- Selective hydrogenation dehalogenation method of ortho-halogenated acylaniline
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The invention discloses a selective hydrogenation dehalogenation method of copper-catalyzed ortho-halogenated acylaniline. The method comprises the following steps: by using ortho-halogenated acylaniline as a starting raw material and copper acetylacetonate/vasicine as a catalyst, adding an organic alkali, reacting in an alcoholic solution at 80-100 DEG C for 12 hours, and regioselectively catalytically hydrogenating ortho-bromine and iodine atoms. The preparation method has the characteristics of simplicity and convenience in operation, wide substrate application range, low cost, high regioselectivity and the like, and has practicability.
- -
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Paragraph 0024-0028
(2021/01/20)
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- Exploration of Cu-catalyzed regioselective hydrodehalogenation of o-haloanilides using EtOH as hydrogen source
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In present work, we have explored a Cu(acac)2/vasicine-catalyzed regioselective hydrodehalogenation methodology of o-haloanilides using EtOH as hydrogen source and solvent. The catalytic system could selectively dehalogenate 2-Br and 2-I, and features regioselective, efficient and functional group tolerance.
- Li, Min-Xin,Li, Mei-Ling,Tang, Yan-Ling,Sun, Yun,Qu, Lu,Huang, Feng,Mao, Ze-Wei
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supporting information
(2021/05/03)
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- A Convenient Stereoselective Method for Synthesis of β-Lactams Under Microwave Irradiation with [BmIm] OH as a Reusable Ionic Liquid
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A promoted synthetic protocol for the β-lactams synthesis in the presence of [BmIm]OH as a basic reagent under microwave irradiation [M.W.I.] is described. The reaction was highly diastereoselective. In all cases, this protocol provided trans-β-lactams as major isomers, and β-lactams were obtained with good yields. Further, the effect of the order of addition of the reagents was particularly investigated; we found that this order is very important. The best results are obtained when the imine is added gradually. This work shows that [BmIm]OH is an advantageous recyclable basic reagent. A qualitative molecular orbital diagram is illustrated to interpret the observed diastereoselectivity.
- Bendeddouche, Choukry K.,Bendeddouche, Souhila,Benhaoua, Hadj
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p. 929 - 935
(2022/03/01)
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- Photocatalyzed Triplet Sensitization of Oximes Using Visible Light Provides a Route to Nonclassical Beckmann Rearrangement Products
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Oximes are valuable synthetic intermediates for the preparation of a variety of functional groups. To date, the stereoselective synthesis of oximes remains a major challenge, as most current synthetic methods either provide mixtures of E and Z isomers or furnish the thermodynamically preferred E isomer. Herein we report a mild and general method to achieve Z isomers of aryl oximes by photoisomerization of oximes via visible-light-mediated energy transfer (EnT) catalysis. Facile access to (Z)-oximes provides opportunities to achieve regio- and chemoselectivity complementary to those of widely used transformations employing oxime starting materials. We show an enhanced one-pot protocol for photocatalyzed oxime isomerization and subsequent Beckmann rearrangement that enables novel reactivity with alkyl groups migrating preferentially over aryl groups, reversing the regioselectivity of the traditional Beckmann reaction. Chemodivergent N- or O- cyclizations of alkenyl oximes are also demonstrated, leading to nitrones or cyclic oxime ethers, respectively.
- Zhang, Xiao,Rovis, Tomislav
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p. 21211 - 21217
(2021/12/27)
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- An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
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Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
- Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
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p. 5627 - 5639
(2021/11/11)
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- Alpha-carbonyl alkenyl ester compound as well as preparation method and application thereof
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The invention provides an alpha-carbonyl alkenyl ester compound and a preparation method thereof. The alpha-carbonyl alkenyl ester compound is also used for reacting with primary or secondary amine to prepare an amide compound. Two steps of reactions are combined to develop an amido bond and peptide bond forming method which takes carboxylic acid and amine as starting raw materials and allene ketone as a condensing agent. Meanwhile, the alpha-carbonyl alkenyl ester compound of the alpha-amino acid is used as a polypeptide synthesis building block for solid-phase synthesis of polypeptide. The method is mild in reaction condition, simple to operate and high in yield. Compared with an existing amido bond condensation reagent, allene ketone has the advantages of being easy and convenient to prepare, good in stability, small in molecular weight and free of racemization when alpha-chiral carboxylic acid is activated and the like. The compound is a novel amido bond and peptide bond condensation reagent.
- -
-
Paragraph 0492-0497
(2021/08/25)
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- Allenone-Mediated Racemization/Epimerization-Free Peptide Bond Formation and Its Application in Peptide Synthesis
-
Allenone has been identified as a highly effective peptide coupling reagent for the first time. The peptide bond was formed with an α-carbonyl vinyl ester as the key intermediate, the formation and subsequent aminolysis of which proceed spontaneously in a racemization-/epimerization-free manner. The allenone coupling reagent not only is effective for the synthesis of simple amides and dipeptides but is also amenable to peptide fragment condensation and solid-phase peptide synthesis (SPPS). The robustness of the allenone-mediated peptide bond formation was showcased incisively by the synthesis of carfilzomib, which involved a rare racemization-/epimerization-free N to C peptide elongation strategy. Furthermore, the successful synthesis of the model difficult peptide ACP (65-74) on a solid support suggested that this method was compatible with SPPS. This method combines the advantages of conventional active esters and coupling reagents, while overcoming the disadvantages of both strategies. Thus, this allenone-mediated peptide bond formation strategy represents a disruptive innovation in peptide synthesis.
