- Aminolysis of 2,2,2-Trichloro-1-arylethanones in Aprotic Solvents
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The kinetics of the reaction of the title substrate with various alkylamines was studied in n-heptane, dichloromethane, dioxane, tetrahydrofuran, and acetonitrile.The reaction was third-order in amine when the solvent was n-heptane or dichloromethane.In the other solvents a second-order dependence on was observed.The fourth-order rate constants for the reaction of n-butylamine with various 2,2,2-trichloro-1-arylethanones in dichloromethane yielded a ρ value of 3.0.In all solvents the observed rate constans decreased with a temperature increase.Two mechanistic possibilities were suggested, the first one in solvents of low donicity, involving a T0 intermediate formed in a concerted process with the participation of an amine dimer; and the second one, a stepwise process in more basic solvents which takes place via a T+/- intermediate.Base-catalyzed collapse of the tetrahedral intermediates is the rate-determining step in both pathways.
- Druzian, Janice,Zucco, Cesar,Rezende, Marcos Caroli,Nome, Faruk
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- Synthesis of CF3-containing isoindolinone derivatives through rhodium-catalyzed oxidative coupling of benzamides with 2-trifluoromethylacrylate
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The oxidative coupling of benzamides with methyl 2- trifluoromethylacrylate proceeds smoothly under rhodium(III) catalysis to produce trifluoromethyl-substituted isoindolinone derivatives. The catalyst system [CpERhCl2]2/AgSbF6 is effective for the oxidat
- Yoshimoto, Risa,Morisaka, Hideaki,Usuki, Yoshinosuke,Shibata, Yu,Tanaka, Ken,Satoh, Tetsuya
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- The direct amidation of α-diketones with amines via TBHP-promoted oxidative cleavage of C(sp2)-C(sp2) bonds
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A novel and efficient direct amidation of α-diketones with amines via TBHP-promoted oxidative cleavage of C(sp2)-C(sp2) bonds has been developed. The strategy provides an alternative approach to amides under metal-free conditions.
- Zhao, Qiong,Li, Hongji,Wang, Lei
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- Nickel-catalyzed aminocarbonylation of aryl halides using carbamoylsilane as an amide source
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The nickel-catalyzed aminocarbonylation of aryl halides using carbamoylsilane as an amide source is developed. The procedure can prepare both tertiary and secondary amides, and is applicable to various carbamoylsilanes and aryl halides containing differen
- Wen, Xue-Ping,Han, Yu-Ling,Chen, Jian-Xin
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- Hydroamination of unactivated alkenes catalyzed by novel platinum(II) N -heterocyclic carbene complexes
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Cationic platinum(II) complexes with bi- or tridentate (pincer) functionalized NHC ligands were found to be catalytically active in the hydroamination of unactivated alkenes. In some cases, the presence of water had an activating effect on the complexes. Reactions with the N-nucleophilic substrate morpholine led to a noncatalytic reaction in which the deprotonation product of the key cationic β-aminoalkyl platinum complex could be isolated and characterized. Surprisingly, attempted protonation of this complex did not give the expected N-alkylated product, indicating either the thermodynamic unfavorability of C-Pt bond cleavage or its kinetic inertness.
- Cao, Peng,Cabrera, Jose,Padilla, Robin,Serra, Daniel,Rominger, Frank,Limbach, Michael
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- Electrophilic Activation of Amides for the Preparation of Polysubstituted Pyrimidines
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In this article we describe the straightforward synthesis of polysubstituted pyrimidines by electrophilic activation of secondary amides in the presence of alkynes. An unusual mechanistic detour leading to pyridine derivatives as products is also presente
- Stopka, Tobias,Adler, Pauline,Hagn, Gerhard,Zhang, Haoqi,Tona, Veronica,Maulide, Nuno
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- Direct synthesis of amides and imines by dehydrogenative homo or cross-coupling of amines and alcohols catalyzed by Cu-MOF
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Oxidative dehydrogenative homo-coupling of amines to imines and cross-coupling of amines with alcohols to amides was achieved with high to moderate yields at room temperature in THF using Cu-MOF as an efficient and recyclable heterogeneous catalyst under mild conditions. Different primary benzyl amines and alcohols could be utilized for the synthesis of a wide variety of amides and imines. The Cu-MOF catalyst could be recycled and reused four times without loss of catalytic activity.
- Anbardan, Soheil Zamani,Bozcheloei, Abolfazl Hassani,Mokhtari, Javad,Yari, Ahmad
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- Amidoethylation of Anthracene Hydride by N-Aroylaziridines: Inner-sphere Single Electron Transfer (SET) and Radical Coupling confirmed
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Regioselectivity (near 1:1) of substitutive ring opening of 1-benzoyl-2-methylaziridine by anthracene hydride is incompatible with common nucleophilic attack and thus confirms the radical coupling path.
- Lin,Stamm
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- POLYAMIDE-BOUND METAL COMPLEX CATALYSTS:SYNTHESIS, CHARACTERIZATION AND CATALYTIC PROPERTIES
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A series polyamides having different numbers of methylene groups in their repeating units have been synthesized by interfacial polycondensation of terephthaloyl chloride with piperazine and aliphatic diamines H2N(CH2)nNH2 (n = 2, 6, 10).These m
- Michalska, Z. M.,Ostaszewski, B.
