- Pd(OAc)2/AgOAc catalytic system based bidentate ligand directed regiocontrolled C-H arylation and alkylation of the C-3 position of thiophene- and furan-2-carboxamides
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A contemporary method is reported for the Pd(OAc)2/AgOAc catalytic system based bidentate ligand directed, regioselective C-H activation and C-C bond formation at the C-3 position of thiophene- and furan-2-carboxamides, which are derived from 8
- Padmavathi, Rayavarapu,Sankar, Rathinam,Gopalakrishnan, Bojan,Parella, Ramarao,Babu, Srinivasarao Arulananda
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- Nickel-Catalyzed Reductive Cross-Coupling of N-Acyl and N-Sulfonyl Benzotriazoles with Diverse Nitro Compounds: Rapid Access to Amides and Sulfonamides
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Herein we report a Ni-catalyzed reductive transamidation of conveniently available N-acyl benzotriazoles with alkyl, alkenyl, and aryl nitro compounds, which afforded various amides with good yields and a broad substrate scope. The same catalytic reaction conditions were also applicable for N-sulfonyl benzotriazoles, which could undergo smooth reductive coupling with nitroarenes and nitroalkanes to afford the corresponding sulfonamides.
- Qu, Erdong,Li, Shangzhang,Bai, Jin,Zheng, Yan,Li, Wanfang
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supporting information
p. 58 - 63
(2021/12/27)
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- A practical and sustainable protocol for direct amidation of unactivated esters under transition-metal-free and solvent-free conditions
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In this paper, a NaOtBu-mediated synthesis approach was developed for direct amidation of unactivated esters with amines under transition-metal-free and solvent-free conditions, affording a series of amides in good to excellent yields at room temperature. In particular, an environmentally friendly and practical workup procedure, which circumvents the use of organic solvents and chromatography in most cases, was disclosed. Moreover, the gram-scale production of representative products3a,3wand3auwas efficiently realized by applying operationally simple, sustainable and practical procedures. Furthermore, this approach was also applicable to the synthesis of valuable molecules such as moclobemide (a powerful antidepressant), benodanil and fenfuram (two commercial agricultural fungicides). These results demonstrate that this protocol has the potential to streamline amide synthesis in industry. Meanwhile, quantitative green metrics of all the target products were evaluated, implying that the present protocol is advantageous over the reported ones in terms of environmental friendliness and sustainability. Finally, additional experiments and computational calculations were carried out to elucidate the mechanistic insight of this transformation, and one plausible mechanism was provided on the basis of these results and the related literature reports.
- Chen, Cheng,Cheng, Hua,Du, Min-Chen,Qian, Liang,Qin, Xin,Sang, Wei,Yao, Wei-Zhong,Yuan, Ye,Zhang, Rui
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supporting information
p. 3972 - 3982
(2021/06/17)
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- Visible-Light-Promoted Iron-Catalyzed N-Arylation of Dioxazolones with Arylboronic Acids
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A visible-light-promoted and simple iron salt-catalyzed N-arylation was achieved efficiently under external photosensitizer-free conditions. Arylboronic acids and bench-stable dioxazolones were used for this cross-coupling reaction. This reaction features high reactivity, wide substrate scope, good functional group tolerance, simple operation procedure, and mild reaction conditions. Preliminary mechanistic investigations were conducted to support a radical pathway. This method may contribute to shift the paradigm of iron-catalyzed C-N bond construction and nitrene transfer chemistry.
- Tang, Jing-Jing,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
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p. 13955 - 13961
(2021/11/20)
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- Fe-mediated synthesis of: N -aryl amides from nitroarenes and acyl chlorides
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Amides are prevalent in nature and valuable functional compounds in agrochemical, pharmaceutical, and materials industries. In this work, we developed a selective and mild method for the synthesis of N-aryl amides. Starting from commercially available nitroarenes and acyl halides, N-aryl amides with good yields can be obtained in water. Especially in the process of transformation, Fe dust is the only reductant and additive, and the reaction can be easily performed on a large scale.
- Wu, Yundong,Guo, Lei,Liu, Yuxuan,Xiang, Jiannan,Jiang, Jun
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p. 15290 - 15295
(2021/05/19)
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- Chromium-catalyzed ligand-free amidation of esters with anilines
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Amides are important structural motifs in pharmaceutical and agrochemical chemistry because of the intriguing biological active properties. We report here the amidation of commercially available esters with anilines that was promoted by low-cost and air-stable chromium(III) pre-catalyst combined with magnesium, providing access to amides. This reaction occurs without the use of external ligands in a simple operation. Mechanistic studies indicate that a reactive aminated Cr species responsible for the amidation can be considered, which may be formed by reaction of low-valent Cr with aniline followed by reduction with hydrogen evolution.
