- 2-Oxo-Driven N2 Elimination Induced Decarbonylative Cyclization Reaction in Benzotriazoles to 6-Aminophenanthridines
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An efficient functional group induced strategy for the synthesis of 6-aminophenanthridines (6AP) has been developed as a result of an in situ generated novel system "CO-CH(N1N2)". This reaction presents a new mode of N2 ex
- Battula, Satyanarayana,Kumar, Atul,Ahmed, Qazi Naveed,Gupta, Ajai Prakash
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- One-Pot Synthesis of α-Ketoamides from α-Keto Acids and Amines Using Ynamides as Coupling Reagents
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A one-pot strategy for α-keto amide bond formation have been developed by using ynamides as coupling reagents under extremely mild reaction conditions. Diversely structural α-ketoamides were afforded in up to 98% yield for 36 examples. This reaction features advantages such as practical coupling procedure, wide functional group tolerance, and extremely mild conditions and has potential applications in synthetic and medicinal chemistry.
- Ma, Jianting,Cui, Xue,Xu, Junyu,Tan, Yinfeng,Wang, Yan,Wang, Xuesong,Li, Youbin
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supporting information
p. 3661 - 3667
(2022/02/07)
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- Desulfurizing agent for thioamides
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Thioamides treated with thionyl chloride in an ionic liquid were successfully converted into amides.
- Polushina,Zavarzin,Krayushkin,Rodionova,Yarovenko
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p. 383 - 385
(2021/03/03)
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- Selective electrochemical oxidation of aromatic hydrocarbons and preparation of mono/multi-carbonyl compounds
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A selective electrochemical oxidation was developed under mild condition. Various mono-carbonyl and multi-carbonyl compounds can be prepared from different aromatic hydrocarbons with moderate to excellent yield and selectivity by virtue of this electrochemical oxidation. The produced carbonyl compounds can be further transformed into α-ketoamides, homoallylic alcohols and oximes in a one-pot reaction. In particular, a series of α-ketoamides were prepared in a one-pot continuous electrolysis. Mechanistic studies showed that 2,2,2-trifluoroethan-1-ol (TFE) can interact with catalyst species and generate the corresponding hydrogen-bonding complex to enhance the electrochemical oxidation performance. [Figure not available: see fulltext.]
- Li, Zhibin,Zhang, Yan,Li, Kuiliang,Zhou, Zhenghong,Zha, Zhenggen,Wang, Zhiyong
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p. 2134 - 2141
(2021/09/29)
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- Preparation method of alpha-carbonyl amide compound
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The invention discloses a preparation method of an alpha-carbonyl amide compound. The method comprises the following steps: under the action of a catalyst, taking oxygen as an oxidant, and carrying out oxidative amidation reaction on an alpha-diazoketone compound shown in a chemical formula 2 and a cyclic secondary amine compound shown in a chemical formula 3 in an organic solvent to obtain the alpha-carbonyl amide compound shown in a chemical formula 1, wherein the formulas 1, 2 and 3 are also shown in the speification. According to the preparation method disclosed by the invention, the alpha-carbonyl amide compound is obtained by taking oxygen as the oxidizing agent and catalyzing alpha-diazoketone and cyclic secondary amine to be subjected to oxidative amidation reaction through cuprous iodide, the reaction condition is mild, the reaction time is short, and the byproduct of the reaction is only nitrogen, so that the method is an effective way for green and efficient preparation of the alpha-carbonyl amide compound.
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Paragraph 0069-0084
(2021/08/14)
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- Diversification of α-ketoamides: Via transamidation reactions with alkyl and benzyl amines at room temperature
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A wide range of N-tosyl α-ketoamides underwent transamidation with various alkyl amines in the absence of a catalyst, base, or additive. On the other hand, transamidation in N-Boc α-ketoamides was achieved in the presence of Cs2CO3. The reactions proceede
- Junaid, Qazi Mohammad,Kandasamy, Jeyakumar,Popuri, Sureshbabu,Sabiah, Shahulhameed,Singh, Shweta
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p. 7134 - 7140
(2021/08/30)
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- Cu(OAc)2 and acids promoted the oxidative cleavage of α-aminocarbonyl compounds with amines: efficient and selective synthesis of 2-t-amino-2-imino-carbonyl and 2-amino-2-oxocarbonyl
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A novel and efficient method for the synthesis of 2-t-amino-2-imino-carbonyl (C) and 2-amino-2-oxocarbonyl (D) compounds has been discovered through a copper-promoted oxidating amidation reactions between α-amino -carbonyl compounds and amines. Promoted by the crucial copper species, perfect selectivity and good to excellent yields could be achieved. This transformation is achieved through C[sbnd]N bond oxidative cleavage and formation a novel C[sbnd]N bond. This reaction system has a broad reaction scope, providing a facile pathway for the α-functionalization of α-amino ketones.