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- The Mechanisms of Photochemical Reactions of o-Sulfobenzoic Imides
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The photochemical processes of N-propyl-o-sulfobenzoic imide to the amides were investigated in ethanol and monocyclic aromatics, such as benzene, anisole, toluene, polymethylbenzenes, and benzonitrile. It was clarified that although both the S1 and T1 states took part in those photochemical reactions, the mechanisms were different in ethanol and those aromatics. The mechanism in ethanol is thought to involve hydrogen-atom abstraction from ethanol by a diradical formed after the extrusion of sulfur dioxide. The mechanism in aromatics involved an energy transfer from the singlet excited aromatic molecules to the sulfobenzoic imide and the addition of the resulting diradicals to the partner aromatics. Although the sulfobenzoic imide sensitized to a triplet state by acetophenone in benzene resulted as well in the formation of the arylated benzamide, this process was minor in comparison with the process via the S1 state. This was attributed to the triplet multiplicity of the diradical. The reactions of the sulfobenzoic imide with p-xylene and mesitylene were less predominant than those with toluene and anisole, which was attributable to a steric effect of plural methyl groups on the ring. The fact that no formation of the arylated benzamides took place in the case of benzonitrile could be explained by a strong inductitive effect of a cyano group of benzonitrile.
- Ono, Isao,Sato, Shohei,Fukuda, Kiyoshi,Inayoshi, Tomoko
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- Electrolysis of trichloromethylated organic compounds under aerobic conditions catalyzed by the B12 model complex for ester and amide formation
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The electrolysis of benzotrichloride at -0.9 V vs. Ag/AgCl in the presence of the B12 model complex, heptamethyl cobyrinate perchlorate, in ethanol under aerobic conditions using an undivided cell equipped with a platinum mesh cathode and a zinc plate anode produced ethylbenzoate in 56% yield with 92% selectivity. The corresponding esters were obtained when the electrolysis was carried out in various alcohols such as methanol, n-propanol, and i-propanol. Benzoyl chloride was detected by GC-MS during the electrolysis as an intermediate for the ester formation. When the electrolysis was carried out under anaerobic conditions, partially dechlorinated products, 1,1,2,2-tetrachloro-1,2-diphenylethane and 1,2-dichlorostilibenes (E and Z forms), were obtained instead of an ester. ESR spin-trapping experiments using 5,5,-dimethylpyrroline N-oxide (DMPO) revealed that the corresponding oxygen-centered radical and carbon-centered radical were steadily generated during the electrolyses under aerobic and anaerobic conditions, respectively. Applications of the aerobic electrolysis to various organic halides, such as substituted benzotrichlorides, are described. Furthermore, the formation of amides with moderate yields by the aerobic electrolysis of benzotrichloride catalyzed by the B12 model complex in the presence of amines in acetonitrile is reported.
- Shimakoshi, Hisashi,Luo, Zhongli,Inaba, Takuya,Hisaeda, Yoshio
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- A mild and clean method for oxidative formation of amides from aldehydes and amines
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A metal-free direct oxidative formation of amides from aldehydes and amines using a hypervalent iodine(III) reagent or an ion-supported hypervalent iodine(III) reagent as a recyclable oxidant under mild conditions is reported. Georg Thieme Verlag Stuttgart.
- Fang, Chen,Qian, Weixing,Bao, Weiliang
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- One-pot synthesis of amides from carboxylic acids activated using thionyl chloride
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A one-pot synthesis of secondary and tertiary amides from carboxylic acids and amines by using SOCl2 has been developed. Also when sterically hindered amines were used as the starting materials, excellent yields of the corresponding amides were obtained. The amidation of N-protected α-amino acids with secondary amines proceeds effectively with good yields. The process works well also in the presence of acid sensitive groups and occurs with almost complete retention of stereochemical integrity of chiral substrates. This protocol could be extended to industrial large-scale production processes.
- Leggio,Belsito,De Luca,Di Gioia,Leotta,Romio,Siciliano,Liguori
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- pKa-dependent formation of amides in water from an acyl phosphate monoester and amines
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(Chemical Equation Presented) Acyl phosphate monoesters are readily prepared biomimetically activated anionic derivatives of carboxylic acids that react rapidly with amines in water to form amides. A plot of the logarithms of the rate constants for the reactions of a series of primary amines with benzoyl methyl phosphate depends on the pKa of the conjugate acids of the amines (βnuc ≈ 0.9). This provides a simple and quantitative basis for regioselective acylation with these reagents.
- Wodzinska, Jolanta,Kluger, Ronald
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- A study on reactions of an alkynylsilane with oxone-KX (X = Cl, Br, I) and its one-pot transformation into an amide/ester
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Oxyhalogenation reactions of a variety of alkynylsilanes were studied using oxone as mild oxidant and KCl, KBr, and KI as halogen sources. In this study, reaction of an alkynylsilane with oxone-KX (X = Cl or Br) produced trichloromethyl/tribromomethyl ketones inhigh yields. Under similar conditions, however, reactions of alkynylsilanes with oxone-KI were found to give exclusively 1,2,2-triiodovinyl derivatives in high yields. In this study, new methods were deveoped for effcient one-pot tranformation of alkynylsilanes into amides and esters by reaction with amines and alcohols respectively via trihalomethyl ketone.