- Chen, Changpeng,Ling, Liang,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 762 - 766
(2021/04/14)
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- A metal-free picolinamide assisted electrochemical ortho-trifluoromethylation of arylamines
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An eco-friendly and effective electrochemical process was developed for the ortho-trifluoromethylation of arylamines using CF3SO2Na as the trifluoromethyl source, affording the desired products in moderate to good yields with high regioselectivity under mild reaction conditions. Importantly, the requirement for both transition metals and oxidants utilized in previous methods were avoided. A radical mechanism was proposed on the basis of various control experiments.
- Wang, Kai,Hou, Jiahao,Wei, Tingting,Zhang, Changjun,Bai, Renren,Xie, Yuanyuan
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supporting information
(2020/12/21)
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- Simple Synthesis of Amides via Their Acid Chlorides in Aqueous TPGS-750-M
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The technology of surfactant chemistry is employed for amide bond construction via the reaction of acyl chlorides with amines in 2 wt % TPGS-750-M aqueous solution. Specifically, this highly efficient method enables a chromatography-free scalable process and recycling of the TPGS-750-M solution.
- Shi, Min,Ye, Ning,Chen, Wei,Wang, Hui,Cheung, Chiming,Parmentier, Michael,Gallou, Fabrice,Wu, Bin
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supporting information
p. 1543 - 1548
(2020/11/23)
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- Synthesis of amides from acid chlorides and amines in the bio-based solvent Cyrene
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Cyrene as a bio-alternative dipolar aprotic solvent: a waste minimizing and molar efficient protocol for the synthesis of amides from acid chlorides and primary amines in the bio-available solvent Cyrene is disclosed. This protocol removed the use of toxic solvents, such as dimethylformamide and dichloromethane. A simple aqueous work-up procedure for the removal of the high boiling solvent Cyrene resulted in up to a 55-fold increase in molar efficiency (Mol E.%) versus standard operating procedures. In order to rapidly compare the molar efficiency of this process against other methodologies an Excel based Mol. E% calculator was developed that automates many of the calculations. An investigation into the hydration of Cyrene found that it readily hydrates to form a geminal diol in the presence of water and that this process is exothermic.
- Bousfield, Thomas W.,Pearce, Katharine P. R.,Nyamini, Simbarashe B.,Angelis-Dimakis, Athanasios,Camp, Jason E.
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supporting information
p. 3675 - 3681
(2019/07/09)
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- Iodine-mediated aryl transfer reaction from arylhydrazine hydrochlorides to nitriles
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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
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supporting information
p. 3628 - 3635
(2019/05/29)
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- Solvent- and transition metal-free amide synthesis from phenyl esters and aryl amines
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A general, economical, and environmentally friendly method of amide synthesis from phenyl esters and aryl amines was developed. This new method has significant advantages compared to previously reported palladium-catalyzed approaches. The reaction is performed transition metal- and solvent-free, using a cheap and environmentally benign base, NaH. This approach enabled us to obtain target amides in high yields with high atom economy.
- Rzhevskiy, Sergey A.,Ageshina, Alexandra A.,Chesnokov, Gleb A.,Gribanov, Pavel S.,Topchiy, Maxim A.,Nechaev, Mikhail S.,Asachenko, Andrey F.
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p. 1536 - 1540
(2019/01/24)
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- Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
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The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
- Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
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p. 4087 - 4101
(2019/04/30)
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- Combining Eosin y with Selectfluor: A Regioselective Brominating System for Para-Bromination of Aniline Derivatives
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A mild, metal-free, and absolutely para-selective bromination of aniline derivatives has been developed in excellent yields, wherein the organic dye Eosin Y is employed as the bromine source in company with Selectfluor. Neither air nor moisture sensitive, this facile reaction proceeds smoothly at room temperature and completes within a short time. Mechanistic studies indicate a radical pathway; therefore, the existence of an in situ generated brominating reagent, "Selectbrom", is postulated, which may reasonably account for the unique regioselectivity for the para-bromination of N-acyl- as well as N-sulfonylanilines.