- Chen, De,Cheng, Chaozhihui,Zeng, Sheng,Luo, Yongyue,Zhang, Jiajia,Deng, Wei,Zeng, Zebing,Wang, Ruijia,Xiang, Jiannan
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- Electrochemical Synthesis of α-Ketoamides under Catalyst-, Oxidant-, and Electrolyte-Free Conditions
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A catalyst-, oxidant-, electrolyte-free method for the preparation of α-ketoamides through the direct electrochemical amidation of α-ketoaldehydes and amines with innocuous hydrogen as the sole byproduct at ambient temperature was developed. The present reaction features clean and mild conditions, excellent functional-group tolerance, and high atom economy and scalability, enabling facile applications in pharmaceutical chemistry.
- Chen, Jin-Yang,Wu, Hong-Yu,Gui, Qing-Wen,Han, Xiao-Ran,Wu, Yan,Du, Kui,Cao, Zhong,Lin, Ying-Wu,He, Wei-Min
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supporting information
p. 2206 - 2209
(2020/03/13)
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- Structure–activity relationships (SARs) of α- ketothioamides as inhibitors of phosphoglycerate dehydrogenase (PHGDH)
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For many years now, targeting deregulation within cancer cells’ metabolism has appeared as a promising strategy for the development of more specific and efficient cancer treatments. Recently, numerous reports highlighted the crucial role of the serine synthetic pathway, and particularly of the phosphoglycerate dehydrogenase (PHGDH), the first enzyme of the pathway, to sustain cancer progression. Yet, because of very weak potencies usually in cell-based settings, the inhibitors reported so far failed to lay ground on the potential of this approach. In this paper, we report a structure–activity relationship study of a series of α-ketothioamides that we have recently identified. Interestingly, this study led to a deeper understanding of the structure–activity relationship (SAR) in this series and to the identification of new PHGDH inhibitors. The activity of the more potent compounds was confirmed by cellular thermal shift assays and in cell-based experiments. We hope that this research will eventually provide a new entry point, based on this promising chemical scaffold, for the development of therapeutic agents targeting PHGDH.
- Spillier, Quentin,Ravez, Séverine,Unterlass, Judith,Corbet, Cyril,Degavre, Charline,Feron, Olivier,Frédérick, Rapha?l
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- Cu-Catalyzed aerobic oxidative cleavage of C(sp3)–C(sp3) bond: Synthesis of α-ketoamides
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A novel synthesis of α-ketoamides from Cu-catalyzed aerobic oxidative C(sp3)–C(sp3) bond cleavage of hydrocinnamaldehydes has been developed. Readily available and environmentally benign oxygen is used as the oxidant. This reaction avoids the use of noble metal catalysts or specialized oxidants, and chemoselectively yields α-ketoamide. Moreover, based on various control experiments, a reasonable mechanism is proposed.
- Fang, Zheng,Guo, Kai,Liu, Chengkou,Yang, Man,Zhang, Jingming
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supporting information
(2020/11/02)
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- Amine-Mediated Bond Cleavage in Oxidized Lignin Models
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Introducing amines/ammonia into lignin cracking will allow novel bond cleavage pathways. Herein, a method of amines/ammonia-mediated bond cleavage in oxidized lignin β-O-4 models was studied using a copper catalyst at room temperature, demonstrating the effect of the amine source on the selectivity of products. For primary and secondary aliphatic amines, lignin ketone models underwent oxidative Cα?Cβ bond cleavage and Cα?N bond formation to generate aromatic amides. For ammonia, the competition between oxygen and ammonia determined the selectivity between Cα?N and Cβ?N bond formation, generating amides and α-keto amides, respectively. For tertiary amines, the lignin models underwent oxidative Cα?Cβ bond cleavage to benzoic acids. Control experiments indicated that amines act as nucleophiles attacking at the Cα or Cβ position of the oxidized β-O-4 linkage to be cleaved. This study represents a novel example that the breakage of oxidized lignin model can be regulated by amines with a copper catalyst.
