- Iron-Catalyzed Oxidation of 4-Substituted N,N-Dimethylanilines with Molecular Oxygen in the Presence of Benzoyl Cyanide
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The oxidation of 4-substituted N,N-dimethylanilines with molecular oxygen using a catalytic amount of iron(III) chloride efficiently proceeded in the presence of benzoyl cyanide to give the corresponding N-cyanomethyl-N-methylanilines along with N-methylformanilides.
- Murata, Satoru,Teramoto, Koji,Miura, Masahiro,Nomura, Masakatsu
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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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- 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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- Copper-catalyzed synthesis of α-amino nitriles through methyl transfer from DMF to aromatic amines
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A copper-catalyzed activation of C(sp3)-H bonds of DMF at room temperature was developed, which results in methyl transfer to aromatic amines for efficient synthesis of exceedingly valuable α-amino nitriles. This process features excellent functional group tolerance, a broad substrate scope, and high activity under ambient conditions.
- Yuan, Zaifeng,Li, Na,Zhu, Chunyu,Xia, Chengfeng
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supporting information
p. 2854 - 2857
(2018/03/23)
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- Seven-coordinated chiral uranyl(VI) salen complex as effective catalyst for C–H bond activation of dialkylanilines under visible light
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A new chiral uranyl(VI) complex incorporating a tetradentate salen ligand is reported. The synthesized uranyl complex is studied by microanalyses, spectroscopic and X-ray diffraction studies. The structural studies reveal a slightly distorted pentagonal bipyramid coordination environment around uranyl ion. Interestingly, the uranyl complex was found to be potential visible light active catalyst for C–H bond functionalization of dialkylanilines, and afforded moderate to excellent yield of corresponding α-aminonitriles when exposed to visible light for 8?h in the presence of NaCN and acetic acid as cyanide source, and H2O2as oxidant.
- Azam, Mohammad,Al-Resayes, Saud I.,Trzesowska-Kruszynska, Agata,Kruszynski, Rafal,Kumar, Pawan,Jain, Suman L.
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p. 177 - 183
(2017/01/28)
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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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- Potassium thiocyanate as source of cyanide for the oxidative α-cyanation of tertiary amines
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Oxidation at the sulfur of the safe-to-handle potassium thiocyanate releases cyanide units that are trapped in the presence of co-oxidized tertiary amines to form α-amino nitriles. These cyanations work in aqueous solutions and do not require a catalyst,
- Wagner, Alexander,Ofial, Armin R.
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p. 2848 - 2854
(2015/03/18)
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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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- 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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- 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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- Ruthenium-catalyzed oxidative cyanation of tertiary amines with hydrogen peroxide and sodium cyanide
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(Chemical Equation Presented) Versatile intermediates for the synthesis of N-aryl-α-amino acids and N,N-disubstituted 1,2-diamines can now be synthesized with high efficiency by the ruthenium-catalyzed oxidative cyanation of tertiary amines. The use of hy
- Murahashi, Shun-Ichi,Komiya, Naruyoshi,Terai, Hiroyuki
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p. 6931 - 6933
(2007/10/03)
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