- Huang, Binbin,Zhao, Yating,Yang, Chao,Gao, Yuan,Xia, Wujiong
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supporting information
p. 3799 - 3802
(2017/07/26)
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- Amide compound with antitumor activity and application of amide compound
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The invention belongs to the technical field of pharmaceutical chemistry and particularly provides an amide compound with antitumor activity and application of the amide compound. The structural formula of the amide compound is shown as R1CONHR2, wherein R1 and R2 are independently selected from aryl or heterocycle. The biological activity test result of the compound shows that the compound has a good inhibition effect on histone methyl SET7. Good antitumor aspect development application prospects are achieved.
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Paragraph 0056; 0057; 0058; 0059; 0060
(2017/08/02)
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- Pd-PEPPSI: A general Pd-NHC precatalyst for Buchwald-Hartwig cross-coupling of esters and amides (transamidation) under the same reaction conditions
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Amides are of fundamental interest in many fields of chemistry involving organic synthesis, chemical biology and biochemistry. Here, we report the first catalytic Buchwald-Hartwig coupling of both common esters and amides by highly selective C(acyl)-X (X = O, N) cleavage to rapidly access aryl amide functionality via a cross-coupling strategy. Reactions are promoted by versatile, easily prepared, well-defined Pd-PEPPSI type precatalysts, and proceed in good to excellent yields and with excellent chemoselectivity for the acyl bond cleavage. The method is user friendly because it employs commercially-available, moisture- and air-stable precatalysts. Notably, for the first time we demonstrate selective C(acyl)-N and C(acyl)-O cleavage/Buchwald-Hartwig amination under the same reaction conditions, which allows for streamlining amide synthesis by avoiding restriction to a particular acyl metal precursor. Of broad interest, this study opens the door to using a family of well-defined Pd(ii)-NHC precatalysts bearing pyridine "throw-away" ligands for the selective C(acyl)-amination of bench-stable carboxylic acid derivatives.
- Shi, Shicheng,Szostak, Michal
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supporting information
p. 10584 - 10587
(2017/09/29)
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- A Cross-Coupling Approach to Amide Bond Formation from Esters
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A palladium-catalyzed cross-coupling between aryl esters and anilines is reported, enabling access to diverse amides. The reaction takes place via activation of the C-O bond by oxidative addition with a Pd-NHC complex, which enables the use of relatively non-nucleophilic anilines that otherwise require stoichiometric activation with strong bases in order to react. High yields of aromatic, aliphatic, and heterocyclic products are obtained. A range of activated esters are evaluated in the presence and absence of catalyst, demonstrating that the catalytic methodology substantially increases the types of electrophiles that can be utilized for amide bond formation in the absence of harsh bases.
- Ben Halima, Taoufik,Vandavasi, Jaya Kishore,Shkoor, Mohanad,Newman, Stephen G.
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p. 2176 - 2180
(2017/08/09)
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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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- 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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- Copper(II) incorporated functionalized polystyrene catalyzed: N -arylation of amides under solvent free condition with broad substrate scope
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We demonstrate here, a new polystyrene supported Cu(ii) catalyzed proficient synthetic methodology for the facile N-arylation of aromatic, aliphatic, cyclic and heterocyclic amides with aryl halides under neat conditions. The catalyst, PS-Cu(ii)-ala, was prepared through the grafting of copper metal on a polystyrene-β-alanine imine network. The catalyst shows a wide range of substrate scope and excellent functional group tolerance, and produces the desired anilides in mostly high yields. The material is thoroughly characterized by DRS-UV, FT-IR, AAS, FE-SEM, TGA analysis and energy dispersive X-ray (EDX) studies. The catalyst can be easily recovered from the reaction medium and reused without significant loss of its catalytic activity suggesting future potential of this catalyst.
- Islam, Md. Mominul,Halder, Mita,Roy, Anupam Singha,Chatterjee, Sauvik,Bhaumik, Asim,Islam, Sk. Manirul
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p. 109692 - 109701
(2016/11/30)
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- Formation of Amides from Imines via Cyanide-Mediated Metal-Free Aerobic Oxidation
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A new protocol for the direct formation of amides from imines derived from aromatic aldehydes via metal-free aerobic oxidation in the presence of cyanide is described. This protocol was applicable to various aldimines, and the desired amides were obtained in moderate to good yields. Mechanistic studies suggested that this aerobic oxidative amidation might proceed via the addition of cyanide to imines followed by proton transfer from carbon to nitrogen in the original imines, leading to carbanions of α-amino nitriles, which undergo subsequent oxidation with molecular oxygen in air to provide the desired amide compounds.