- Li, Hongji,Liu, Meijiang,Liu, Huifang,Luo, Nengchao,Zhang, Chaofeng,Wang, Feng
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p. 4660 - 4665
(2020/07/04)
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- POP-Pd(ii) catalyzed easy and safe: In situ carbonylation towards the synthesis of α-ketoamides from secondary cyclic amines utilizing CHCl3 as a carbon monoxide surrogate
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A novel complex catalyst, POP-palladium(ii), has been synthesized. The developed catalyst has been characterized by XRD, EDX, scanning electron microscopy (FE-SEM), HR-TEM, FTIR spectroscopy, UV-vis spectroscopy, TGA and BET isotherm analysis. The reactiv
- Islam, Sk Safikul,Riyajuddin, Sk,Molla, Rostam Ali,Yasmin, Nasima,Ghosh, Kaushik,Islam, Sk. Manirul
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p. 1979 - 1987
(2020/02/13)
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- Synthesis of Carbamates from Alkyl Bromides and Secondary Amines Using Silver Carbonate
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Synthesis of alkyl carbamates from alkyl bromides and secondary amines using silver carbonate as a carbonate source under mild condition is described. Various secondary amines and bromo derivatives were converted into alkyl carbamate derivatives in 33 to 62 % yield.
- Acharya, Vanitha,Mal, Sanjib,Kilaru, Jagadeesh P.,Montgomery, Mark G.,Deshpande, Sudhindra H.,Sonawane, Ravindra P.,Manjunath, Bhanu N.,Pal, Sitaram
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supporting information
p. 378 - 387
(2020/01/22)
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- Double carbonylation of iodoarenes in the presence of a pyridinium SILP-Pd catalyst
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The efficiency of a palladium catalyst, immobilised on a supported ionic liquid phase (SILP) with adsorbed 1-butyl-4-methylpyridinium chloride, was investigated in aminocarbonylation reactions. Double carbonylation was found to be the main reaction using different iodoarenes and aliphatic amines as substrates. Application of aniline derivatives as nucleophiles led to the exclusive formation of substituted benzamides. The stabilisation effect of the adsorbed pyridinium ionic liquid was compared to that of imidazolium and phosphonium derivatives. It was proved that the pyridinium SILP-palladium catalyst could be reused in at least 10 cycles. Recyclability was tested in five successive runs for all of the substrates.
- Nagy, Enik?,Nagy, Petra,Papp, Máté,Skoda-F?ldes, Rita,Urbán, Béla
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- C-H/C-C Functionalization Approach to N-Fused Heterocycles from Saturated Azacycles
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Herein we report the synthesis of substituted indolizidines and related N-fused bicycles from simple saturated cyclic amines through sequential C-H and C-C bond functionalizations. Inspired by the Norrish-Yang Type II reaction, C-H functionalization of azacycles is achieved by forming α-hydroxy-β-lactams from precursor α-ketoamide derivatives under mild, visible light conditions. Selective cleavage of the distal C(sp2)-C(sp3) bond in α-hydroxy-β-lactams using a Rh-complex leads to α-acyl intermediates which undergo sequential Rh-catalyzed decarbonylation, 1,4-addition to an electrophile, and aldol cyclization, to afford N-fused bicycles including indolizidines. Computational studies provide mechanistic insight into the observed positional selectivity of C-C cleavage, which depends strongly on the groups bound to Rh trans to the phosphine ligand.
- Ham, Jin Su,Park, Bohyun,Son, Mina,Roque, Jose B.,Jurczyk, Justin,Yeung, Charles S.,Baik, Mu-Hyun,Sarpong, Richmond
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supporting information
p. 13041 - 13050
(2020/09/01)
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- Palladium nanoparticles on a pyridinium supported ionic liquid phase: a recyclable and low-leaching palladium catalyst for aminocarbonylation reactions
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A new SILP (Supported Ionic Liquid Phase) palladium catalyst was prepared and characterized by 13C and 29Si CP MAS NMR, DTG, FTIR and TEM. The presence of the grafted pyridinium cations on the surface of the support was found to result in the formation of highly dispersed Pd nanoparticles with their diameter in the range of 1-2 nm. The catalyst was proved to be active not only in the aminocarbonylation of some model compounds but also in the synthesis of active pharmaceutical ingredients. Catalyst recycling and palladium leaching studies were carried out for the first time in aminocarbonylations leading to CX-546(1-(1,4-benzodioxan-6-ylcarbonyl)piperidine), Moclobemide, Nikethamide and a precursor of Finasteride. The latter reaction proves that not only aryl iodides but also an iodoalkene can be converted into the products with the help of the heterogeneous catalyst. The results show that the conditions should be always fine-tuned in the reactions of different substrates to achieve optimal results. Palladium loss was also observed to depend considerably on the nature of the reaction partners. This journal is
- Adamcsik, Bernadett,Nagy, Enik?,Pekker, Péter,Skoda-F?ldes, Rita,Szabó, Péter,Urbán, Béla
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p. 23988 - 23998
(2020/07/14)
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- Cu-Catalysed oxidative amidation of cinnamic acids/arylacetic acids with 2° amines: An efficient synthesis of α-ketoamides
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A new and convenient copper-catalysed synthesis of α-ketoamides has been accomplished using readily available cinnamic acids/arylacetic acids and 2° amines in an open atmosphere. The reaction between cinnamic acid and amine involves the formation of enamine followed by its aerobic oxidation, whereas the reaction of arylacetic acid with amine involves amide formation followed by benzylic methylene oxidation.
