nazish, Mohd,Neogi, Subhadip,Kureshy, Rukhsana I.,Khan, Noor-ul H.
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p. 298 - 304
(2019/02/26)
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- New catalytic effect of thiourea on the oxidative cyanation of N-aryltetrahydroisoquinolines
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Thiourea itself has been introduced as a mild and efficient organocatalyst for the oxidative α -cyanation of N-aryltetrahydroisoquinolines (THIQs) with trimethylsilyl cyanide (TMSCN), giving the corresponding products in good to excellent yields. Experime
- Ullah, Bakhtar,Zhou, Yuli,Chen, Jingwen,Bao, Zongbi,Yang, Yiwen,Yang, Qiwei,Ren, Qilong,Zhang, Zhiguo
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supporting information
p. 348 - 351
(2019/01/04)
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- Iron-catalysed carbene-transfer reactions of diazo acetonitrile
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A continuous-flow protocol for the synthesis of diazo acetonitrile was developed. It was further applied in iron-catalysed insertion reactions of diazo acetonitrile into N-H and S-H bonds to yield valuable α-substituted acetonitrile, including gram-scale synthesis.
- Empel, Claire,Hock, Katharina J.,Koenigs, Rene M.
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supporting information
p. 7129 - 7133
(2018/10/24)
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- Metal-Free Aerobic Oxidative Cyanation of Tertiary Amines: Azobis(isobutyronitrile) (AIBN) as a Sole Cyanide Source
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An aerobic oxidative cyanation for the synthesis of α-aminonitriles was reported. The formation of C(sp3)-CN bonds was achieved under a metal-free condition by utilizing azobis(isobutyronitrile) as a sole organic cyanide source with the combination of pivalic acid and sodium acetate as additives.
- Liu, Peng-Yu,Zhang, Chao,Zhao, Shi-Chen,Yu, Fang,Li, Fei,He, Yu-Peng
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p. 12786 - 12790
(2017/12/08)
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- Method for synthesizing alpha-aminonitrile by adopting AIBN as individual cyan source
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The invention relates to a method for synthesizing alpha-aminonitrile by adopting AIBN as an individual cyan source. The method comprises the following steps: adding tertiary amine into a container, sequentially adding 2,2'-azodiisobutyronitrile (AIBN), p
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Paragraph 0018-0020; 0022
(2017/09/01)
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- A highly efficient heterogeneous ruthenium-catalysed oxidative α-cyanation of tertiary amines leading to α-aminonitriles
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Oxidative α-cyanation of tertiary amines was achieved by using an MCM-41-immobilised N-alkylethylenediamine ruthenium(III) complex (MCM-41-2N-RuCl3) as catalyst in MeOH at 60 oC in the presence of H2O2 as oxidant and NaCN
- Wang, Xiaoming,Xiao, Ruian,Ai, Jingting,Cai, Mingzhong
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p. 576 - 580
(2017/11/14)
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- Synthesis of α-aminonitriles via a FeSO4-mediated oxidative cyanation of tertiary amines with benzoyl cyanide and molecular oxygen or TBHP
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An iron-mediated oxidative cyanation of tertiary amines with benzoyl cyanide and molecular oxygen or TBHP has been achieved. This reaction furnished α-cyanated tertiary amines under mild reaction conditions in good to excellent yields (up to 94%) with gre
- Zhang, Lianpeng,Gu, Xin,Lu, Ping,Wang, Yanguang
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p. 2359 - 2363
(2016/04/19)
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- Iron-catalysed sequential reaction towards α-aminonitriles from secondary amines, primary alcohols and trimethylsilyl cyanide
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We have developed a one-pot iron-catalysed sequential reaction of secondary amines with primary alcohols, trimethylsilyl cyanide and TBHP under mild reaction conditions to give the corresponding α-aminonitriles.
- Shen, Hang,Hu, Liangzhen,Liu, Qing,Hussain, Muhammad Ijaz,Pan, Jing,Huang, Mingming,Xiong, Yan
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p. 2776 - 2779
(2016/02/19)
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- Preparation method for alpha-cyanoamine
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The invention discloses a preparation method for alpha-cyanoamine. According to the method, the product alpha-cyanoamine is prepared through nucleophilic substitution in a mixed solvent in the presence of an oxidizing agent with an amine compound and cyanoacetic acid as reactants, iodide as a catalyst and sodium acetate as alkali. The catalyst used in the method has high reactivity; reaction conditions are mild; the application scope of a substrate is wide; post-treatment is convenient; the yield of the target product is high; preparation process is simple, green and environment-friendly; and used raw materials are widely available.