- Seo, Hong-Ahn,Cho, Yeon-Ho,Lee, Ye-Sol,Cheon, Cheol-Hong
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p. 11993 - 11998
(2016/01/09)
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- Highly efficient dehydrogenative cross-coupling of aldehydes with amines and alcohols
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A common protocol for the synthesis of amides, esters and α-ketoesters via cross dehydrogenative coupling of aldehydes and amines/alcohols has been developed. The method is applicable to a wide variety of alcohols and amines as well as aliphatic and aromatic aldehydes. Also, the use of acetaldehyde for acetylation and ethyl glyoxalate to access 2-oxo-amino esters is presented for the first time.
- Deshidi, Ramesh,Rizvi, Masood Ahmad,Shah, Bhahwal Ali
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p. 90521 - 90524
(2015/11/11)
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- Polyethylene glycol as a recyclable reaction medium for gold-catalysed direct oxidative amide synthesis from aldehydes and amines
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Polyethylene glycol (PEG) was used as the recyclable reaction medium for gold-catalysed oxidative amidation of aldehydes with amines by using tert-butyl hydroperoxide (TBHP, 70% aqueous) as the oxidant. The reaction proceeded efficiently to provide the corresponding products in moderate to good yields under mild conditions. Both the catalysts and solvent can be easily recovered and reused by simple extraction without significant loss of activity.
- Jiang, Hui-Liang,Zhao, Jie
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p. 654 - 656
(2016/01/25)
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- Copper-catalyzed oxidative amidation between aldehydes and arylamines under mild conditions
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A facile strategy to prepare amide bonds has been developed. A series of amide compounds, including heterocyclic amide compounds, were obtained with moderate to good yields ranging from 31-88% by using copper iodide (CuI) to catalyze the oxidative amidation between aldehydes and amines under solvent-free conditions at room temperature in air.
- Ding, Yongzheng,Zhang, Xian,Zhang, Dongyang,Chen, Yuting,Wu, Zhibing,Wang, Peiyi,Xue, Wei,Song, Baoan,Yang, Song
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supporting information
p. 831 - 833
(2015/02/19)
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- A new method for the synthesis of substituted 3-amino-1,2,4- triazoles
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A number of 4,5-substituted-3-amino-1,2,4-triazoles have been synthesized from different anilines. The compounds are characterized on the basis of 1H NMR and mass spectral data.
- Bezbarua, Maitreyee Sarma,Kataky
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p. 425 - 428
(2019/01/21)
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- Copper-catalyzed regioselective synthesis of N-aryl amides from aldoximes and aryl halides
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Ligand-assisted copper-catalyzed reaction of aldoximes with aryl halides is described for the regioselective synthesis of N-aryl amides. This protocol is simple and compatible with a wide range of functional groups attached to the aryl ring of the halides as well as aldoximes. Copyright
- Panda, Niranjan,Mothkuri, Raghavender,Nayak, Dinesh Kumar
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supporting information
p. 1602 - 1605
(2014/03/21)
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- Copper-Catalyzed Regioselective Synthesis of N-Aryl Amides from Aldoximes and Aryl Halides
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Ligand-assisted copper-catalyzed reaction of aldoximes with aryl halides is described for the regioselective synthesis of N-aryl amides. This protocol is simple and compatible with a wide range of functional groups attached to the aryl ring of the halides as well as aldoximes.
- Panda, Niranjan,Mothkuri, Raghavender,Nayak, Dinesh Kumar
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supporting information
p. 1602 - 1605
(2015/10/05)
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- Aerobic oxidative transformation of primary alcohols and amines to amides promoted by a hydroxyapatite-supported gold catalyst in water
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In the presence of an easily prepared hydroxyapatite-supported gold catalyst, namely Au/HAP, various kinds of structurally diverse primary alcohols including benzylic and aliphatic ones, and amines involving aromatic and secondary ones could be converted into the corresponding amides in water with up to 99% yield. Meanwhile, on the basis of experimental observations and literatures, a plausible reaction pathway was described to elucidate the reaction mechanism.