- Sharma, Anup Kumar,Jaiswal, Anjali,Singh, Krishna Nand
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supporting information
p. 9348 - 9351
(2019/11/11)
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- Visible-Light Mediated Photooxidative Synthesis of α-Keto Amides
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Photocatalytic amidation of α-keto aldehydes is herein investigated. This transformation was achieved using rose bengal as photocatalyst at room temperature under ambient air and under irradiation of a 20 W white LED bulb. The method is mild, efficient an
- Monga, Aparna,Pandey, Amar Prakash,Sharma, Anuj
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supporting information
p. 3554 - 3559
(2019/06/13)
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- Stabilized Cu2O nanoparticles on rGO highly catalyzed direct oxidative coupling synthesis of Α-ketoamides with molecular oxygen
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In this study, a green, efficient, recyclable Cu2O nanoparticles on reduced graphene oxide (Cu2O-NPs@rGO) carbon-based composite catalyst was synthesized by facile one-pot hydrothermal method. And Cu2O-NPs@rGO catalyst was
- Lu, Weiyang,Sun, Wei,Tan, Xiaofeng,Wang, Bin,Yang, Hua,Gao, Lingfeng,Zheng, Gengxiu
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- 1,2-dicarbonyl compound and synthesis method thereof
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The invention discloses a method for synthesizing a 1,2-dicarbonyl compound (1,2-dicarbonylamide or alpha-diketone compound), wherein 1,2-dicarbonyl thioester compounds used as 1,2-dicarbonyl reagentsreact with amine compounds or boric anhydride compounds under appropriate conditions to respectively synthesize a series of 1,2-dicarbonyl compounds. According to the present invention, the 1,2-dicarbonyl compound is obtained by using the stable 1,2-dicarbonyl thioester compound as the dicarbonylation reagent through one-step construction under mild conditions, such that the disadvantage that thetraditional method uses the unstable alpha-carbonyl acyl chloride to synthesize the 1,2-dicarbonyl compound is avoided.
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Paragraph 0055; 0088-0091
(2019/10/01)
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- Photoredox-Catalyzed Tandem Demethylation of N,N-Dimethyl Anilines Followed by Amidation with α-Keto or Alkynyl Carboxylic Acids
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We report herein, a biomimetic approach for highly selective monodemethylation of N,N-dimethyl anilines to generate secondary amines and subsequent coupling with α-ketocarboxylic acids or alkynyl carboxylic acids to form α-ketoamides or alkynamides respectively under visible light photoredox catalyst in a single operation. From the deuterium-labeling experiment, it was probed that demethylation is the slowest step in this tandem process. Whereas, control experiments and spectroscopic studies revealed that photoredox catalyst is also involved in the subsequent amidation step. The reaction proceeds smoothly at room temperature providing moderate to excellent yield of the coupling products. The amides have also been converted to a series of biologically active spiro compounds. (Figure presented.).
- Das, Pritha,Begam, Hasina Mamataj,Bhunia, Samir Kumar,Jana, Ranjan
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supporting information
p. 4048 - 4054
(2019/07/19)
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- Development of palladium catalysts immobilized on supported phosphonium ionic liquid phases
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The application of heterogeneous palladium catalysts supported on phosphonium ion modified silica was investigated in aminocarbonylation reactions of aryl iodides. In contrast to catalysts immobilized on supports decorated with imidazolium ions, the application of phosphonium type supported ionic liquid phases made it possible to carry out double carbonylation with good selectivity in apolar toluene which led to a considerable decrease in the amount of leached palladium. An even better stabilization of the palladium catalyst could be achieved by introducing dicationic organic moieties incorporating both imidazolium and phosphonium ions on the surface of the support. At the same time, the former catalyst, obtained from the supported phosphonium ionic liquid phase was found to be superior in monocarbonylations. The amide products were obtained in good yields by the proper choice of the reaction conditions, such as reaction temperature and pressure and that of the base.
- Urbán, Béla,Skoda-F?ldes, Rita
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p. 302 - 306
(2018/12/04)
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- Metal-Free C=C Double Bond Cleavage on Enaminones for the Synthesis of α-Ketoamides by Free-Radical Aerobic Oxygenation
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The tandem oxidation of the enaminone C=C double bond as well as subsequent C-N bond formation are realized under metal-free conditions by thermo-induced free radical transformation. In the presence of benzoyl peroxide (BPO) and N-iodosuccinimide (NIS), a
- Yang, Yiming,Zhong, Guofeng,Fan, Junfen,Liu, Yunyun
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supporting information
p. 4422 - 4425
(2019/06/24)
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- Water dispersed gold nanoparticles catalyzed aerobic oxidative cross-dehydrogenative coupling: An efficient synthesis of α-ketoamides in water
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An effective green synthesis of α-ketoamides was developed for the first time in water via gold nanoparticles (AuNPs) catalyzed aerobic oxidative cross-dehydrogenative coupling of secondary amines with phenylglyoxals with a broad substrate scope.