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Paragraph 0070; 0071
(2016/10/07)
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- Highly efficient and recyclable magnetic nanoparticles-supported gold(III)-bipy catalyst for oxidative α-cyanation of tertiary amines
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Oxidative α-cyanation of tertiary amines with trimethylsilyl cyanide was achieved by using a magnetic nanoparticles-supported gold(III)-bipy complex as catalyst to afford the corresponding α-aminonitriles in good to excellent yields in the presence of ter
- Yang, Weisen,Wei, Li,Yi, Feiyan,Cai, Mingzhong
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p. 4059 - 4067
(2016/07/06)
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- Potassium ion cationized polyether cyanide [K+{PEG}CN-] as a novel cyanide source for oxidative cyanation of tertiary amines
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Potassium ions cationized polyether cyanide [K+{PEG}CN-] was readily synthesized by mixing potassium cyanide and PEG400 at room temperature and used as a cost effective and comparatively safer alternative to the toxic sodium cyanide/acetic acid system for generating in situ HCN for the oxidative cyanation of tertiary amines with hydrogen peroxide using RuCl3 as catalyst. This method affords a facile approach to the synthesis of α-aminonitriles in high yields under solvent-free and acid-free reaction conditions.
- Panwar, Vineeta,Ray, Siddharth S.,Jain, Suman L.
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p. 4184 - 4186
(2015/06/22)
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- Cyanoacetic Acid as a Masked Electrophile: Transition-Metal-Free Cyanomethylation of Amines and Carboxylic Acids
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Using cyanoacetic acid as a masked electrophile, a new cyanomethylation reaction of amines and carboxylic acids was developed, producing a variety of α-aminonitriles and cyanomethyl esters with good yields and excellent functionality tolerance. This protocol features simple manipulation, inexpensive reagents, and a wide substrate scope. Iodoacetonitrile was generated in situ from the iodination-decarboxylation of cyanoacetic acid in this transformation.
- Wang, Hongxiang,Shao, Ying,Zheng, Hao,Wang, Hanghang,Cheng, Jiang,Wan, Xiaobing
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supporting information
p. 18333 - 18337
(2015/12/24)
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- Magnetically recyclable iron oxide nanoparticles for the α-cyanation of amines under acid-free conditions and the formal synthesis of praziquantel
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A sustainable protocol for the α-cyanation of amines has been developed using cheap and affordable iron oxide nanoparticles under acid free conditions with an easy-to-handle, user-friendly cyanide source, ethyl cyanoformate. The magnetic property of the i
- Patil, Mahendra,Kapdi, Anant R.,Kumar, A. Vijay
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p. 54505 - 54509
(2015/06/30)
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- Magnetic graphitic carbon nitride: Its application in the C-H activation of amines
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Magnetic graphitic carbon nitride, Fe@g-C3N4, has been synthesized by adorning a graphitic carbon nitride (g-C3N4) support with iron oxide via non-covalent interaction. The magnetically recyclable catalyst showed excellent reactivity for the expeditious C-H activation and cyanation of amines.
- Verma, Sanny,Nasir Baig,Han, Changseok,Nadagouda, Mallikarjuna N.,Varma, Rajender S.
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supporting information
p. 15554 - 15557
(2015/10/28)
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- A TiO2 immobilized Ru(ii) polyazine complex: A visible-light active photoredox catalyst for oxidative cyanation of tertiary amines
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A chemically functionalized nanocrystalline TiO2 grafted ruthenium(ii) polyazine complex was found to be an efficient visible light photoredox catalyst for the oxidative cyanation of tertiary amines to the corresponding α-aminonitriles in high to excellent yields, using molecular oxygen as an oxidant and sodium cyanide in acetic acid as a cyanide source. The developed photoredox catalyst could be easily recovered by simple filtration and reused for several runs with consistent catalytic activity.
- Kumar, Pawan,Varma, Sanny,Jain, Suman L.