- Wang, Wentao,Cong, Yu,Zhang, Leilei,Huang, Yanqiang,Wang, Xiaodong,Zhang, Tao
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supporting information
p. 124 - 127
(2014/01/06)
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- A class of 5-nitro-2-furancarboxylamides with potent trypanocidal activity against Trypanosoma brucei in vitro
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Recently, the World Health Organization approved the nifurtimox- eflornithine combination therapy for the treatment of human African trypanosomiasis, renewing interest in nitroheterocycle therapies for this and associated diseases. In this study, we have synthesized a series of novel 5-nitro-2-furancarboxylamides that show potent trypanocidal activity, ~1000-fold more potent than nifurtimox against in vitro Trypanosoma brucei with very low cytotoxicity against human HeLa cells. More importantly, the most potent analogue showed very limited cross-resistance to nifurtimox-resistant cells and vice versa. This implies that our novel, relatively easy to synthesize and therefore cheap, 5-nitro-2-furancarboxylamides are targeting a different, but still essential, biochemical process to those targeted by nifurtimox or its metabolites in the parasites. The significant increase in potency (smaller dose probably required) has the potential for greatly reducing unwanted side effects and also reducing the likelihood of drug resistance. Collectively, these findings have important implications for the future therapeutic treatment of African sleeping sickness.
- Zhou, Linna,Stewart, Gavin,Rideau, Emeline,Westwood, Nicholas J.,Smith, Terry K.
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supporting information
p. 796 - 806
(2013/03/28)
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- An improved protocol for synthesis of N-arylamides and benzoxazoles by the copper-catalyzed reaction of aryl halides with nitriles
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An improved protocol for the synthesis of N-arylamides and benzoxazoles by the copper-catalyzed reaction of aryl halides with nitriles has been developed. Use of acetaldoxime as the hydrolysis reagent instead of H2O facilitates the operation of the reaction. The significantly decreased amount of nitriles, along with use of weak base K2CO3 instead of strong base KOH, makes this transformation atom-efficient and environmentally benign. A variety of N-arylamides and benzoxazole derivatives can be synthesized according to this approach.
- Zhang, Dong-Xue,Xiang, Shi-Kai,Hu, Hao,Tan, Wen,Feng, Chun,Wang, Bi-Qin,Zhao, Ke-Qing,Hu, Ping,Yang, Hua
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p. 10022 - 10029
(2013/11/06)
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- Aerobic oxidative coupling of alcohols and amines over Au-Pd/resin in water: Au/Pd molar ratios switch the reaction pathways to amides or imines
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A facile switch of the reaction pathways of aerobic oxidative coupling of alcohols and amines from amidation to imination was realized for the first time by tuning the Au/Pd ratios in ion-exchange resin supported Au-Pd alloy catalysts (Au-Pd/resin). Amides were obtained with high yields on Au6Pd/resin while imines were obtained over AuPd4/resin. Various alcohols and amines underwent oxidative coupling smoothly in water to afford the desired products with good to excellent yields. Further investigation on the reaction mechanism suggested the synergistic effect between Au and Pd determined the adsorption strength of the aldehyde intermediate, which in turn dictated the reaction pathways. That is, on Au-rich alloys (e.g., Au6Pd) absorbed aldehyde species was formed, followed by further oxidation to yield amides, while on Pd-rich alloys (e.g., AuPd4), free aldehyde was generated, which then underwent condensation with amines to produce imines. The discovery might provide avenues to develop new efficient catalysts for the green synthesis of special chemicals.
- Zhang, Leilei,Wang, Wentao,Wang, Aiqin,Cui, Yitao,Yang, Xiaofeng,Huang, Yanqiang,Liu, Xiaoyan,Liu, Wengang,Son, Jin-Young,Oji, Hiroshi,Zhang, Tao
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supporting information
p. 2680 - 2684
(2013/10/08)
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- The catalytic activity of titania nanostructures in the synthesis of amides under solvent-free conditions
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Different shapes and phases of titania nanostructures with the uniform size distribution were synthesized by hydrothermal sol-gel technique. The influence of annealing temperature on the crystalline character, size and phase of the prepared nanomaterials were evidenced from the diffraction analysis. Infrared spectroscopic analysis ensured the structural confirmation of the sulfated titania nanostructures. Catalytic activity of the synthesized nanometric materials in direct amidation of aromatic and aliphatic carboxylic acids with aromatic amines was evaluated. Among the materials studied, sulfated titania nanotubes with the anatase phase exhibited excellent catalytic activity. The employed solvent-free protocol is greener and eradicates the drawbacks associated with the hazardous solvents employed in the prevailing solution phase methodologies.