- Thirukovela, Narasimha Swamy,Balaboina, Ramesh,Vadde, Ravinder,Sekhar Vasam, Chandra
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supporting information
p. 3749 - 3752
(2018/09/17)
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- Copper-catalyzed oxidative synthesis of 2-oxo-acetamidines from one-pot three-component reaction of aryl methyl ketones, secondary amines and anilines
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Some novel 2-oxo-acetamidines were synthesized via one-pot three-component reaction of acetophenones, secondary amines and anilines in presence of CuI as catalyst. The reaction involved in a oxidation process of C (sp3)–H bonds of acetophenones
- Dutta, Leema,Bhuyan, Pulak J.
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p. 5770 - 5778
(2018/08/22)
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- UV Assisted High-Efficient Synthesis of α-Ketoamides using Air Promoted by A Non-Metal Catalyst in Aqueous Solution
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Presented here is the first example of UV (λ=210 nm) promoted procedure proceeding in aqueous media at room temperature using ambient air as the oxidant for efficient synthesis of an array of α-ketoamides of all types using a non-metal catalyst N-iodosuccinimide with a loading of 20 mol%. With UV, oxygen in the air was efficiently utilized as the green oxidant, some control experiments were carried out and a plausible mechanism was proposed, disclosing that in aqueous solution, the oxidation process was actually triggered by dioxygen radical anion (O2.?), while not molecular oxygen. A variety of secondary amines and primary amines as well as ammonia were employed as the amine moieties, and the desired product primary-, secondary-, and tertiary α-ketoamides were afforded in good to excellent yields of up to 96 %.
- Li, Jianhui,He, Shaopo,Zhang, Kuan,Quan, Ziyi,Shan, Qiheng,Sun, Zhongliang,Wang, Bo
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p. 4868 - 4873
(2018/10/15)
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- Cu(i)/{Nb6O19} catalyzed: N -acylation of arylacetic acids with amines under aerobic conditions
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The method described herein is a general, efficient and green approach to synthesize α-ketoamides from arylacetic acids and amines. Employing a simple copper(i)/{Nb6O19} catalyst system, the reaction offers a facile process to give functionalized α-ketoamides from readily available arylacetic acids under aerobic conditions. The merit of this new strategy is that it expands the syntheses of α-ketoamides from stable, inexpensive and widely available acylation reagents such as arylacetic acids in one step.
- Li, Pei-He,Wang, Zheng,Fu, Hui,Dai, Qi-Pu,Hu, Chang-Wen
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supporting information
p. 12471 - 12474
(2018/11/23)
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- Aerobic oxidative amidation of alkynes using titanium oxide encapsulated cuprous iodide nanoparticles (CuI@TiO2)
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A catalyst consisting of titanium oxide encapsulated cuprous iodide nanoparticles was prepared via a sol-gel method using inexpensive raw materials and was harnessed successfully in the oxidative amidation of alkynes via an environmentally benign and sustainable protocol. The mechanism of action of this transformation was thoroughly discussed. The robustness of the catalyst was elucidated by the synthesis of diverse analogues of α-ketoarylamide from a variety of electron rich and poor substrates via a simple procedure in moderate to high yields, with no generation of toxic by-products, in good recyclability up to five cycles, under solvent free and aerobic conditions. The chemical nature, morphology and loading of the CuI@TiO2 nanocatalyst were investigated by TEM, SEM, XPS, EDX, powder XRD, BET, TGA and ICP-MS.
- Dutta, Pratip Kumar,Dhar, Basabbijayi,Sen, Subhabrata
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p. 12062 - 12071
(2018/07/24)
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- Double carbonylation of iodoarenes in the presence of reusable palladium catalysts immobilised on supported phosphonium ionic liquid phases
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The first heterogeneous carbonylation reaction carried out with palladium catalysts immobilised on phosphonium ion modified silica supports is reported. The supported ionic liquid phases were characterised by solid state NMR and FT-IR measurements. The presence of the phosphonium ions on the surface made it possible to carry out double carbonylation in apolar toluene efficiently that resulted in reduced metal leaching. The introduction of dicationic moieties on the solid support has been proved to lead to a further increase in catalyst stability. The catalysts were proved to produce α-ketoamide products with excellent selectivity in the carbonylation of iodoarenes with aliphatic amines while monocarbonylation was the only reaction observed with aniline derivatives. The catalysts could be recycled and used in at least 10 subsequent runs under optimised conditions.