- Wang, Penghui,Wang, Xuewei,Wang, Zhengning,Zhao, Junfeng
-
supporting information
p. 10374 - 10381
(2021/07/26)
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- Iron-catalyzed oxidative amidation of acylhydrazines with amines
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A new approach for amide bond formation via a mild and efficient Iron-catalyzed cross-coupling reaction of acylhydrazines and amines using TBHP as oxidant is described. This protocol is compatible with a wide range of amines and acylhydrazines. In addition, the synthetic application of the reaction is presented.
- Wang, Yi-Jie,Zhang, Guo-Yu,Shoberu, Adedamola,Zou, Jian-Ping
-
supporting information
(2021/08/18)
-
- Tungsten-Catalyzed Transamidation of Tertiary Alkyl Amides
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Transamidation has recently emerged as a straightforward and convenient means to diversify amides. However, the kinetically and thermodynamically demanding transamidation of notoriously robust, fully alkyl-substituted tertiary amides still remains a longstanding challenge. Here, we describe a method for the activation of tertiary alkyl amides to streamline transamidation using simple tungsten(VI) chloride as a catalyst and chlorotrimethylsilane as an additive. The highly electrophilic and oxophilic tungsten catalyst enables the selective scission of a C-N bond of tertiary alkyl amides to effect transamidation of a myriad of structurally and electronically diverse tertiary alkyl amides and amines. Mechanistic study implies that the synergistic effect of the catalyst and the additive could pronouncedly induce the nucleophilic acyl substitution of tertiary alkyl amide with amine to realize transamidation.
- Feng, Fang-Fang,Liu, Xuan-Yu,Cheung, Chi Wai,Ma, Jun-An
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p. 7070 - 7079
(2021/06/30)
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- Copper-catalyzed transformation of alkyl nitriles to N -arylacetamide using diaryliodonium salts
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This work reports a simple and efficient method for the copper-catalyzed redox-neutral transformation of alkyl nitriles using eco-friendly diaryliodonium salts and leading to N-arylacetamides. The method features high efficiency, broad substrate scope and good functional group tolerance.
- Sallio, Romain,Payard, Pierre-Adrien,Pakulski, Pawe?,Diachenko, Iryna,Fabre, Indira,Berteina-Raboin, Sabine,Colas, Cyril,Ciofini, Ilaria,Grimaud, Laurence,Gillaizeau, Isabelle
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p. 15885 - 15889
(2021/05/19)
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- Palladium Catalyzed Aminocarbonylation of Benzylic Ammonium Triflates with Nitroarenes: Synthesis of Phenylacetamides
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A palladium catalyzed reductive aminocarbonylation of benzylic ammonium triflates with nitroarenes for the synthesis of phenylacetamides was developed. Using Pd(acac)2/DPPF catalyst system, a range of different substituted phenylacetamides were prepared in moderate to good yields from benzylic ammonium triflates and nitroarenes through Csp3?N bond cleavage. A variety of alkyl, aryl, and halide substituents on both substrates can be used, and many useful functional groups can be tolerated. (Figure presented.).
- Yang, Li-Miao,Li, Shan-Shan,Zhang, You-Ya,Lu, Jin-Liang,Deng, Jing-Tong,Ma, Ai-Jun,Zhang, Xiang-Zhi,Zhang, Shu-Yu,Peng, Jin-Bao
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p. 2061 - 2065
(2021/02/26)
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- Solar and visible-light active nano Ni/g-C3N4photocatalyst for carbon monoxide (CO) and ligand-free carbonylation reactions
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In this study, we investigate the amino and alkoxycarbonylation reaction between various substituted aryl halides, benzyl iodides, and iodocyclohexane with different types of amines and alcohols in the absence of carbon monoxide gas and ligands. Similar reactions are carried out at high temperatures, in the presence of appropriate ligands, stoichiometric amounts of bases, and gaseous carbon monoxide, which endanger the health of organic chemists. We present a novel method that does not utilize ligands, bases, gaseous CO, and special conditions. This procedure is a redox reaction carried out by new economic nano Ni/g-C3N4at room temperature and under visible light. Mo(CO)6was used toin situgenerate CO, to resolve the problems caused by the use of CO gas. This protocol has the ability to be used on a gram scale by using a continuous flow reactor.