- Nagarajan, Sangaraiah,Ran, Park,Shanmugavelan, Poovan,Sathishkumar, Murugan,Ponnuswamy, Alagusundaram,Suk Nahm, Kee,Gnana Kumar
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p. 1312 - 1319
(2012/10/29)
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- Palladium-catalyzed direct arylations of five-membered heteroarenes bearing N-monoalkylcarboxamide substituents
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The palladium-catalyzed direct arylation of furan, thiophene, pyrrole, or pyrazole derivatives bearing CONHR substituents on C2, C3, or C5 with aryl bromides was studied. The use of KOAc as the base, DMAc as the solvent, and PdCl(C3H5)(dppb) as the catalyst was found to give regioselectively and without decarbamoylation the arylated heteroaromatics. Under these conditions, the amide substituent on the heteroaromatic does not act as a directing group. A wide range of functional groups such as acetyl, formyl, ester, nitrile, trifluoromethyl, and fluoro on the aryl bromide is tolerated. The palladium-catalyzed direct arylation of furan, thiophene, pyrrole, or pyrazole derivatives bearing CONHR substituents on C2, C3, or C5 with aryl bromides was studied. The use of KOAc as the base, DMAc as the solvent, and PdCl(C3H5)(dppb) as the catalyst was found to give regioselectively the arylated heteroaromatics.
- Laidaoui, Nouria,Roger, Julien,Miloudi, Abdellah,El Abed, Douniazad,Doucet, Henri
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experimental part
p. 4373 - 4385
(2011/10/09)
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- An efficient protocol for the amidation of carboxylic acids promoted by trimethyl phosphite and iodine
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A practical, one-pot protocol is described for the conversion of carboxylic acids into amides through carboxyl activation by the reagent combination of trimethyl phosphite and iodine. This method integrates several advantages: (1) it allows amines to be chemoselectively acylated with excellent results in the presence of sulfur and oxygen nucleophiles; (2) the method shows wide generality in respect of solvent, base, and substrate; (3) the reagents used are widely available and much less expensive than common coupling reagents, and (4) the process is remarkably convenient, permitting extraction, recrystallization, and column chromatography as optional work-up procedures. The chemoselectivity and generality of the method, the low cost, and wide availability of reagents combined with the ease of use make it a very favorable process.
- Luo, Qun-Li,Lv, Lina,Li, Yu,Tan, Jian-Ping,Nan, Wenhui,Hui, Qun
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supporting information; experimental part
p. 6916 - 6922
(2012/01/06)
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- Highly efficient amide synthesis from alcohols and amines by virtue of a water-soluble gold/DNA catalyst
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Gold takes to water: The synthesis of amides directly from alcohols and amines was realized by using a water-soluble Au/DNA nanohybrid as the catalyst. The interactions between the gold nanoparticles, DNA, and water lead to high catalytic efficiency under mild reaction conditions. The wide substrate scope includes less-basic aromatic amines, and this catalyst is recyclable.
- Wang, Ye,Zhu, Dapeng,Tang, Lin,Wang, Sujing,Wang, Zhiyong
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supporting information; experimental part
p. 8917 - 8921
(2011/10/31)
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- Dithiocarbamate and DBU-promoted amide bond formation under microwave condition
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Dithiocarbamate and DBU-promoted amide bond formation under microwave condition has been reported. The versatility of this synthetic protocol has been demonstrated with various carboxylic acids and different dithiocarbamates. The products thus obtained ha
- Kumar, Katari Naresh,Sreeramamurthy, Kintali,Palle, Sadananda,Mukkanti, Khagga,Das, Parthasarathi
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experimental part
p. 899 - 902
(2010/05/03)
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- Challenges associated with the synthesis of unusual o-carboxamido stilbenes by the Heck protocol: Intriguing substituent effects, their toxicological and chemopreventive implications
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The syntheses of fourteen unusual o-carboxamido stilbenes by the Heck protocol revealed surprising complexity related to intriguing substituent effects with mechanistic implications. The unexpected cytotoxic and chemopreventive properties also seem to be substituent dependent. For example, although stilbene 15d (with a 4-methoxy substituent) showed cytotoxicity on HT29 colon cancer cells with an IC50 of 4.9 μM, the 3,4-dimethoxy derivative (15c) is inactive. It is interesting to observe that the 3,5-dimethoxy derivative (15e) showed remarkable chemopreventive activity in WRL-68 fetal hepatocytes, surpassing the gold standard, resveratrol. The resveratrol concentration needed to be 5 times higher than that of 15e to produce comparable elevation of NQO1.