- Urbán, Béla,Szabó, Péter,Srankó, Dávid,Sáfrán, Gy?rgy,Kollár, László,Skoda-F?ldes, Rita
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p. 195 - 205
(2018/01/05)
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- Organic ligand-free carbonylation reactions with unsupported bulk Pd as catalyst
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Herein, surprising results for bulk Pd-catalyzed carbonylation reactions are presented. Three types of carbonylation reactions can be realized efficiently under organic ligand-free conditions, namely, hydroaminocarbonylation of olefins, aminocarbonylation of aryl iodides and oxidative carbonylation of amines, which almost cover all the known mechanisms in carbonylation reactions. Notably, the bulk Pd catalyst system exhibited better catalytic activity than the classical homogeneous PdCl2/(2-OMePh)3P catalyst system. This study will create a momentous and new field of green carbonylation reactions.
- Liu, Shujuan,Wang, Hongli,Dai, Xingchao,Shi, Feng
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supporting information
p. 3457 - 3462
(2018/08/06)
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- A METAL FREE PROCESS FOR THE PREPARATION OF ALPHA-SUBSTITUTED CARBONYL COMPOUNDS FROM ALKENES
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The present invention discloses a novel metal free process for the regioselective synthesis of α-substituted carbonyl compounds of formula I from alkene, X is selected from the following compounds (A, B).
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Page/Page column 20-21; 22
(2017/06/19)
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- Solvent-free one-pot oxidation of ethylarenes for the preparation of α-ketoamides under mild conditions
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Here we developed a highly efficient solvent-free, one-pot procedure for synthesizing α-ketoamides from ethylarenes and amines, by oxidizing a C-H bond sp3 center. A copper catalyst was employed, and the reactions proceeded smoothly at ambient temperatures. Most of the tested ethylarenes and amines were successfully converted to their corresponding α-ketoamides in moderate to excellent yields of up to 93% with three equivalents of the oxidant tert-butyl hydroperoxide.
- Liu, Fuyan,Zhang, Kuan,Liu, Yanfeng,Chen, Shan,Chen, Yiping,Zhang, Dela,Lin, Chunfu,Wang, Bo
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p. 7158 - 7162
(2017/02/05)
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- Versatile palladium-catalyzed double carbonylation of aryl bromides
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A versatile palladium-catalyzed double carbonylation of aryl bromides has been developed. Using Pd(OAc)2/BuPAd2 as the catalyst system and DBU as the base, under relatively low CO pressure, various α-ketoamides were produced in good
- Shen, Chaoren,Fink, Cornel,Laurenczy, Gabor,Dyson, Paul J.,Wu, Xiao-Feng
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supporting information
p. 12422 - 12425
(2017/11/23)
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- Mono- and double carbonylation of aryl iodides with amine nucleophiles in the presence of recyclable palladium catalysts immobilised on a supported dicationic ionic liquid phase
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Silica modified with organic dicationic moieties proved to be an excellent support for palladium catalysts used in the aminocarbonylation of aryl iodides. By an appropriate choice of the reaction conditions, the same catalyst could be used for selective mono- or double carbonylations leading to amide and α-ketoamide products, respectively. The best catalyst could be recycled for at least 10 consecutive runs with a loss of palladium below the detection limit. By the application of the new support, efficient catalyst recycling could be achieved under mild reaction conditions (under low pressure and in a short reaction time). Palladium-leaching data support a mechanism with dissolution - re-precipitation of the active palladium species.
- Papp,Szabó,Srankó,Sáfrán,Kollár,Skoda-F?ldes
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p. 44587 - 44597
(2017/09/26)
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- Air-Assisted 2-Oxo-Driven Dehydrogenative α,α-Diamination of 2-Oxo Aldehydes to 2-Oxo Acetamidines
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An air-assisted, functional-group-driven, mild, additive-free, three-component synthetic approach to different 2-oxo acetamidines from 2-oxo aldehydes, secondary amines, and anilines was successfully developed. Mechanistically, the transformation proceeds through a highly unstable system (RCOCHN1N2) that rearranges at room temperature and undergoes air-assisted dehydrogenation to different 2-oxo acetamidines.