- Sriramoju, Vinodkumar,Jillella, Raveendra,Kurva, Srinivas,Madabhushi, Sridhar
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- AMINE-BORANES AS BIFUNCTIONAL REAGENTS FOR DIRECT AMIDATION OF CARBOXYLIC ACIDS
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The present invention generally relates to a process for selective and direct activation and subsequent amidation of aliphatic and aromatic carboxylic acids to afford an amide R3CONR1R2. That the process is capable of delivering gaseous or low-boiling point amines provides a major advantage over existing methodologies, which involves an intermediate of triacyloxyborane-amine complex [(R3CO2)3—B—NHR1R2]. This procedure readily produces primary, secondary, and tertiary amides, and is compatible with the chirality of the acid and amine involved. The preparation of known pharmaceutical molecules and intermediates has also been demonstrated.
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Paragraph 0008-0009; 0063-0064
(2022/03/04)
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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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- Direct Amidation of Esters by Ball Milling**
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The direct mechanochemical amidation of esters by ball milling is described. The operationally simple procedure requires an ester, an amine, and substoichiometric KOtBu and was used to prepare a large and diverse library of 78 amide structures with modest to excellent efficiency. Heteroaromatic and heterocyclic components are specifically shown to be amenable to this mechanochemical protocol. This direct synthesis platform has been applied to the synthesis of active pharmaceutical ingredients (APIs) and agrochemicals as well as the gram-scale synthesis of an active pharmaceutical, all in the absence of a reaction solvent.
- Barreteau, Fabien,Battilocchio, Claudio,Browne, Duncan L.,Godineau, Edouard,Leitch, Jamie A.,Nicholson, William I.,Payne, Riley,Priestley, Ian
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supporting information
p. 21868 - 21874
(2021/09/02)
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- Cobalt-catalyzed alkene hydrogenation by reductive turnover
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Earth abundant metal catalysts hold advantages in cost, environmental burden and chemoselectivity over precious metal catalysts. Differences in reactivity for a given metal center result from ligand field strength, which can promote reaction through either open- or closed-shell carbon intermediates. Herein we report a simple protocol for cobalt-catalyzed alkene reduction. Instead of using an oxidative turnover mechanism that requires stoichiometric hydride, we find a reductive turnover mechanism that requires stoichiometric proton. The reaction mechanism appears to involve coordination and hydrocobaltation of terminal alkenes.
- van der Puyl, Vincent,McCourt, Ruairi O.,Shenvi, Ryan A.
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supporting information
(2021/04/19)
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- Copper and N-Heterocyclic Carbene-Catalyzed Oxidative Amidation of Aldehydes with Amines
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A one-pot two-step oxidative process has been developed for the tert-butyl hydroperoxide mediated transformation of aldehydes and amines into amides catalyzed by copper(I) iodide and an N-heterocyclic carbene. The process is additive-free and does not require the amine to be transformed into its hydrochloride salts. The method is simple and practicable, has a broad substrate scope, and uses economical, feasible, and abundant reagents.
- Singh, Ashmita,Narula, Anudeep Kumar
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supporting information
p. 718 - 722
(2021/02/26)
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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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- NaOTs-promoted transition metal-free C-N bond cleavage to form C-X (X = N, O, S) bonds
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Multifunctional transformation of amide C-N bond cleavage is reported. The protocol applies to benzamide, thioamide, alcohols, and mercaptan under similar reaction conditions catalyzed by NaOTs. It is noteworthy that NaOTs can not only be recycled and reused for up to three cycles without significant loss in catalytic activity, but also catalyze gram-grade reactions. This study provides a novel solution with mild conditions and a simple procedure for transformation of multiple amides.
- Chen, Wei,Liu, Sicheng,Liu, Tingting,Majeed, Irfan,Ye, Xiaojing,Zeng, Zhuo,Zhang, Yuqi,Zhu, Yulin
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supporting information
p. 8566 - 8571
(2021/10/20)
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- Photochemical Activation of Aromatic Aldehydes: Synthesis of Amides, Hydroxamic Acids and Esters
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A cheap, facile and metal-free photochemical protocol for the activation of aromatic aldehydes has been developed. Utilizing thioxanthen-9-one as the photocatalyst and cheap household lamps as the light source, a variety of aromatic aldehydes have been activated and subsequently converted in a one-pot reaction into amides, hydroxamic acids and esters in good to high yields. The applicability of this method was highlighted in the synthesis of Moclobemide, a drug against depression and social anxiety. Extended and detailed mechanistic studies have been conducted, in order to determine a plausible mechanism for the reaction.
- Nikitas, Nikolaos F.,Apostolopoulou, Mary K.,Skolia, Elpida,Tsoukaki, Anna,Kokotos, Christoforos G.
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p. 7915 - 7922
(2021/05/03)
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- Weak base-promoted selective rearrangement of oxaziridines to amidesviavisible-light photoredox catalysis
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The selective rearrangement of oxaziridines to amidesviaa single electron transfer (SET) pathway is unexplored. In this study, we present a weak base-promoted selective rearrangement of oxaziridines to amidesviavisible-light photoredox catalysis. The developed method shows excellent functional group tolerance with a broad substrate scope and good to excellent yields. Furthermore, control experiments and density functional theory (DFT) calculations are performed to gain insight into the reactivity and selectivity.