- Kee, Chin Hui,Ariffin, Azhar,Awang, Khalijah,Takeya, Koichi,Morita, Hiroshi,Hussain, Salmaan Inayat,Chan, Kok Meng,Wood, Pauline J.,Threadgill, Michael D.,Lim, Chuan Gee,Ng, Seikweng,Weber, Jean Frederic F.,Thomas, Noel F.
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experimental part
p. 5646 - 5660
(2011/02/18)
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- Palladium-catalyzed cyclocarbonylation of o-lodoanilines with Imidoyl Chlorides to produce quinazolin-4(3H)-ones
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A wide variety of substituted quinazolin-4(3H)-ones were prepared in 63-91% yields by the palladium-catalyzed cyclocarbonylation of o-iodoanilines with imidoyl chlorides and carbon monoxide. The reaction is believed to proceed via in situ formation of an amidine, followed by oxidative addition, CO insertion, and intramolecular cyclization to give the substituted quinazolin-4(3H)-ones.
- Zheng, Zhaoyan,Alper, Howard
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supporting information; experimental part
p. 829 - 832
(2009/04/07)
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- Facile preparation of amides from azo compounds by SmI2
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Azo compounds are conveniently reduced by SmI2/THF system and successively acylated smoothly with aromatic and aliphatic acyl chlorides or acid anhydrides to afford corresponding amides in one pot under mild and neutral conditions.
- Li, Xue,Zhang, Yongmin
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p. 1576 - 1578
(2007/10/03)
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- A catalyst system for the formation of amides by reaction of carboxylic acids with blocked isocyanates
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A catalyst for the reaction of blocked isocyanates (blocking agent diisopropylamine and dimethyl pyrazole) and carboxylic acids was identified. Magnesium and in some instances calcium salts proved to be highly active as catalyst. This reaction gives amides in quantitative yield and excellent selectivity and is suitable for coating and general chemical purposes.
- Gertzmann,Gürtler
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p. 6659 - 6662
(2007/10/03)
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- Synthesis and screening of anilides having olefinic and alkyl moiety in the side chain as chemical hybridizing agents for wheat (Triticum aestivum L.)
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Induction of male sterility by deployment of chemical hybridizing agents (CHAs) holds immense potential in heterosis breeding of wheat. A total of 21 anilides having different aromatic substitutions and side-chain variation were synthesized and screened as CHAs on three genotypes of wheat viz., PBW 343, HW 2046, and HD 2733, at winter season. Various anilides having vinyl moiety in the acyl side chain were synthesized by condensation between substituted anilines with different esters or acid chlorides. Another lead in the form of N-alkyl anilines also became evident. The percent male sterility data caused by CHAs revealed the significant contribution of anilides containing vinyl double bond incorporated in the form of closed ring structure viz., furyl moiety as the side chain. 4′-Fluoro-furyl anilide (1) and 4′-bromo-furyl anilide (2) are found to be promising lead CHAs for the design of highly active molecules. QSAR analysis revealed a direct relationship of field effect exemplified by the Swain-Lupton constant Fp for the aromatic substitution but an inverse relationship of molar refractivity MR for the side chain. The negative influences of parachor for the acyl domain have been underlined. The real guiding principle for selectivity of CHA action was found to be the π value. The CHAs act by mimicking UDP-glucose, the key substrate in the synthesis of callose, or lead to an imbalance in acid-base equilibrium in pollen mother cells resulting in dissolution of callose wall by premature callase secretion.
- Chakraborty, Kajal,Devakumar
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p. 5959 - 5968
(2007/10/03)
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- Determination of aromaticity indices of thiophene and furan by nuclear magnetic resonance spectroscopic analysis of their anilides
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A series of m- and p-substituted anilides of benzoic acid, 2-thienoic acid, and 2-furoic acid were prepared and their 1H and 13C nmr spectroscopic characteristics were examined. In general, good correlations were observed between the chemical shifts of proton and carbon signals of the acyl aromatic rings and the Hammett σ. Plots of the chemical shift values of the carbonyl carbons of the benzanilides against those of the 2-thienamides and 2-furamides gave an excellent correlation and the values of the slopes are 0.79 and 0.52, respectively, in dimethyl sulfoxide-d6. The slopes could be considered as a set of aromaticity index.