- Kumar, Atul,Battini, Narsaiah,Kumar, Raju Ranjith,Athimoolam,Ahmed, Qazi Naveed
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supporting information
p. 3344 - 3348
(2016/07/23)
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- I2-promoted aerobic oxidative coupling of acetophenes with amines under metal-free conditions: Facile access to α-ketoamides
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A novel and efficient I2-promoted oxidative coupling of acetophenes with amines to α-ketoamides is presented, which employs O2 as an environmentally friendly oxidant under metal-free conditions. Based on a series of control experimen
- Guo, Shiyu,Fang, Zheng,Yang, Zhao,Liu, Chengkou,Dai, Zhongxue,Zhao, Lihuan,Guo, Kai
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p. 1503 - 1507
(2016/01/16)
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- Microwave-assisted direct oxidative synthesis of α-ketoamides from aryl methyl ketones and amines by a water soluble Cu(i)-complex
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A stable and isolable bis[(tetrabutylammonium) di-μ-iodo-diiododicuprate(i)] complex has been identified for the direct oxidative synthesis of α-ketoamides from substituted aryl methyl ketones and secondary amines in the presence of molecular oxygen. Grat
- Nekkanti, Shalini,Veeramani, Karuna,Praveen Kumar, Niggula,Shankaraiah, Nagula
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p. 3439 - 3447
(2016/06/13)
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- SeO2mediated efficient synthesis of amides and α-ketoamides of secondary amines with wide substrate scope
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SeO2mediated oxidative amidation of acetophenones, phenylacetylenes, and phenylacetaldehydes to α-ketoamides and aldehydes to amides is reported. Amidation selectively proceeds with secondary amines. α-Ketoamide derivatives of natural products 16-dehydropregnenolone acetate (8), pregnenolone acetate (10), and progesterone (11) were synthesized.
- Meena, Samdarshi,Singh, Rohit,Vishwakarma, Ram A.,Aga, Mushtaq A.,Jain, Shreyans K.
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supporting information
p. 3715 - 3717
(2016/07/26)
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- Cu(i)-Functionalized SBA-16: An efficient catalyst for the synthesis of α-ketoamides under moderate conditions
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An efficient catalyst based on the cage-like mesoporous material SBA-16 as the support and Cu(i) as active sites has been successfully prepared. The catalyst demonstrated high catalytic activity (up to 88%) in the direct oxidative synthesis of α-ketoamides between acetophenone and piperidine, employing O2 from open air as the oxidant without other additives. A heterogeneous catalyst was applied in this reaction for the first time, and the catalyst could be easily separated from the reaction system by filtration and reused several times without a significant loss of activity.
- Zhang, Xueyao,Yang, Honglei,Huo, Yong,Li, Jing,Ma, Jianxin,Ma, Jiantai
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p. 8972 - 8983
(2016/06/09)
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- One pot synthesis of α-ketoamides from ethylarenes and amines: a metal free difunctionalization strategy
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One-pot and metal free synthesis of α-ketoamides has been described through in situ generation of aryl ketones from easily available ethylarenes followed by amidation with various amines. This multiple oxidation protocol involves catalytic I2-pyridine-TBHP (t-butyl hydroperoxide) mediated oxidative benzylic carbonylation and sequential NaI-TBHP mediated oxidative amidation without using any solvent.
- Ramanathan, Mani,Kuo, Chun-Kai,Liu, Shiuh-Tzung
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p. 11446 - 11453
(2016/12/16)
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- Room temperature copper-catalyzed oxidative amidation of terminal alkynes for the synthesis of α-ketoamides using: O -benzoyl hydroxylamines as aminating reagent and oxidant
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A novel and convenient copper-catalyzed oxidative amidation for the synthesis of α-ketoamides has been successfully developed, which uses easily available O-benzoyl hydroxylamines as aminating reagent and oxidant. The reaction proceeds smoothly at room temperature and is compatible with a range of substrates to give the desired products in moderate to good yields.
- Shen, Guodong,Zhao, Lingyu,Wang, Yichen,Zhang, Tongxin
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p. 78307 - 78310
(2016/09/09)
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- Copper-TEMPO-catalyzed synthesis of α-ketoamides: Via tandem sp3C-H aerobic oxidation and amination of phenethyl alcohol derivatives
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An efficient copper-TEMPO-catalyzed one-pot synthesis of α-ketoamides from phenethyl alcohol derivatives was developed firstly. Moreover, molecular oxygen in open air was employed as the oxidant with a broad substrate scope, which makes this methodology more practical. Based on some control experiments, a plausible mechanism was proposed.