- Hosseini-Sarvari, Mona,Akrami, Zahra
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p. 956 - 969
(2021/02/26)
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- Efficient nitriding reagent and application thereof
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The invention discloses an efficient nitriding reagent and application thereof, wherein the nitriding reagent comprises nitrogen oxide, an active agent, a reducing agent and an organic solvent. By applying the nitriding reagent, nitrogen-containing compounds such as amide, nitrile and the like can be produced, and the method is simple in condition, low in waste discharge amount and simple in reaction equipment.
- -
-
Paragraph 0186-0189
(2021/03/31)
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- Manganese Catalyzed Direct Amidation of Esters with Amines
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The transition metal catalyzed amide bond forming reaction of esters with amines has been developed as an advanced approach for overcoming the shortcomings of traditional methods. The broad scope of substrates in transition metal catalyzed amidations remains a challenge. Here, a manganese(I)-catalyzed method for the direct synthesis of amides from a various number of esters and amines is reported with unprecedented substrate scope using a low catalyst loading. A wide range of aromatic, aliphatic, and heterocyclic esters, even in fatty acid esters, reacted with a diverse range of primary aryl amines, primary alkyl amines, and secondary alkyl amines to form amides. It is noteworthy that this approach provides the first example of the transition metal catalyzed amide bond forming reaction from fatty acid esters and amines. The acid-base mechanism for the manganese(I)-catalyzed direct amidation of esters with amines was elucidated by DFT calculations.
- Fu, Zhengqiang,Wang, Xinghua,Tao, Sheng,Bu, Qingqing,Wei, Donghui,Liu, Ning
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p. 2339 - 2358
(2021/02/03)
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- Manganese(I) Catalyzed α-Alkenylation of Amides Using Alcohols with Liberation of Hydrogen and Water
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Herein, unprecedented manganese-catalyzed direct α-alkenylation of amides using alcohols is reported. Aryl amides are reacted with diverse primary alcohols, which provided the α,β-unsaturated amides in moderate to good yields with excellent selectivity. Mechanistic studies indicate that Mn(I) catalyst oxidizes the alcohols to their corresponding aldehydes and also plays an important role in efficient C═C bond formation through aldol condensation. This selective olefination is facilitated by metal-ligand cooperation by the aromatization-dearomatization process operating in the catalytic system. Biorenewable alcohols are used as alkenylation reagents for the challenging α-alkenylation of amides with the highly abundant base metal manganese as a catalyst, which results in water and dihydrogen as the only byproduct, making this catalytic transformation attractive, sustainable, and environmentally benign.
- Pandia, Biplab Keshari,Gunanathan, Chidambaram
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p. 9994 - 10005
(2021/07/31)
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- Efficient and accessible silane-mediated direct amide coupling of carboxylic acids and amines
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A straightforward method for the direct synthesis of amides from amines and carboxylic acids without exclusion of air or moisture using diphenylsilane with N-methylpyrrolidine has been developed. Various amides are made efficiently, and broad functional group compatibility is shown through a Glorius robustness study. A gram-scale synthesis demonstrates the scalability of this method. This journal is
- D'Amaral, Melissa C.,Jamkhou, Nick,Adler, Marc J.
-
supporting information
p. 288 - 295
(2021/01/28)
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- Efficient Pd-Catalyzed Hydrodehalogenation of o -Haloanilides in Water
-
In the present work, we have developed a practical methodology for the hydrodehalogenation of o -haloanilides using PdCl 2at 100 °C under mild conditions in water. The catalytic system could selectively dehalogenate both aryl chloride and aryl bromide and exhibit a broad functional group tolerance.
- Gao, Hui,Li, Minxin,Mao, Zewei,Rao, Gaoxiong,Tang, Yanling
-
supporting information
p. 1121 - 1125
(2020/07/03)
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- Copper-Catalyzed Radical N-Demethylation of Amides Using N-Fluorobenzenesulfonimide as an Oxidant
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An unprecedented N-demethylation of N-methyl amides has been developed by use of N-fluorobenzenesulfonimide as an oxidant with the aid of a copper catalyst. The conversion of amides to carbinolamines involves successive single-electron transfer, hydrogen-atom transfer, and hydrolysis, and is accompanied by formation of N-(phenylsulfonyl)benzenesulfonamide. Carbinolamines spontaneously decompose to N-demethylated amides and formaldehyde, because of their inherent instability.
- Yi, Xuewen,Yi, Xuewen,Lei, Siyu,Liu, Wangsheng,Che, Fengrui,Yu, Chunzheng,Liu, Xuesong,Wang, Zonghua,Zhou, Xin,Zhang, Yuexia
-
supporting information
p. 4583 - 4587
(2020/05/05)
-
- Direct synthesis of amides from nonactivated carboxylic acids using urea as nitrogen source and Mg(NO3)2or imidazole as catalysts
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A new method for the direct synthesis of primary and secondary amides from carboxylic acids is described using Mg(NO3)2·6H2O or imidazole as a low-cost and readily available catalyst, and urea as a stable, and easy to manipulate nitrogen source. This methodology is particularly useful for the direct synthesis of primary and methyl amides avoiding the use of ammonia and methylamine gas which can be tedious to manipulate. Furthermore, the transformation does not require the employment of coupling or activating agents which are commonly required.