- Park, Jin,Park, Sehoon,Jang, Gwang Seok,Kim, Ran Hui,Jung, Jaehoon,Woo, Sang Kook
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p. 9995 - 9998
(2021/10/06)
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- Benzyne-Mediated Esterification Reaction
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A benzyne-mediated esterification of carboxylic acids and alcohols under mild conditions has been realized, which is made possible via a selective nucleophilic addition of carboxylic acid to benzyne in the presence of alcohol. After a subsequent transesterification with alcohol, the corresponding esters can be produced efficiently. This benzyne-mediated protocol can be used on the modification of Ibuprofen, cholesterol, estradiol, and synthesis of nandrolone phenylpropionate. In addition, benzyne can also be used to promote lactonization and amidation reaction.
- Li, Yang,Shi, Jiarong,Zhao, Jinlong
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supporting information
p. 7274 - 7278
(2021/10/01)
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- Visible-light-induced direct construction of amide bond from carboxylic acids with amines in aqueous solution
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A novel visible-light-promoted N-acylation for the synthesis of amides from easily available carboxylic acids with amines in the presence of I2 within 2.5 h in aqueous solution has been developed. Using sunlight as the visible light source greatly reduces the cost of experiments and produces almost no toxic effects. Hence, this study provides an alternative catalytic system for the construction of a wide range of amides with readily available materials. Moreover, the strategy was successfully applied in the preparation of N-(3-(2,6-dimethoxyphenoxy)-7-nitroquinoxalin-2-yl)benzohydrazide, which displayed a signification anti-proliferation effect on A549, MCF-7 and HCT116 cell lines.
- Wang, Jin,Hou, Huiqing,Hu, Yongzhi,Lin, Jin,Wu, Min,Zheng, Zhiqiang,Xu, Xiuzhi
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supporting information
(2021/02/09)
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- Amine-boranes as Dual-Purpose Reagents for Direct Amidation of Carboxylic Acids
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Amine-boranes serve as dual-purpose reagents for direct amidation, activating aliphatic and aromatic carboxylic acids and, subsequently, delivering amines to provide the corresponding amides in up to 99% yields. Delivery of gaseous or low-boiling amines as their borane complexes provides a major advantage over existing methodologies. Utilizing amine-boranes containing borane incompatible functionalities allows for the preparation of functionalized amides. An intermolecular mechanism proceeding through a triacyloxyborane-amine complex is proposed.
- Choudhary, Shivani,Hamann, Henry J.,Ramachandran, P. Veeraraghavan
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supporting information
(2020/11/13)
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- Copper-catalyzed aerobic oxidative C-C bond cleavage of simple ketones for the synthesis of amides
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A Cu-catalyzed oxidative amidation of simple ketones with amines via carbon-carbon (C-C) bond cleavage has been developed. A number of aryl and alkyl ketones could be easily converted to amides using cheap copper salt as the catalyst and O2 as the oxidant with a wide range of amines, including primary and secondary amines. This method shows a notable advantage of the broad scope for the substrate, thus providing a practical approach to amides. A plausible mechanism is proposed based on the preliminary experiments.
- Li, Ke,Liu, Wei,Liu, Yu-Feng,Yang, Guo-Ping,Zeng, Kai
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p. 6958 - 6964
(2020/10/02)
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- An unprecedented cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides
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A novel and facile cobalt-catalyzed selective aroylation of primary amines with aroyl peroxides was developed for the synthesis of aryl amides. It was unprecedented that C[sbnd]N bond formation product was selectively generated without the common N[sbnd]O bond formation product. Aroyl peroxides act as the sole aroylation reagent without additional base or oxidant. The reactions proceeded under mild conditions and showed broad substrates scope with a series of primary amines and aroyl peroxides.
- Li, Dong,Li, Jiale,Li, Juanjuan,Yuan, Songdong,Zhang, Qian
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- Triethyl Phosphite/Benzoyl Peroxide Mediated Reductive Dealkylation of O-Benzoylhydroxylamines: A Cascade Synthesis of Secondary Amides
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A new triethyl phosphite/benzoyl peroxide (BPO) mediated system has been developed for the synthesis of secondary amides with good to excellent yields in a single step. This unprecedented cascade process involves sequential reduction of N–O bond and benzoylation followed by dealkylation of N–C bond of O-benzoylhydroxylamines (O-BHA). The methodology is versatile as it tolerates a variety of aromatic and aliphatic O-BHA as substrates to access secondary amides.
- Aegurla, Balakrishna,Mandle, Ram D.,Shinde, Prasad G.,Parit, Ratan S.,Kamble, Sanjay P.,Sudalai, Arumugam,Senthilkumar, Beeran
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supporting information
p. 4235 - 4238
(2020/07/04)
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- Iridium-Catalyzed Direct C-H Amidation Producing Multicolor Fluorescent Molecules Emitting Blue-to-Red Light and White Light
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We report a powerful strategy, iridium-catalyzed direct C-H amidation (DCA) for synthesizing various fluorescent sulfonamides that emit light over the entire visible spectrum with excellent efficiency (up to 99% yields). By controlling electronic characters of the resulting sulfonamides, a wide range of blue-to-red emissions was predictably obtained via an excited-state intramolecular proton-transfer process. Furthermore, we even succeeded in a white-light generation, highlighting that this DCA is an excellent synthetic method to prepare a library of fluorophores.
