- Chemistry of gold(III) with pyridine-carboxamide ligands
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The pyridine-carboxamide ligand PhNHC(O)2-C5H4N reacts with Na+[AuCl4]- either by cation exchange, to give [PhNHC(O)2-C5H4NH][AuCl4], or by ligand substitution to give
- Nasser, Nasser,Puddephatt, Richard J.
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Read Online
- 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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- 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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- 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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- Surface engineered Iridium-based magnetic photocatalyst paving a path towards visible light driven C-H arylation and cyanation reaction
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The report presents the fabrication and application of a highly versatile, magnetic and robust iridium based photoredox nanocatalyst. Herein, Ir(PPy)3 based photocatalyst sites have been chemically engineered over the magnetic nanoparticles to encompass the captivating features of homogeneous iridium photocatalyst with the magnetically recyclable core. A household photoreactor was designed and fabricated to achieve highly selective visible light driven oxidative C-H arylation and C-H cyanation under sustainable and ambient reaction conditions utilizing the Ir@PyBz@ASMNPs photoredox nanocatalyst. The environment friendly Ir@PyBz@ASMNPs shows excellent photocatalytic activity, broad substrate adaptability and outstanding recyclability compared to the analogous homogeneous catalysts. Indeed, the Ir@PyBz@ASMNPs possess some key features including high surface area, high iridium metal loading and excellent stability. This work is expected to enlighten and provide new insights in the rational design of high performance and recoverable photoredox nanocatalyst through surface engineering strategy.
- Gaur, Rashmi,Gawande, Manoj B.,Kaushik, Bhawna,Rana, Pooja,Sharma, Priti,Sharma, Rakesh K.,Yadav, Priya,Yadav, Sneha
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p. 297 - 308
(2021/08/23)
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- 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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- Synthesis method of alpha-cyanide
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The invention relates to the field of synthesis of chemical products, in particular to a synthesis method of alpha-cyanide, the synthesis method comprises the following steps: starting from easily available tertiary amine compounds, respectively taking ch
- -
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Paragraph 0053-0054
(2021/08/19)
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- Electrochemical strategies for: N -cyanation of secondary amines and α C -cyanation of tertiary amines under transition metal-free conditions
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Transition metal-free electrochemical approaches for the N-cyanation of secondary amines and the α C-cyanation of tertiary amines have been well established, with products being obtained in moderate to good yields and with good functional group tolerance under ambient conditions. The synthetic application of the protocols has been highlighted through scale-up experiments in a galvanostatic mode. Preliminary mechanistic investigation has confirmed that TBAB played a critical role in N-cyanation transformation and has indicated that the transformation might proceed via a free radical process. This journal is
- Cai, Hu,Fu, Yaping,Fu, Zhengjiang,Guo, Shengmei,Hao, Guangguo,Yi, Xuezheng,Yin, Jian,Zhong, Tingting
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supporting information
p. 9422 - 9427
(2021/12/09)
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- Site-Selective Electrochemical C-H Cyanation of Indoles
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An electrochemical approach for the site-selective C-H cyanation of indoles employing readily available TMSCN as cyano source has been developed. The electrosynthesis relies on the tris(4-bromophenyl)amine as a redox catalyst, which achieves better yield and regioselectivity. A variety of C2- and C3-cyanated indoles were obtained in satisfactory yields. The reactions are conducted in a simple undivided cell at room temperature and obviate the need for transition-metal reagent and chemical oxidant.
- Li, Laiqiang,Hou, Zhong-Wei,Li, Pinhua,Wang, Lei
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supporting information
p. 5983 - 5987
(2021/08/16)
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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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- Metal-based surface active ionic liquids: Self-assembling characteristics and C[sbnd]C bond functionalization of tertiary amines with TMSCN in aqueous micellar solutions
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Metal-based surface active ionic liquids (MSAILs), 1-alkyl-3-methyl imidazoliumtetrachloromanganate [Cnmim][MnCl4]2 ? (n= 8,10,12) have been synthesized and characterized for self-assembling behavior in aqueous
- Kulshrestha, Akshay,Kumar, Gaurav,Khan,Kumar, Arvind
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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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- 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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- 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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- Redox-neutral C–H cyanation of tetrahydroisoquinolines under photoredox catalysis
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Redox-neutral cyanation of C–H bond adjacent to a nitrogen atom was achieved by using the combination of a photoredox catalyst and p-toluenesulfonyl cyanide. The reaction of tetrahydroisoquinolines proceeded smoothly, affording the corresponding cyanated products selectively in good to high yield. Although the reaction rate became slower in the case of the substrates having electron-withdrawing groups, high yields were achieved by elongating the reaction time. Although the yields were only moderate, the reaction conditions were also applicable to N,N-dialkylanilines.