- Blacker, A. John,Chhatwal, A. Rosie,Lomax, Helen V.,Marcé, Patricia,Williams, Jonathan M. J.
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p. 5808 - 5818
(2020/06/21)
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- An Efficient Palladium-Catalysed Aminocarbonylation of Benzyl Chlorides
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An improved procedure for the aminocarbonylation of benzyl chloride derivatives using carbon monoxide and either primary or secondary amines has been developed. Studying the competing background alkylation reaction allowed the solvent and base to be selected for a simple catalyst screen, which, in turn, enabled the discovery of a method for the preparation of 2-arylacetamides under mild conditions, with minimal side-products using an inexpensive phosphine ligand. This non-traditional optimisation strategy allowed us to overcome the background alkylation, which has been cited as justification for the development of more complex and less atom-economical approaches.
- Oram, Niall,Richardson, Jeffery,Rilvin-Derrick, Eloise
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p. 369 - 372
(2020/02/27)
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- Compound containing bipyrazole ring, intermediate thereof and application thereof
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The invention discloses a compound containing a bipyrazole ring, and an intermediate and application thereof. The invention provides the compound containing a bipyrazole ring, as shown in a formula Iwhich is described in the specification. The compound can be used as a ligand, is high in selectivity, and is suitable for the application range of amide in C-N coupling and the C-C coupling reactionof arylboronic acid and aryl chloride, especially coupling with aryl chloride.
- -
-
Paragraph 0251-0253
(2020/05/14)
-
- Preparation method of compound containing bipyrazole ring and intermediate thereof
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The invention discloses a preparation method of a compound containing a bipyrazole ring and an intermediate of the compound. The preparation method of a bipyrazole ring-containing compound as shown ina formula I comprises the following steps: (1) adding alkali into a mixture of a bipyrazole ring compound as shown in a formula I-1 and a solvent for replacement reaction to obtain a mixed system; and (2) adding an organic phosphorus compound shown as a formula I-2 into the mixed system in the step (1), and carrying out a phosphonation reaction shown in the specification, so as to obtain the bipyrazole ring-containing compound shown as the formula I, wherein R1 and R2 are independently a C1-C6 alkyl group, a C3-C8 cycloalkyl group and a phenyl group, R3 is a C1-C6 alkyl group, and X is halogen. The prepared compound containing a bipyrazole ring can be used as a ligand, and is suitable for the application range of amide in C-N coupling and the C-C coupling reaction of arylboronic acid andaryl chloride.
- -
-
Paragraph 0251-0253
(2020/05/14)
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- BF3·OEt2-promoted tandem Meinwald rearrangement and nucleophilic substitution of oxiranecarbonitriles
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Tandem Meinwald rearrangement and nucleophilic substitution of oxiranenitriles was realized. Arylacetic acid derivatives were readily synthesized from 3-aryloxirane-2-carbonitriles with amines, alcohols, or water in the presence of boron trifluoride under microwave irradiation, and the designed synthetic strategy includes introducing a cyano leaving group into arylepoxides and capturing the in situ generated toxic cyanide with boron trifluoride, making the reaction efficient, safe, and environmentally benign. The reaction occurs through an acid-promoted Meinwald rearrangement, producing arylacetyl cyanides, followed by an addition-elimination process with nitrogen or oxygen-containing nucleophilic amines, alcohols or water. The current method provides a new application of the tandem Meinwald rearrangement.
- Xu, Chuangchuang,Xu, Jiaxi
-
p. 127 - 134
(2019/12/26)
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- Visible Light-Induced Amide Bond Formation
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A metal-, base-, and additive-free amide bond formation reaction was developed under an organic photoredox catalyst. This green approach showed excellent functional selectivity without affecting other functional groups such as alcohols, phenols, ethers, esters, halogens, or heterocycles. This method featured a broad substrate scope, good compatibility with water and air, and high yields (≤95%). The potential utilities were demonstrated by the synthesis of important drug molecules such as paracetamol, melatonin, moclobemide, and acetazolamide.
- Song, Wangze,Dong, Kun,Li, Ming
-
supporting information
p. 371 - 375
(2019/11/29)
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- Method for preparing amide by visible light-induced metal-free participation (by machine translation)
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The method for preparing the amide in the, preparation method of the novel amide disclosed by the invention has the advantages that, the reaction: conditions are mild, the 9 - reaction conditions are mild, and the yield 71%. of the reaction conditions is not lower than the reaction conditions . (by machine translation)
- -
-
Paragraph 0079-0082
(2020/02/14)
-
- An Electrochemical Beckmann Rearrangement: Traditional Reaction via Modern Radical Mechanism
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Abstract: Electrosynthesis as a potential means of introducing heteroatoms into the carbon framework is rarely studied. Herein, the electrochemical Beckmann rearrangement, i. e. the direct electrolysis of ketoximes to amides, is presented for the first time. Using a constant current as the driving force, the reaction can be easily carried out under neutral conditions at room temperature. Based on a series of mechanistic studies, a novel radical Beckmann rearrangement mechanism is proposed. This electrochemical Beckmann rearrangement does not follow the trans-migration rule of the classical Beckmann rearrangement.