- Hwang, Soon-Hyeok,Choi, Tae-Lim
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p. 2935 - 2940
(2020/04/20)
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- One-pot synthesis of amides via the oxidative amidation of aldehydes and amines catalyzed by a copper-MOF
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An efficient method for the oxidative amidation of aldehydes with primary aromatic and aliphatic amines has been developed for the synthesis of a wide variety of amides using inexpensive Cu2(BDC)2DABCO (Cu-metal-organic framework [MOF]) as a recyclable heterogeneous catalyst, and N-chlorosuccinimide and aqueous tert-butyl hydroperoxide as oxidants in acetonitrile. This amidation reaction is operationally straightforward and provides secondary amides in good yields in most cases, utilizing inexpensive and readily available reagents under mild conditions.
- Jamalifard, Samira,Mokhtari, Javad,Mirjafary, Zohreh
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p. 22749 - 22754
(2019/08/01)
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- Method for preparing derivatives of benzamide under microwave condition in aqueous phase
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The invention discloses a method for preparing derivatives of benzamide under a microwave condition in an aqueous phase. A coupling reaction is carried out between substituted benzoic acid and amine under the microwave condition in the aqueous phase. The method for preparing the derivatives of benzamide is environmentally friendly, easy and convenient to operate, safe, low in cost and efficient. Compared with the prior art, the method can be applicable to a large number of functional groups, is high in yield, produces fewer by-products, and further is easy to operate, safe, low in cost and environmentally friendly. A formula is shown in the description.
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Paragraph 0019; 0021
(2019/03/28)
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- Methyl-triflate-mediated dearylmethylation of: N -(arylmethyl)carboxamides via the retro-Mannich reaction induced by electrophilic dearomatization/rearomatization in an aqueous medium at room temperature
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We have developed a protocol for the dearylmethylation of N-(arylmethyl)carboxamides under metal-free conditions in an aqueous medium at room temperature. This protocol involves methyl triflate-mediated successive C-C and C-N bond cleavages (retro-Mannich reaction) induced by electrophilic dearomatization/rearomatization. The dearomatization/rearomatization strategy can be expected to inspire the development of novel transformations based on the C-C bond cleavage in an environmentally benign manner.
- Peng, Hui,Ma, Jinhui,Luo, Wenkun,Zhang, Guangwen,Yin, Biaolin
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supporting information
p. 2252 - 2256
(2019/05/17)
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- Synthesis of Amides by Mild Palladium-Catalyzed Aminocarbonylation of Arylsilanes with Amines Enabled by Copper(II) Fluoride
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A general Pd-catalyzed synthesis of amides by oxidative aminocarbonylation of arylsilanes under mild conditions was accomplished for the first time. The reaction is promoted by a commercially available copper(II) fluoride, which acts as a dual silane activator and mild oxidant, enabling highly efficient aminocarbonylation of versatile arylsilanes at atmospheric CO pressure. The reaction is tolerant of a wide range of arylsilanes and various sensitive halide functional groups as well as a broad scope of amines are compatible with this oxidative process using cheap CO. A significant aspect involves the increased efficiency by the catalyst system. The reaction represents a segue into the powerful Pd-catalyzed oxidative transformations of organosilanes.
- Zhang, Jin,Hou, Yanyan,Ma, Yangmin,Szostak, Michal
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p. 338 - 345
(2019/01/10)
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- Secondary/tertiary amide compound and synthesis method thereof
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The invention discloses a secondary/tertiary amide compound and a synthesis method thereof. The method comprises the following steps: adding arylsilane and an amine compound, a catalyst and an additive to a solvent, introducing CO under a certain pressure, carrying out a carbonylation reaction, and carrying out separation and purification to obtain the secondary/tertiary amide. The method for preparing the secondary/tertiary amide by the carbonylation reaction has the advantages of concision, high efficiency, directness in the reaction, high atom economy, and wide sources and good stability ofa substrate. The reaction system of the invention does not require inert gas protection, and has mild conditions, and the target product is easy to separate and the yield reaches up to 92% under optimized reaction conditions.
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Paragraph 0115; 0116; 0117; 0118; 0120
(2019/01/21)
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- Generation of alkyl radicals from alkylsilyl peroxides and their applications to C-N or C-O bond formations
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This article describes a novel method for the generation of alkyl radicals from alkylsilyl peroxides and their applications to the Cu-catalyzed mono-N-alkylation of amides or arylamines, and to the O-alkylation of carboxylic acids. The use of alkylsilyl peroxides as alkyl radical sources includes the following synthetic advantages: i) various alkylsilyl peroxides can be readily synthesized from the corresponding alcohols and be stored at bench, and ii) a variety of alkyl radicals can be generated efficiently under mild conditions.