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p. 4514 - 4519
(2014/03/21)
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- Rhenium-catalyzed oxidative cyanation of tertiary amines with TMSCN
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Oxidative cyanation of sp3 C-H bonds at the α position of tertiary amines by using TMSCN as the cyanide donor and a novel high-valent rhenium(V) complex was developed. The reaction offers the corresponding α-aminonitriles in good yields with tert-butyl hydroperoxide as the oxidant under mild and acid-free reaction conditions. Oxidative cyanation of sp3 C-H bonds at the α position of tertiary amines by using TMSCN as the cyanide donor and novel high-valent rhenium(V) complex catalysts is developed. The reactions offer the corresponding α-aminonitriles in good yields by using tert-butyl hydroperoxide as the oxidant under mild and acid-free reaction conditions at room temperature. Copyright
- Lin, Aijun,Peng, Hao,Abdukader, Ablimit,Zhu, Chengjian
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p. 7286 - 7290
(2013/11/19)
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- Cobalt-Catalyzed oxidative α-cyanation of tertiary aromatic amines with trimethylsilyl cyanide and tert -butyl hydroperoxide
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In this Letter is described that a cobalt(II)-tert-butyl hydroperoxide oxidizing system was used to catalyze the α-cyanation of aromatic tertiary amines in the presence of trimethylsilyl cyanide to produce the corresponding α-aminonitriles in good yields. Georg Thieme Verlag Stuttgart. New York.
- Sakai, Norio,Mutsuro, Akihiro,Ikeda, Reiko,Konakahara, Takeo
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p. 1283 - 1285
(2013/07/19)
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- Iron-catalyzed generation of α-amino nitriles from tertiary amines
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The use of iron(II) chloride as catalyst, trimethylsilyl cyanide as source of cyanide ions, and tert-butyl hydroperoxide as oxidant enabled the conversion of aromatic, benzylic, and aliphatic tertiary amines into α-Amino nitriles under mild conditions. Chemoselective functionalization of N-CH3 to N-CH2CN was achieved in the presence of Nbenzyl and N-alkyl groups. N,N-Dialkylanilines, PhNR2, with R=Et, Bu, Bn furnished the alkyl-(aryl)aminoacetonitriles PhN(R)CH2CN as the main products accompanied by α-Amino nitriles generated by ordinary a-cyanation of the aniline PhNR2. Formation of PhN(R)CH2CN was rationalized by oxidative degradation of N,N-dialkylanilines to N-alkylanilines, their condensation with formaldehyde, generated by oxidation of the solvent methanol, and final trapping of the thus formed iminium ions by cyanide.
- Wagner, Alexander,Han, Wei,Mayer, Peter,Ofial, Armin R.
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supporting information
p. 3058 - 3070
(2014/03/21)
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- A ruthenium-carbamato-complex derived from a siloxylated amine and carbon dioxide for the oxidative α-cyanation of aromatic and cyclic tertiary amines
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The ruthenium carbamate complex derived from 3-trimethoxysilyl-1-propyl amine and carbon dioxide was found to be a novel catalyst for the oxidative cyanation of aromatic and cyclic tertiary amines to corresponding α-amino nitriles in high to excellent yields by using hydrogen peroxide and molecular oxygen as enviro-economic oxidants. The developed protocol suggested an efficient alternative for recycling carbon dioxide.
- Kumar, Subodh,Kumar, Pawan,Jain, Suman L.
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p. 24013 - 24016
(2013/11/19)
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- Iron nanoparticles supported on graphene oxide: A robust, magnetically separable heterogeneous catalyst for the oxidative cyanation of tertiary amines
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Well-dispersed iron nanoparticles supported on chemically derived graphene oxide containing uniform distribution of iron nanoparticles (FeNPs) throughout the surface was synthesized and was used as a heterogeneous catalyst for oxidative cyanation of tertiary amines to the corresponding α- aminonitriles in high to excellent yields using hydrogen peroxide with sodium cyanide in acetic acid. After the reaction the catalyst could easily be separated by the influence of an external magnet and reused for several runs without any significant change in the catalytic activity and without leaching of the metal during the reaction. Copyright
- Verma, Deepak,Verma, Sanny,Sinha, Anil K.,Jain, Suman L.