- Tang, Li,Wang, Zhi-Lv,He, Yan-Hong,Guan, Zhi
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p. 4929 - 4936
(2020/08/21)
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- Nitromethane as a nitrogen donor in Schmidt-type formation of amides and nitriles
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The Schmidt reaction has been an efficient and widely used synthetic approach to amides and nitriles since its discovery in 1923. However, its application often entails the use of volatile, potentially explosive, and highly toxic azide reagents. Here, we report a sequence whereby triflic anhydride and formic and acetic acids activate the bulk chemical nitromethane to serve as a nitrogen donor in place of azides in Schmidt-like reactions. This protocol further expands the substrate scope to alkynes and simple alkyl benzenes for the preparation of amides and nitriles.
- Jiao, Ning,Liu, Jianzhong,Qiu, Xu,Song, Song,Wei, Jialiang,Wen, Xiaojin,Zhang, Cheng,Zhang, Ziyao
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supporting information
p. 281 - 285
(2020/01/28)
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- Direct amide formation in a continuous-flow system mediated by carbon disulfide
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Amide bonds are ubiquitous in nature. They can be found in proteins, peptides, alkaloids, etc. and they are used in various synthetic drugs too. Amide bonds are mainly made by the use of (i) hazardous carboxylic acid derivatives or (ii) expensive coupling agents. Both ways make the synthetic technology less atom economic. We report a direct flow-based synthesis of amides. The developed approach is prominently simple and various aliphatic and aromatic amides were synthetized with excellent yields. The reaction in itself is carried out in acetonitrile, which is considered as a less problematic dipolar aprotic solvent. The used coupling agent, carbon disulfide, is widely available and has a low price. The utilized heterogeneous Lewis acid, alumina, is a sustainable material and it can be utilized multiple times. The technology is considerably robust and shows excellent reusability and easy scale-up is carried out without the need of any intensive purification protocols.
- Orsy, Gy?rgy,Fül?p, Ferenc,Mándity, István M.
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p. 7814 - 7818
(2020/12/28)
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- Synthesis of α-ketoamides using potassium superoxide (KO2) as an oxidizing agent
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A simple and convenient method for the synthesis of α-ketoamides by the oxidation of aryl acetamides using potassium superoxide (KO2) as an oxidizing agent is disclosed here. The scope of the developed method is successfully tested with fifteen substrates. In addition, the utility of method has been demonstrated by synthesizing an orexin receptor antagonist, a medicinally interesting compound.
- Vasudevan,Routholla, Ganesh,Teja Illa, Giri,Reddy, D. Srinivasa
-
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- Phenysilane and Silicon Tetraacetate: Versatile Promotors for Amide Synthesis
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Phenylsilane was reevaluated as a useful coupling reagent for amide synthesis. At room temperature, a wide range of amides and peptides were obtained in good to excellent yields (up to 99 %). For the first time, Weinreb amides synthesis mediated by a hydrosilane were also documented. Comparative experiments with various acetoxysilanes suggested the involvement of a phenyl-triacyloxysilane. From this mechanistic study, silicon tetraacetate was shown as an efficient amine acylating agent.
- Morisset, Eléonore,Chardon, Aurélien,Rouden, Jacques,Blanchet, Jér?me
-
supporting information
p. 388 - 392
(2020/01/24)
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- Visible-light-induced Beckmann rearrangement by organic photoredox catalysis
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A facile and general strategy for efficient direct conversion of oximes to amides using an inexpensive organic photocatalyst and visible light is described. This radical Beckmann rearrangement can be performed under mild conditions. Various alkyl aryl ketoximes and diaryl ketoximes can be effectively converted into the corresponding amides in excellent yields.
- Tang, Li,Wang, Zhi-Lv,Wan, Hai-Lan,He, Yan-Hong,Guan, Zhi
-
supporting information
p. 6182 - 6186
(2020/09/01)
-
- Ruthenium-Catalyzed Oxidative Amidation of Alkynes to Amides
-
Complex CpRuCl(PPh3)2 catalyzes reactions of terminal alkynes with 4-picoline N-oxide and primary and secondary amines to afford the corresponding amides. The reactions occur in chlorinated solvent and aqueous medium, showing applications in peptide chemistry. Stoichiometric studies reveal that the true catalysts of the processes are the vinylidene cations [CpRu(=C=CHR)(PPh3)2]+ which are oxidized to the Ru(η2-CO)-ketenes by the N-oxide. Finally, nucleophilic additions of primary and secondary amines to the free ketenes yield the corresponding amides.