- Ide, Takafumi,Shimizu, Kazunori,Egami, Hiromichi,Hamashima, Yoshitaka
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supporting information
p. 3258 - 3261
(2018/07/25)
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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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- Cobalt(II)/ N -Hydroxyphthalimide-Catalyzed Cross-Dehydrogenative Coupling Reaction at Room Temperature under Aerobic Condition
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This work reports a cobalt(II)/N-hydroxyphthalimide (NHPI)-catalyzed cross-dehydrogenative oxidative coupling of N-aryl tetrahydroisoquinolines with various pro-nucleophiles, such as indoles, nitroalkanes, and trialkylphosphites, active methylene compound
- Patil, Mahendra R.,Dedhia, Noopur P.,Kapdi, Anant R.,Kumar, A.Vijay
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p. 4477 - 4490
(2018/04/26)
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- Photoredox-Catalyzed Cα-H Cyanation of Unactivated Secondary and Tertiary Aliphatic Amines: Late-Stage Functionalization and Mechanistic Studies
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This paper describes the development and mechanistic studies of a general, high-yielding amine Cα-H cyanation protocol via photoredox catalysis. Inexpensive NaCN is employed as the cyanide source and air is the external oxidant, resulting in mild and highly functional group tolerant conditions. Notably, efficient Cα-H cyanations of secondary and tertiary aliphatic amines and of complex, biologically active compounds (drugs) can be performed using the established methodology. Mechanistic studies suggest that the carboxylic acid additive has three effects: formation of a stabilizing hemiaminal intermediate, prevention of catalyst decomposition by protonating the substrate, and modulation of fluorescence quenching of the photoexcited catalyst species.
- Yilmaz, Ozgur,Oderinde, Martins S.,Emmert, Marion H.
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supporting information
p. 11089 - 11100
(2018/09/12)
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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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- 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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- 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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- 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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- CURE ACCELERATORS FOR ANAEROBIC CURABLE COMPOSITIONS
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Cure accelerators for anaerobic curable compositions, such as adhesives and sealants, are provided, and which are defined with reference to the compounds shown in structure I where A is CH2 or benzyl, R is C1-10 alkyl, R′ is H or Cs
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Paragraph 0086; 0091
(2017/07/14)
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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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- 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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- 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 0018; 0019
(2016/10/07)
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- Alpha-aminonitrile synthetic method
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The invention discloses a one-pot alpha-aminonitrile synthetic method and belongs to the technical field of organic chemistry synthesis. Various benzene ring halogen substituted or nitrogen alkyl or aryl substituted secondary amine, fatty alcohol and aromatic alcohol are taken as raw materials, peroxide is taken as the oxidizing agent, trimethylsilyl cyanide is taken as the nucleophilic cyaniding reagent, various kinds of molysite are taken as the catalyst, and one-step oxidation-condensation-nucleophilic reaction, concentration and purification are conducted in a solvent at room temperature or under the heating condition to generate a finished product. The method has certain universality, reaction conditions are mild, requirements for production equipment are low, technology is simple, raw materials are easy to obtain, and popularization is easy. By the adoption of the method, high-yield and high-quality alpha-aminonitrile can be prepared. The method can be widely applied to industrial production of alpha-aminonitrile. The prepared alpha-aminonitrile can be widely applied to synthesis of bioactive compounds or functional materials including alpha-amino acid, 1,2-diamine, tetrahydroquinoline, alpha-amino-aldehyde, ketone or beta-amino alcohol and has broad market application prospects.
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Paragraph 0055; 0062; 0064
(2017/01/19)
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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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- α-Cyanation of Aromatic Tertiary Amines using Ferricyanide as a Non-Toxic Cyanide Source
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The reaction of aromatic tertiary amines with potassium ferricyanide directly provides the useful α-amino nitriles. The inexpensive iron complex functions both as an oxidant and as a cyanide source. The presence of molecular oxygen speeds up the reaction which can be performed in aqueous tert-butanol or even in ethanol-based mixtures like Tequila. While amine cyanations usually employ highly toxic cyanide sources, potassium ferricyanide is even less toxic than table salt. No expensive metal complexes are required as catalysts and the co-product of the cyanation, Prussian blue, has no known toxicity and is rather used as an antidote.