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p. 860 - 865
(2013/09/02)
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- Azobisisobutyronitrile initiated aerobic oxidative transformation of amines: Coupling of primary amines and cyanation of tertiary amines
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In the presence of a catalytic amount of radical initiator AIBN, primary amines are oxidatively coupled to imines and tertiary amines are cyanated to α-aminonitriles. These "metal-free" aerobic oxidative coupling reactions may find applications in a wide
- Liu, Lianghui,Wang, Zikuan,Fu, Xuefeng,Yan, Chun-Hua
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supporting information
p. 5692 - 5695
(2013/01/15)
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- Visible-light photoredox catalyzed oxidative Strecker reaction
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An aerobic photocatalytic oxidative cyanation of tertiary amines providing valuable α-aminonitriles in good to excellent yields was developed. Mild reaction conditions and low catalyst loading are attractive features of the protocol. The Royal Society of
- Rueping, Magnus,Zhu, Shaoqun,Koenigs, Rene M.
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supporting information; experimental part
p. 12709 - 12711
(2012/01/05)
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- Gold-complexes catalyzed oxidative α-cyanation of tertiary amines
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Oxidative α-cyanation of tertiary amines is catalyzed by gold complexes with trimethylsilyl cyanide to afford the corresponding α-aminonitriles in the presence of tert-butyl hydroperoxide in good to excellent yields under acid-free conditions at room temp
- Zhang, Yan,Peng, Hao,Zhang, Ming,Cheng, Yixiang,Zhu, Chengjian
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supporting information; experimental part
p. 2354 - 2356
(2011/04/15)
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- Acetone cyanohydrin: A convenient alternative of toxic sodium cyanide/acetic acid for oxidative cyanation of tertiary amines
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Acetone cyanohydrin was found to be a facile, convenient and comparatively safer alternative to toxic sodium cyanide/acetic acid system for generating in situ HCN for the oxidative cyanation of tertiary amines to α-aminonitriles in high yields with hydrog
- Verma, Sanny,Jain, Suman L.,Sain, Bir
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experimental part
p. 882 - 885
(2012/02/04)
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- Iron catalyzed oxidative cyanation of tertiary amines
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Iron(ii) and iron(iii) salts catalyze the oxidative α-cyanation of tertiary amines by trimethylsilyl cyanide in the presence of tert-butylhydroperoxide under acid-free conditions at room temperature.
- Han, Wei,Ofial, Armin R.
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supporting information; scheme or table
p. 5024 - 5026
(2010/01/06)
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- Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen or hydrogen peroxide and sodium cyanide: Sp3 C-H bond activation and carbon-carbon bond formation
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Ruthenium-catalyzed oxidative cyanation of tertiary amines with molecular oxygen in the presence of sodium cyanide and acetic acid gives the corresponding α-aminonitriles, which are highly useful intermediates for organic synthesis. The reaction is the first demonstration of direct sp3 C-H bond activation α to nitrogen followed by carbon-carbon bond formation under aerobic oxidation conditions. The catalytic oxidation seems to proceed by (i) α-C-H activation of tertiary amines by the ruthenium catalyst to give an iminium ion/ruthenium hydride intermediate, (ii) reaction with molecular oxygen to give an iminium ion/ruthenium hydroperoxide, (iii) reaction with HCN to give the α-aminonitrile product, H2O2, and Ru species, (iv) generation of oxoruthenium species from the reaction of Ru species with H2O2, and (v) reaction of oxoruthenium species with tertiary amines to give α-aminonitriles. On the basis of the last two pathways, a new type of ruthenium-catalyzed oxidative cyanation of tertiary amines with H2O2 to give α-aminonitriles was established. The α-aminonitriles thus obtained can be readily converted to α-amino acids, diamines, and various nitrogen-containing heterocyclic compounds.
- Murahashi, Shun-Ichi,Nakae, Takahiro,Terai, Hiroyuki,Komiya, Naruyoshi
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scheme or table
p. 11005 - 11012
(2009/02/05)
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- Aerobic Ruthenium-Catalyzed Oxidative Cyanation of Tertiary Amines with Sodium Cyanide
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RuCl3-catalyzed oxidative cyanation of tertiary amines with sodium cyanide under molecular oxygen (1 atm) at 60 °C gives the corresponding α-aminonitriles, which are versatile synthetic intermediates of various compounds such as amino acids and
- Murahashi, Shun-Ichi,Komiya, Naruyoshi,Terai, Hiroyuki,Nakae, Takahiro
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p. 15312 - 15313
(2007/10/03)
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