- Sakurai, Shunya,Kato, Terumasa,Sakamoto, Ryu,Maruoka, Keiji
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p. 172 - 179
(2018/12/11)
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- Visible Light-Driven, One-pot Amide Synthesis Catalyzed by the B12 Model Complex under Aerobic Conditions
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A visible light responsive catalytic system with the B12 complex as the catalyst and [Ir(dtbbpy)(ppy)2]PF6 as the photosensitizer was developed. It provides a convenient and efficient way to synthesize amides. Based on this method, trichlorinated organic compounds were converted into amides in the presence of an amine under aerobic conditions at room temperature in a one-pot procedure. Various trichlorinated organic compounds and an amine source, such as primary, secondary, and cyclic amines, have been evaluated for this transformation, providing the expected products in moderate to excellent yields. Notably, product formation depended on the reaction atmosphere where the amide was obtained under aerobic conditions while partially dechlorinated products were obtained under anaerobic conditions. As this protocol is free from hazardous reagents, extra additives, noble metals, and dangerous gas, the present method provides a novel and efficient approach for amide synthesis under mild and easily controlled conditions.
- Tian, Hui,Shimakoshi, Hisashi,Ono, Toshikazu,Hisaeda, Yoshio
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p. 237 - 240
(2018/12/13)
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- Mild, Selective Ru-Catalyzed Deuteration Using D2O as a Deuterium Source
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A method for the selective deuteration of polyfunctional organic molecules using catalytic amounts of [RuCl2(PPh3)3] and D2O as a deuterium source is presented. Through variation of additives like CuI, KOH, and various amounts of zinc powder, orthogonal chemoselectivities in the deuteration process are observed. Mechanistic investigation indicates the presence of different, defined Ru-complexes under the given specific conditions.
- Eisele, Pascal,Ullwer, Franziska,Scholz, Sven,Plietker, Bernd
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supporting information
p. 16550 - 16554
(2019/12/11)
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- A carbonylation reaction of carbon monoxide in the method of preparing amide
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The invention belongs to the technical field of synthesis of amides, discloses a process for the carbonylation of carbon monoxide in the method of preparing amide, the method is to cheap and easy to obtain the halogenated aromatic hydrocarbon and organic amine compounds as the substrate of reaction, to carbon monoxide as carbonyl source, under light-struck, halogenated aromatic hydrocarbons are cracked to produce free radical, by free-radical addition process to obtain the amide compound. Compared with the traditional carbonylation reaction, the carbon monoxide pressure is extremely low, can react to the atmospheric pressure. This process does not need to rely on any metal catalyst of the booster, mild reaction conditions, environmental protection, with a shorter synthetic route and high utilization efficiency of the atoms, the reaction system with higher substrate tolerance, green sustainable light source as the driving force, the atom economy is high, application prospect.
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Paragraph 0024; 0025; 0026; 0027; 0028-0032; 0111-0112; 0146
(2018/07/30)
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- Synthesis of Secondary Amides through the Palladium(II)-Catalyzed Aminocarbonylation of Arylboronic Acids with Amines or Hydrazines and Carbon Dioxide
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A new Pd-catalyzed aminocarbonylation of arylboronic acids with amines or phenylhydrazines has been developed. Various secondary amides were produced from readily available substrates and cheap common metal catalysts in a CO atmosphere (balloon). Remarkably, we presents the first example of aminocarbonylations between arylboronic acids and phenylhydrazines.
- Zhang, Jin,Ma, Yuqiang,Ma, Yangmin
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supporting information
p. 1720 - 1725
(2018/04/24)
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- An efficient procedure for chemoselective amidation from carboxylic acid and amine (ammonium salt) under mild conditions
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Presented here is an efficient one-pot and catalyst-free procedure for the synthesis of amides starting from carboxylic acids and amine/ammonium salts using 2,2-dichloro-1,3-diisopropylimidazolidine-4,5-dione as the coupling agent. Reactions can proceed smoothly even with those bearing thermosensitive group(s) at ambient temperature, and the corresponding products of primary, secondary and tertiary amides can be afforded in moderate to excellent yields of up to 96%.
- Li, Jianhui,He, Shaopo,Fu, Haiqing,Chen, Xin,Tang, Min,Zhang, Dela,Wang, Bo
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p. 2289 - 2303
(2017/12/26)
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- Visible-Light-Driven Oxidation of N -Alkylamides to Imides Using Oxone/H 2 O and Catalytic KBr
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Imides are prepared conveniently by visible-light-driven oxidations of various N -alkylamides under mild conditions. The majority of the reactions proceed efficiently by using Oxone as the oxidant in the presence of a catalytic amount of KBr in H 2 O/CH 2 Cl 2 under irradiation by an 8 W white LED at room temperature. Experimental studies suggest that an imine, obtained from the substrate amide via a radical process, is the key intermediate.
- Mei, Chong,Hu, Yixin,Lu, Wenjun
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supporting information
p. 2999 - 3005
(2018/05/25)
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- Method used for preparing amides via catalysis of halogenated aromatic hydrocarbons, amines, and carbon monoxide carbonylation with precious metal
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The invention discloses a method used for preparing amides via catalysis of halogenated aromatic hydrocarbons, amines, and carbon monoxide carbonylation with precious metal. According to the method, palladium acetate and triphenyl phosphine are taken as catalysts; a super strong alkali system is composed of potassium hydroxide and dimethyl sulphoxide, p-benzoquinone is taken as an oxidizing agent, carbon monoxide gas is taken as a carbonyl source, aniline is taken as a solvent, iodobenzene is taken as a substrate, carbonylation of iodobenzene into azophenyl benzamide at room temperature under normal pressure is realized. The method is high in conversion rate; reaction conditions are mild; less environment pollution is caused; the method is beneficial for large scale industrialized production, and promising application prospect and economic benefits are achieved.