- Nauth, Alexander M.,Otto, Nicola,Opatz, Till
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supporting information
p. 3424 - 3428
(2016/01/25)
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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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- 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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- 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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- Iron-catalyzed Cα-H oxidation of tertiary, aliphatic amines to amides under mild conditions
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De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe-catalyzed Cα-H functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild Cα-H cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis. Let′s iron it out! The title reaction enables the oxidative synthesis of amides directly from tertiary, noncyclic alkyl amines under synthetically useful, mild conditions through a biologically inspired approach employing oxidative iron catalysis. Mechanistic studies suggest that hemiaminals are likely intermediates in this reaction and that the catalytic system can be employed for other Cα-H oxidations of amines.
- Legacy, Christopher J.,Wang, Anqi,O'Day, Brian J.,Emmert, Marion H.
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supporting information
p. 14907 - 14910
(2016/02/05)
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- Direct oxidative cyanation of tertiary amines promoted by in situ generated hypervalent iodine(III)-CN intermediate
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An environmentally benign and metal-free cyanation method of tertiary amines oxidated by hypervalent iodine(III) intermediate generated in situ from PIFA (or DIB) and TMSCN has been developed. A variety of substituent groups on amines are tolerated to the oxidation of α-C-H bond to form C-C bond in the absence of metal catalysts with yields of up to 74%.
- Shen, Hang,Zhang, Xiaohui,Liu, Qing,Pan, Jing,Hu, Wen,Xiong, Yan,Zhu, Xiangming
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supporting information
p. 5628 - 5631
(2015/09/21)
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- Unexpected C=N bond formation via NaI-catalyzed oxidative de-tetra-hydrogenative cross-couplings between N,N-dimethyl aniline and sulfamides
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A direct and convenient C=N bond formation reaction was reported, which was a de-tetra-hydrogenative cross-coupling (DTCC) reaction between N,N-dimethyl aniline and sulfamide under transition-metal-free conditions, and to give sulfonyl amidine derivatives in moderate to high yields.
- Zheng, Yang,Mao, Jincheng,Chen, Jie,Rong, Guangwei,Liu, Defu,Yan, Hong,Chi, Yongjian,Xu, Xinfang
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p. 50113 - 50117
(2015/06/25)
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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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- Nucleophilic attack of α-aminoalkyl radicals on carbon-nitrogen triple bonds to construct α-amino nitriles: An experimental and computational study
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A new reactivity pattern of α-aminoalkyl radicals, involving nucleophilic attack on Ci£N triple bonds under thermal conditions, has been developed to construct α-amino nitriles. In contrast to previous C-H functionalization of tertiary amines involving α-aminoalkyl radicals, this methodology does not require the use of photocatalytic conditions or a transition-metal catalyst. Inexpensive and nontoxic phenylacetonitrile was chosen as cyano source for this α-aminonitrile forming reaction. A plausible mechanism is proposed based upon experimental and computational results. An α-aminoalkyl radical intermediate and benzoyl cyanide have been shown to be key intermediates in this Copyright
- Zhang, Chao,Liu, Chunmei,Shao, Ying,Bao, Xiaoguang,Wan, Xiaobing
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p. 17917 - 17925
(2014/01/17)
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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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- A versatile C-H functionalization of tetrahydroisoquinolines catalyzed by iodine at aerobic conditions
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A versatile aerobic catalytic system (I2 and O2/TBHP) for C-H functionalization is reported. This CDC (cross-dehydrogentive coupling) reaction is compatible with a large number of nucleophiles and is performed under ambient reaction
- Dhineshkumar, Jayaraman,Lamani, Manjunath,Alagiri, Kaliyamoorthy,Prabhu, Kandikere Ramaiah
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supporting information
p. 1092 - 1095
(2013/03/29)
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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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- Ruthenium complexes with an anthyridine-based ligand. Synthesis, characterization and catalytic activity
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Complexation of 2, 7-bis(2-pyridinyl)-9-phenylanthyridine (4) with [RuCl2(CO)3(THF)] and [(η6-p-cy-mene) RuCl2]2 provided the mono-nuclear complex [(4)Ru(CO) 3Cl][RuCl3(CO)3
- Lo, Ying-Hao,Liu, Yi-Hung,Peng, Shie-Ming,Liu, Shiuh-Tzung
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p. 839 - 845
(2013/11/06)
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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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- Efficient synthesis of hydroxytyrosol from 3,4-dihydroxybenzaldehyde
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Hydroxytyrosol is a naturally occurred orthodiphenolic component of olive oil. A variety of biological functions for this molecule have been reported. We report herein an efficient and practical method for the chemical synthesis of hydroxytyrosol from 2,3-dihydroxybenzaldehyde. Taylor & Francis Group, LLC.
- Zhang, Zhao-Li,Chen, Jinglei,Xu, Qiongming,Rao, Cui,Qiao, Chunhua
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experimental part
p. 794 - 798
(2012/01/17)
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