- álvarez-Pérez, Andrea,Esteruelas, Miguel A.,Izquierdo, Susana,Varela, Jesús A.,Saá, Carlos
-
supporting information
p. 5346 - 5350
(2019/07/08)
-
- Iodine-mediated aryl transfer reaction from arylhydrazine hydrochlorides to nitriles
-
An iodine-promoted, metal-, base-, and solvent-free cross-coupling reaction was developed for the synthesis of various useful secondary amides via an aryl N-addition reaction of aryl groups to cyano groups. This aryl transfer reaction proceeds with arylhydrazine hydrochlorides serving as the aryl donors. A labelling experiment shows that the N atom in the product comes from the cyano group of the nitriles, which are low in cost. A plausible radical-driven mechanism is also proposed.
- Zhang, Zhiguo,Li, Xiang,Li, Yinghua,Guo, Yan,Zhao, Xunan,Yan, Yan,Sun, Kai,Zhang, Guisheng
-
supporting information
p. 3628 - 3635
(2019/05/29)
-
- o-Phthalic Anhydride/Zn(OTf)2 co-catalyzed Beckmann rearrangement under mild conditions
-
o-Phthalic anhydride/Zn(OTf)2 co-catalyzed Beckmann rearrangement was developed, producing the corresponding amide in up to 99% yield with acid-sensitive functionalities tolerated well, and the scale of the reaction could be enlarged to 77 mmol and the excellent yield was maintained. A successive procedure was developed. Moreover, the reaction was carried out at rt under nearly neutral conditions, and the workup was concise. These features illustrated the potential of the protocol in amide synthesis.
- Xu, Ze-Feng,Zhang, Teng,Hong, Wenjun
-
supporting information
p. 3113 - 3117
(2019/05/08)
-
- A solid-supported arylboronic acid catalyst for direct amidation
-
An efficient heterogeneous amidation catalyst has been prepared by co-polymerisation of styrene, DVB with 4-styreneboronic acid, which shows wide substrate applicability and higher reactivity than the equivalent homogeneous phenylboronic acid, suggesting potential cooperative catalytic effects. The catalyst can be easily recovered and reused; suitable for use in packed bed flow reactors.
- Du, Yihao,Barber, Thomas,Lim, Sol Ee,Rzepa, Henry S.,Baxendale, Ian R.,Whiting, Andrew
-
supporting information
p. 2916 - 2919
(2019/03/27)
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- Chromium-Catalyzed Activation of Acyl C-O Bonds with Magnesium for Amidation of Esters with Nitroarenes
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Here, we report a chromium-catalyzed activation of acyl C-O bonds with magnesium for amidation of esters with nitroarenes. Low-cost chromium(III) chloride shows high reactivity in promoting amidation by using magnesium as reductant and chlorotrimethylsilane as additive. It provides a step-economic strategy to the synthesis of centrally important amide motifs using inexpensive and air-stable nitroarenes as amino sources.
- Ling, Liang,Chen, Changpeng,Luo, Meiming,Zeng, Xiaoming
-
supporting information
(2019/03/19)
-
- Hydrative syntheses of amides from alkynes catalyzed by an Au(I) complex containing pyridyl-functionalized NHC ligand
-
An Au(I)-NHC complex [L1AuBr] (1) with appended pyridyl group on the ligand scaffold is synthesized and its catalytic efficacy for the direct synthesis of the amide from alkyne and sodium azide in acidic water is evaluated. Catalyst 1 readily converts a wide range of internal and terminal alkynes to the corresponding amides with low catalyst loading in TFA/DCE (2 mL, 1:1 v/v) at room temperature in short reaction time (2 h) and without the use of Ag(I) additive. A related catalyst that is devoid of the pyridyl fragment displays significantly lower activity illustrating the role of the promoter ligand for water activation. Mechanistic studies reveal an initial alkyne hydration to ketone followed by the Schmidt reaction to afford the amide.
- Singh, Kuldeep,Pal, Nilay Kumar,Guha, Chirajyoti,Bera, Jitendra K.
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-
- Cu-mediated selective bromination of aniline derivatives and preliminary mechanism study
-
A simple and efficient bromination of aniline, aniline derivatives, and analogs have been developed. Forty three examples were given and the highest yield reached was 98%. Different substrates including substituted aniline, pyridin-amine, N-substituted aniline, N,N-disubstituted aniline, N-phenyl-amide, N-phenyl-sulfonamide, and nitrogen-containing heterocycles were all reactive and selectively generated desired bromo-products. The method can be applied to synthesize drug intermediate and quinoxaline derivatives.
- Zhao, Hong-Yi,Yang, Xue-Yan,Lei, Hao,Xin, Minhang,Zhang, San-Qi
-
supporting information
p. 1406 - 1415
(2019/05/01)
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- Nickel (II)-Catalyzed efficient aminocarbonylation of unreactive alkanes with formanilides—Exploiting the deformylation behavior of imides
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Challenging functionalization of C(sp3)-H has recently attracted much attention of organic chemists. In this paper, we developed a Ni(acac)2-catalyzed activation of unreactive alkanes with formanilides in the presence of carbon monoxide to furnish moderate to excellent yields of amides. This is the first example of aminocarbonylation of inert alkanes using nickel-based catalyst, and formanilides is disclosed to be an interesting amine source owing to the peculiar deformylation nature of imide intermediates.