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Paragraph 0019; 0046; 0060
(2017/10/07)
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- Mono- and double carbonylation of aryl iodides with amine nucleophiles in the presence of recyclable palladium catalysts immobilised on a supported dicationic ionic liquid phase
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Silica modified with organic dicationic moieties proved to be an excellent support for palladium catalysts used in the aminocarbonylation of aryl iodides. By an appropriate choice of the reaction conditions, the same catalyst could be used for selective mono- or double carbonylations leading to amide and α-ketoamide products, respectively. The best catalyst could be recycled for at least 10 consecutive runs with a loss of palladium below the detection limit. By the application of the new support, efficient catalyst recycling could be achieved under mild reaction conditions (under low pressure and in a short reaction time). Palladium-leaching data support a mechanism with dissolution - re-precipitation of the active palladium species.
- Papp,Szabó,Srankó,Sáfrán,Kollár,Skoda-F?ldes
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p. 44587 - 44597
(2017/09/26)
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- Atom economical synthesis of: N -alkylbenzamides via the iron(III) sulfate catalyzed rearrangement of 2-alkyl-3-aryloxaziridines in water and in the presence of a surfactant
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A green and mild synthetic route to N-alkylbenzamides involves eco-friendly one pot synthesis of 2-alkyl-3-aryloxaziridines from N-alkylamines and benzaldehydes followed by iron(iii) sulfate catalyzed rearrangement to the corresponding amides in water as the solvent and in the presence of sodium dodecyl sulfate as the surfactant. This green approach affords N-alkylbenzamides in high overall yields under simple and minimum manipulation.
- Kra?em, Jamil,Ollevier, Thierry
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p. 1263 - 1267
(2017/08/15)
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- Alkylsilyl Peroxides as Alkylating Agents in the Copper-Catalyzed Selective Mono-N-Alkylation of Primary Amides and Arylamines
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The copper-catalyzed selective mono-N-alkylation of primary amides or arylamines using alkylsilyl peroxides as alkylating agents is reported. The reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with respect to the alkylsilyl peroxides, as well as to the primary amides and arylamines. Mechanistic studies suggest that the present reaction should proceed through a free-radical process that includes alkyl radicals generated from the alkylsilyl peroxides.
- Sakamoto, Ryu,Sakurai, Shunya,Maruoka, Keiji
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supporting information
p. 9030 - 9033
(2017/07/11)
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- Generation of Hydrogen from Water: A Pd-Catalyzed Reduction of Water Using Diboron Reagent at Ambient Conditions
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Production of hydrogen from renewable sources, particularly from water, is an intensive area of research, which has far-reaching relevance in hydrogen economy. A homogeneous catalytic method is presented for producing clean hydrogen gas from water, in a reaction of water with a diboron compound as the reductant, under ambient reaction conditions. The Pd-catalytic system is stable in water and displays excellent recyclability. Hydroxy analogues such as alcohols are compatible with the Pd/B2Pin2 system and generate hydrogen gas efficiently. The B2Pin2-H2O system, in the presence of palladium, is an excellent catalytic system for selective hydrogenation of olefins.
- Ojha, Devi Prasan,Gadde, Karthik,Prabhu, Kandikere Ramaiah
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supporting information
p. 5062 - 5065
(2016/10/14)
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- Green synthesis of primary, secondary, and tertiary amides through oxidative amidation of methyl groups with amine hydrochlorides over recyclable CoFe2O4 NPs
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A practical and efficient method is developed for efficient synthesis of a wide variety of 1°, 2°, and 3° amides through amidation of methylarenes with amine hydrochloride salts, over magnetic CoFe2O4 NPs as a recyclable nanocatalyst, and aqueous tert-butyl hydroperoxide as an oxidant. This economically sound amidation reaction is operationally straightforward and provides desired amides in good to excellent yields, under mild conditions.
- Eidi, Esmaiel,Kassaee, Mohammad Zaman
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p. 106873 - 106879
(2016/11/23)
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- I2/Aqueous TBHP-Catalyzed Coupling of Amides with Methylarenes/Aldehydes/Alcohols: Metal-Free Synthesis of Imides
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We present a metal-free method for the synthesis of imides by the direct coupling of NH-amides with methylarenes under iodine/aqueous TBHP conditions. The optimized conditions worked very well with benzaldehydes and benzyl alcohol and furnished the corresponding imides in good to excellent yields. A series of control and radical scavenger experiments were also performed, which suggested the involvement of radical pathways. The labeling experiment in the presence of 18O-labeled H2O suggested water as a source of oxygen in the imides.