- Liu, Chengkou,Yang, Zhao,Guo, Shiyu,Zeng, Yu,Zhu, Ning,Li, Xin,Fang, Zheng,Guo, Kai
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supporting information
p. 8570 - 8575
(2016/09/28)
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- Copper-Catalyzed C?N Bond Formation via Oxidative Cross-Coupling of Amines with α-Aminocarbonyl Compounds
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A novel and selective method for the simple copper-catalyzed α-amination of α-aminocarbonyl compounds to afford 2-amino-2-iminocarbonyl and 2-amino-2-oxocarbonyl compounds is reported. This transformation is achieved by C(sp3)?H and N?H bond ox
- Liu, Xing-Xing,Wu, Zhao-Yang,He, Yong-Qin,Zhou, Xiao-Qiang,Hu, Ting,Ma, Chao-Wei,Huang, Guo-Sheng
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p. 2385 - 2391
(2016/08/16)
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- A two-step continuous synthesis of α-ketoamides and α-amino ketones from 2° benzylic alcohols using hydrogen peroxide as an economic and benign oxidant
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A practical two-step synthesis of α-ketoamides and α-amino ketones via direct oxidative coupling between 2° benzylic alcohols and amines was developed. Hydrogen peroxide, an economic and environmentally friendly oxidant, was used, and a metal catalyst was unnecessary. Moreover, the continuous-flow technique was employed to increase the functional group tolerance, efficiency and safety.
- Liu, Chengkou,Fang, Zheng,Yang, Zhao,Li, Qingwen,Guo, Shiyu,Guo, Kai
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p. 25167 - 25172
(2016/03/22)
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- Synthesis of α-Keto Amides by a Pyrrolidine/TEMPO-Mediated Oxidation of α-Keto Amines
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A mild procedure has been developed for the synthesis of α-keto amides by α-oxidation of the corresponding α-keto amines mediated by pyrrolidine and TEMPO. The method can also be applied to the synthesis of α-keto thioamides and α-keto amidines.
- Yu, Lu,Somfai, Peter
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supporting information
p. 2587 - 2590
(2016/11/11)
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- Copper-catalyzed, hypervalent iodine mediated C=C bond activation of enaminones for the synthesis of α-keto amides
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An unprecedented C=C bond cleavage of enaminones has been realized by means of copper catalysis in the presence of hypervalent iodine (PhI(OAc)2). The cascade transformation based on this bond cleavage leads to the synthesis of various α-keto amides. Isotope labeling experiments suggest that water has acted as a source of oxygen atoms during the generation of the new carbonyl group.
- Wan, Jie-Ping,Lin, Yunfang,Cao, Xiaoji,Liu, Yunyun,Wei, Li
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supporting information
p. 1270 - 1273
(2016/01/15)
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- Regioselective oxo-amination of alkenes and enol ethers with N-bromosuccinimide-dimethyl sulfoxide combination: A facile synthesis of α-amino-ketones and esters
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An unprecedented conversion of alkenes and enol ethers to the corresponding α-imido carbonyl compounds with excellent regioselectivity and yields has been developed. This oxo-amination process employs readily available N-bromosuccinimide (NBS) and secondary amines as N-sources and dimethyl sulfoxide (DMSO) as the oxidant and also leads to the production of amino alcohols in a single step on reduction, thus broadening the scope of this operationally simple reaction. For the first time, the formation of reactive Me2S+-O-Br species generated by the interaction of NBS with DMSO has been proven.
- Prasad, Pragati K.,Reddi, Rambabu N.,Sudalai, Arumugam
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supporting information
p. 500 - 503
(2016/02/18)
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- Covalent triazine framework-supported palladium as a ligand-free catalyst for the selective double carbonylation of aryl iodides under ambient pressure of CO
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Carbonylation of aryl iodides with amines under atmospheric pressure of CO, catalyzed by Pd/CTFs (covalent triazine frameworks) without any specific additives, leads to the highly selective synthesis of α-ketoamides.
- Wang, Zhifang,Liu, Cuibo,Huang, Yi,Hu, Yuchen,Zhang, Bin
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supporting information
p. 2960 - 2963
(2016/02/19)
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- Aminocatalytic cross-coupling approach via iminium ions to different C-C bonds
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Given the attractive ability of iminium ions to functionalize molecules directly at ostensibly unreactive positions, the reactivity of iminium ions, in which an α CH2 group is replaced by C=O was explored. Background studies on the ability of such iminium cations to promote reactions via an iminium-catalyzed or iminium-equivalent pathway are apparently unavailable. Previously, tandem cross-coupling reactions were reported, in which an iminium ion undergoes nucleophilic 1,2-addition to give a putative three-component intermediate that abstracts a proton in situ and undergoes self-deamination followed by unprecedented DMSO/ aerobic oxidation to generate a-ketoamides. However, later it was observed that iminium ions can generate valuable α-ketoamides through simple aerobic oxidation. In all reactions, iminium ions were generated in situ by reaction of 2-oxoaldehydes with secondary amines.
- Mupparapu, Nagaraju,Battini, Narsaiah,Battula, Satyanarayana,Khan, Shahnawaz,Vishwakarma, Ram A.,Ahmed, Qazi Naveed
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supporting information
p. 2954 - 2960
(2015/02/05)
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