- Han, Zhang,Chaowei, Dai,Lice, Liu,Hongfei, Ma,Hongzhong, Bu,Yufeng, Li
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p. 3712 - 3718
(2018/05/29)
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- [Co(MeTAA)] Metalloradical Catalytic Route to Ketenes via Carbonylation of Carbene Radicals
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An efficient synthetic strategy towards beta-lactams, amides, and esters involving “in situ” generation of ketenes and subsequent trapping with nucleophiles is presented. Carbonylation of carbene radical intermediates using the cheap and highly active cobalt(II) tetramethyltetraaza[14]annulene catalyst [Co(MeTAA)] provides a convenient one-pot synthetic protocol towards substituted ketenes. N-tosylhydrazones are used as carbene precursors, thereby bridging the gap between aldehydes and ketenes. Activation of these carbene precursors by the metalloradical cobalt(II) catalyst affords CoIII-carbene radicals, which subsequently react with carbon monoxide to form ketenes. In the presence of a nucleophile (imine, alcohol, or amine) in the reaction medium the ketene is immediately trapped, resulting in the desired products in a one-pot synthetic protocol. The β-lactams formed upon reaction with imines are produced in a highly trans-selective manner.
- Chirila, Andrei,van Vliet, Kaj M.,Paul, Nanda D.,de Bruin, Bas
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p. 2251 - 2258
(2018/04/09)
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- Palladium-catalyzed carbonylation of benzylic ammonium salts to amides and esters: Via C-N bond activation
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An efficient palladium-catalyzed carbonylation reaction of readily available quaternary ammonium salts with CO is reported for the first time to afford arylacetamides and arylacetic acid esters via benzylic C-N bond cleavage. This protocol features mild reaction conditions under atmospheric pressure of CO, a redox-neutral process without an additional oxidant, and a broad substrate scope for various kinds of amines, alcohols and phenols.
- Yu, Weijie,Yang, Shuwu,Xiong, Fei,Fan, Tianxiang,Feng, Yan,Huang, Yuanyuan,Fu, Junkai,Wang, Tao
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p. 3099 - 3103
(2018/05/22)
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- Direct synthesis of N-arylamides via the coupling of aryl diazonium tetrafluoroborates and nitriles under transition-metal-free conditions
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The direct synthesis of N-arylamides via the coupling of aryl diazonium tetrafluoroborates and nitriles under transition-metal-free conditions has been developed. The reported protocol is practical and represents an efficient method to produce functionalized amides in moderate to good yields.
- Xiong, Biquan,Wang, Gang,Xiong, Tao,Wan, Liming,Zhou, Congshan,Liu, Yu,Zhang, Panliang,Yang, Changan,Tang, Kewen
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supporting information
p. 3139 - 3142
(2018/07/13)
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- Synthesis of acetamide derivatives using S-MWCNT and S-MC as an efficient heterogeneous catalysts
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Sulphate modified multiwalled carbon nanotubes (S-MWCNT) and Mesoporous carbon (S-MC) catalysts were prepared by wet impregnation method. These materials were characterized by different analytical techniques such as Powder-XRD, BET surface area analysis, SEM-EDS and TEM analysis to evaluate their bulk and surface properties. Surface acidity of the catalyst was measured by TPD-NH3 technique, as well as n-butyl amine titration. The estimated surface acidity of S-MWCNT and S-MC using n-butyl amine titration was found to be 0.82 and 1.75 mmol/g respectively. The catalytic activity of these materials was investigated in the synthesis of acetamide derivatives using aromatic acids with substituted aromatic amines in a liquid phase reaction. The reaction conditions were optimized to achieve good % yield of the products. In general S-MC catalyst exhibited good catalytic activity and gave higher % yield of the respective acetamides than S-MWCNT. This is attributed to higher surface acidity of S-MC, however the catalyst was found to be non-recyclable. S-MWCNT exhibited moderate % yield and 100% selectivity towards the formation of products. S-MWCNT catalyst was recycled up to 5 times with a consistent % yield of the respective acetamide derivatives. The synthesized acetamide derivatives were analyzed by M.P, 1HNMR techniques.
- Minchitha,Hareesh,Nagaraju,Kathyayini
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p. 426 - 433
(2017/12/12)
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- Repurposing n-butyl stannoic acid as highly efficient catalyst for direct amidation of carboxylic acids with amines
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This is the first-time report on the repurposing n-butyl stannoic acid as a catalyst for direct amidation of carboxylic acids with amines. Notably, efficient amidation observed in comparison with all other catalytic methods reported up until now. The protocol has successfully applied to the synthesis of a variety of amides. Moderate reaction parameters, clean amidation with excellent yields of desired amides, ability to tolerate a variety of functional groups, easy product isolation; commercial availability and recyclability of the catalyst are key advantages of the current protocol.
- Potadar, Santoshkumar M.,Mali, Anil S.,Waghmode, Krishnakant T.,Chaturbhuj, Ganesh U.