- Aruri, Hariprasad,Singh, Umed,Kumar, Sanjay,Kushwaha, Manoj,Gupta, Ajai Prakash,Vishwakarma, Ram A.,Singh, Parvinder Pal
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supporting information
p. 3638 - 3641
(2016/08/16)
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- Oxygen-Controlled Catalysis by Vitamin B12-TiO2: Formation of Esters and Amides from Trichlorinated Organic Compounds by Photoirradiation
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An oxygen switch in catalysis of the cobalamin derivative (B12)-TiO2 hybrid catalyst for the dechlorination of trichlorinated organic compounds has been developed. The covalently bound B12 on the TiO2 surface transformed trichlorinated organic compounds into an ester and amide by UV light irradiation under mild conditions (in air at room temperature), while dichlorostilbenes (E and Z forms) were formed in nitrogen from benzotrichloride. A benzoyl chloride was formed as an intermediate of the ester and amide, which was detected by GC-MS. The substrate scope of the synthetic strategy is demonstrated with a range of various trichlorinated organic compounds. A photo-duet reaction utilizing the hole and conduction band electron of TiO2 in B12-TiO2 for the amide formation was also developed.
- Shimakoshi, Hisashi,Hisaeda, Yoshio
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supporting information
p. 15439 - 15443
(2016/01/26)
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- Carboxyl activation of 2-mercapto-4,6-dimethylpyrimidine through n-acyl-4,6-dimethylpyrimidine-2-thione: A chemical and spectrophotometric investigation
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2-Mercapto-4,6-dimethylpyrimidine, as effective carboxyl activating group, has been successfully proved by converting it into respective acyl derivatives and the subsequent conversion to the amides and esters respectively using amines, amino alcohols and alcohols. The aminolysis and esterification were monitored chemically and spectrophotometrically. This paved way to establish that the above mercaptopyrimidine derivative is an efficient carboxyl activating group applicable in solid phase peptide synthesis.
- Rajan
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p. 287 - 291
(2015/01/30)
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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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- Catalyst-free amidation of aldehyde with amine under mild conditions
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A highly efficient, catalyst-free and one-pot procedure for the direct synthesis of amides from aldehydes and amines under mild conditions has been developed. Both aliphatic and aromatic aldehydes with primary or secondary amines are successfully converted to the corresponding amides, and it is observed that reactions can proceed in either aqueous or organic media.
- Yang, Hongyin,Hu, Wenjian,Deng, Shengjue,Wu, Tiantian,Cen, Haiman,Chen, Yiping,Zhang, Dela,Wang, Bo
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supporting information
p. 5912 - 5915
(2015/08/11)
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- Copper(I)-Catalyzed Reductive Cross-Coupling of N-Tosylhydrazones with Amides: A Straightforward Method for the Construction of C(sp3)- N Amide Bonds from Aldehydes
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A method for the one-pot synthesis of substituted amides from aldehydes and amides is presented. Namely, condensation of aldehydes with N-tosylhydrazide generated the N-tosylhydrazones which were then reductively cross-coupled in situ with primary or secondary amides in the presence of a copper catalyst to afford secondary or tertiary amides, respectively. The reaction proceeded efficiently for a wide range of aldehydes and amides under the optimized conditions, i.e., 10 mol% of tetrakis(acetonitrile)copper(I) tetrafluoroborate [Cu(CH3CN)4BF4], 1 mol% of tetra-n-butylammonium iodide [(n-Bu)4NI], and sodium hydroxide [NaOH] as base in tetrahydrofuran (THF) at 80 C. As a result, the method provides a straightforward route for the synthesis of substituted amides from readily available aldehydes via a transition metal-catalyzed C(sp3)- N amide bond forming reaction.
- Xu, Peng,Han, Fu-She,Wang, Yan-Hua
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supporting information
p. 3441 - 3446
(2016/01/25)
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- Imidazolium-supported benzotriazole: an efficient and recoverable activating reagent for amide, ester and thioester bond formation in water
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An efficient and recyclable imidazolium-supported benzotriazole reagent (Im-CH2-BtH) as a novel synthetic auxiliary has been synthesized and its utility as a carboxyl group activating reagent via the formation of stable imidazolium-supported acyl benzotriazoles was explored for the synthesis of amides, esters and thioesters in water under microwave conditions. The reagent was reused five times without any noticeable loss in activity. It is moisture insensitive and highly stable under thermal and aerobic conditions. The application of imidazolium-supported N-acetyl benzotriazole leads to synthesis of paracetamol on the gram scale under greener conditions in 93% yield.
- Shakoor, S.M. Abdul,Choudhary, Sunita,Bajaj, Kiran,Muthyala, Manoj Kumar,Kumar, Anil,Sakhuja, Rajeev
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p. 82199 - 82207
(2015/10/12)
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- A new method for the cleavage of nitrobenzyl amides and ethers
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A mild and efficient o- and p-nitrobenzyl cleavage protocol was developed. o- and p-nitrobenzyl groups were easily removed from a variety of substrates using 20% aqueous NaOH in methanol at 75 °C, presumably via oxidation at the benzylic position by oxygen dissolved in the solution. These easily introducible and removable nitrobenzyl groups can serve as valuable protecting groups for the synthesis of multifunctional, complex molecules.
- Han, Seo-Jung,Fernando De Melo, Gabriel,Stoltz, Brian M.
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p. 6467 - 6469
(2015/01/16)
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