- Lee, Chang Kiu,Yu, Ji Sook,Ji, Young Ran
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p. 1219 - 1227
(2007/10/03)
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- Flash vacuum pyrolysis of 3-oxo-2-arylhydrazonopropanals and related derivatives
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Flash vacuum pyrolysis (FVP) of 3-oxo-2-arylhydrazonopropanals at 500°C and 0.02 Torr yielded the corresponding derivatives of anilines, N-formylanilines, N-benzoylanilines and benzoylnitriles. Similar FVP of phenylhydrazonomalononitrile, phenylhydrazonoa
- Ibrahim, Yehia A,Kaul, Kamini,Al-Awadi, Nouria A
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p. 10171 - 10176
(2007/10/03)
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- α-nitrogen activating effect in the room temperature copper-promoted N-arylation of heteroarylcarboxamides with phenyl siloxane or p-toluylboronic acid
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Heteroarylcarboxamides containing α-nitrogens undergo copper-promoted N-phenylation with hypervalent phenyl trimethylsiloxane at room temperature, in the absence of base and in air. Arylboronic acid can substitute for phenyl trimethylsiloxane as the organ
- Lam, Patrick Y.S.,Deudon, Sophie,Hauptman, Elisabeth,Clark, Charles G.
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p. 2427 - 2429
(2007/10/03)
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- Facile and effective synthesis of N-aryl-2-furancarboxamides derivatives under the condition of phase transfer catalysis
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A convenient one-pot procedure is reported for the preparation of N- aryl-2-furancarboxamide derivatives. 2-Furoic acid is activated by benzenesulfonyl chloride under the condition of solid-liquid phase transfer catalysis using solid potassium carbonate a
- Wei, Tai-Bao,Zhang, You-Ming
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p. 2943 - 2947
(2007/10/03)
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- Facile and Effective Synthesis of Unusually Substituted Aromatic N-Phenylamides
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A mild and effective new method for the preparation of a variety of arylamides 3a-i as well as heterocyclic 5a, b and 6 and olefinic amides 7, 9 is described.The reaction of trialkylstannyl-substituted aromatic, heterocyclic or vinylic hydrocarbons with aryl isocyanates in the presence of aluminium trichloride provides the corresponding N-aryl-substituted amides in good to excellent yields.The stannyl group serves as a powerful leaving group superior to hydrogen by several powers of ten which allows, via ipso substitution, to obtain isomer patterns not accessible by normal electrophilic substitution reactions, e. g. substitution in meta position with respect to a methoxy group.
- Kobs, Uwe,Neumann, Wilhelm P.
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p. 2191 - 2194
(2007/10/02)
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- Facile Conversions of Carboxylic Acids into Amides, Esters, and Thioesters Using 1,1'-Oxalyldiimidazole and 1,1'-Oxalyldi(1,2,4-triazole)
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Aliphatic, aromatic, and heteroaromatic carboxylic acids react with 1,1'-oxalyldiimidazole (1) or 1,1'-oxalyldi(1,2,4-triazole) (2) in acetonitrile for 40 min at 40 degC to give the corresponding 1-acylazole intermediates (11), which promptly undergo aminolysis and alcoholysis to form amides (13) including dipeptides (14), esters (16), and thioesters (19).These findings show that both 1 and 2 can be utilized as condensing reagents for the synthesis of carboxylic acid derivatives.Keywords --- 1,1'-oxalyldiimidazole; 1,1'-oxalyldi(1,2,4-triazole); 1,1'-carbonyldiimidazole; 1-acylazole; condensing reagent; amidation; esterification; dipeptide; aminolysis; alcoholysis
- Kitagawa, Tokujiro,Kuroda, Hiroko,Sasaki, Hideaki,Kawasaki, Koichi
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p. 4294 - 4301
(2007/10/02)
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- OXIDATIVE BENZOIN REACTIONS
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A one-pot synthesis (yields over 50percent) of methyl and ethyl esters from aldehydes (and the corresponding alcohol), using aromatic nitrocompounds as oxidizing agents under the catalytic action of cyanide ion or of a conjugate base of a thiazolium ion, is described.A variety of by-products (α-hydroxybenzylidenaniline (16), α-methoxybenzylidenaniline (21), α-cyanobenzylidenaniline (27), N1-hydroxy-N1,N2-diphenylbenzamidine (28), and others) have been identified.
- Castells, J.,Pujol, F.,Llitjos, H.,Moreno-Manas, M.
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p. 337 - 346
(2007/10/02)
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