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supporting information
p. 4582 - 4586
(2018/11/27)
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- Hypervalent Iodine(III)-Promoted Phenyl Transfer Reaction from Phenyl Hydrazides to Nitriles
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A useful transformation of nitriles to N-phenyl amides has been achieved through a novel intermolecular phenyl transfer reaction from phenyl hydrazides and N-addition to nitriles in the presence of PIFA under mild and solvent-free conditions. This cross-coupling reaction includes the oxidative cleavage of sp2 C-N bonds of phenyl hydrazides to form a phenyl radical and the subsequent N-addition to cyanos to form new sp2 C-N bonds and provides efficient access to various N-phenyl amides in moderate to good yields under mild reaction conditions.
- Yan, Yan,Zhang, Zhiguo,Wan, Yameng,Zhang, Guisheng,Ma, Nana,Liu, Qingfeng
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supporting information
p. 7957 - 7963
(2017/08/14)
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- Efficient Heterogeneous Gold(I)-Catalyzed Direct C(sp2)–C(sp) Bond Functionalization of Arylalkynes through a Nitrogenation Process to Amides
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The first heterogeneous gold(I)-catalyzed direct C(sp2)–C(sp) bond functionalization of arylalkynes through a nitrogenation process to amides has been achieved by using an ordered mesoporous silica (MCM-41)-immobilized phosphine gold(I) complex [MCM-41-PPh3-AuCl] as catalyst and silver carbonate (Ag2CO3) as cocatalyst with trimethylsilyl azide (TMSN3) as a nitrogen source, yielding a variety of amides in moderate to excellent yields under mild conditions. This heterogeneous phosphine gold(I) complex shows the same turnover numbers as the homogeneous chloro(triphenylphosphine)gold(I) (Ph3PAuCl) and can easily be recovered by simple filtration of the reaction solution and recycled at least eight times without significant loss of activity, providing a novel, efficient, practical and economic method for the synthesis of amides from alkynes. (Figure presented.).
- Nie, Quan,Yi, Feiyan,Huang, Bin,Cai, Mingzhong
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p. 3968 - 3976
(2017/11/20)
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- Methods for preparing amide compounds using alkynes and methods for preparing peptides using the same
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The present invention relates to a method for preparing an amide compound, which comprises a step of agitating an alkyne and an N-hydroxy compound in an organic solvent in the presence of a transition metal catalyst to form an amide bond, and a method for preparing a peptide using the same. According to the present invention, the amidation reaction does not depend on polar reactivity, such as the conventional simple nucleophilicity and electrophilicity, but is based on a reaction derived from coordination reactivity between an alkyne and a transition metal, and thus shows excellent chemical selectivity. In addition, the method does not require a consumptive step such as attachment and detachment of a protecting group but includes a simple process during the synthesis of a peptide. Thus, the method is very effective for preparing a polypeptide compound. The method also has 100% of atomic economic efficiency since the starting materials are not lost during the reaction.COPYRIGHT KIPO 2017
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Paragraph 0107-0109; 0172-0174; 0180-0182
(2017/09/21)
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- Diphenylsilane as a coupling reagent for amide bond formation
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A simple procedure for amide bond formation using diphenylsilane as a coupling reagent is described. This methodology enables the direct coupling of carboxylic acids with primary and secondary amines, releasing only hydrogen and a siloxane as by-products. Only one equivalent of each partner is needed, providing a more sustainable amidation method producing minimal wastes. This methodology was also extended to the synthesis of peptides and lactams by addition of Hünig's base (DIPEA) and 4-dimethylaminopyridine (DMAP).
- Sayes, Morgane,Charette, André B.
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supporting information
p. 5060 - 5064
(2017/11/09)
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- Novel green acylamide synthesis method through quaternary ammonium salt C-N bond fracture
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The invention provides a novel green acylamide synthesis method through quaternary ammonium salt C-N bond fracture. The structure of the compound is expressed by methods such as H NMR, C, NMR and HRMS and is confirmed. A series of phenmethyl quaternary ammonium salts and aminated compounds are used; under the catalysis effect of PdCl2(dppf), PPh3 is used as a ligand, Na2CO3 is used as the alkali, and corresponding amide compounds are generated in the 100-DEG C CO atmosphere in a pHMe/DMSO mixed solvent. The method has the advantages that the efficiency is high; the toxicity is low; the conditions are mild; the application range of the substrate is wide; the yield is high; the product purity is high; the separation is convenient; the method can be applicable to large-scale preparation; the application prospects are wide.
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Paragraph 0020-0022
(2017/04/19)
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- Amine Activation: Synthesis of N-(Hetero)arylamides from Isothioureas and Carboxylic Acids
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A novel method for N-(hetero)arylamide synthesis based on rarely explored amine activation, rather than classical acid activation, is reported. The activated amines are easily prepared using a three-component reaction with commercial reagents. The new method shows a broad scope including challenging amides not (efficiently) accessible via classical protocols.
- Zhu, Yan-Ping,Sergeyev, Sergey,Franck, Philippe,Orru, Romano V. A.,Maes, Bert U. W.
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supporting information
p. 4602 - 4605
(2016/09/28)
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