- A two-step continuous flow synthesis of amides from alcohol using a metal-free catalyst
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Metal-free oxidative amination of aromatic alcohols in the presence of TBHP provides convenient access to amides in 86-96% yield under mild reaction conditions within 15 min in a two-step continuous flow reactor system. This method avoids expensive transition metal catalysts and integrates alcohol oxidation and amide bond formation, which are usually accomplished separately, into a single operation.
- Gu, Jiajia,Fang, Zheng,Liu, Chengkou,Yang, Zhao,Li, Xin,Wei, Ping,Guo, Kai
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- Heterobimetallic lanthanide/sodium phenoxides: Efficient catalysts for amidation of aldehydes with amines
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Heterobimetallic lanthanide/sodium phenoxides were found to be efficient catalysts for amidation of aldehydes with amines under mild conditions. The reactivity follows the order Nd 2C6H3O iPr) 2C6H3O 2C 6H3O for phenoxide groups. In comparison with the corresponding monometallic complexes, heterobimetallic complexes show higher activity and a wider range of scope of amines. A cooperation of lanthanide and sodium in this process is proposed to contribute to the high activity of the present catalyst.
- Li, Junmei,Xu, Fan,Zhang, Yong,Shen, Qi
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- Metal-free n-Bu4NI-catalyzed direct synthesis of amides from alcohols and N,N-disubstituted formamides
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A facile and efficient protocol for the synthesis of amides has been developed in the absence of transition metals. The reaction was performed with a catalytic amount of n-Bu4NI and aqueous TBHP as an oxidant. Various alcohols with N,N-disubstituted formamides were examined to furnish the desired products in good yields.
- Li, Huamin,Xie, Jin,Xue, Qicai,Cheng, Yixiang,Zhu, Chengjian
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Read Online
- Palladium nanoparticles immobilized on an amine-functionalized MIL-101(Cr) as a highly active catalyst for oxidative amination of aldehydes
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The present work reports the synthesis of well dispersed palladium nanoparticles immobilized on an amino functionalized nanoscale metal-organic framework MIL-101(Cr), by using a facile polyol method. The resulting Pd/NH2-MIL-101(Cr) nanocomposite is established to be an active heterogeneous catalyst for oxidative amination of aldehydes under solvent free conditions using hydrogen peroxide as an oxidant. The synthesized Pd/NH2-MIL-101(Cr) is characterized by powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, field emission scanning electron microscopy, Brunauer-Emmett-Teller (BET) surface area analysis, Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and atomic absorption spectroscopy (AAS). The catalyst could easily be recovered and recycled without any significant loss of its catalytic activity.
- Saikia, Mrinal,Saikia, Lakshi
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- Preparation of N,N-dimethyl aromatic amides from aromatic aldehydes with dimethylamine and iodine reagents
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Various N,N-dimethyl aromatic amides were obtained in good to moderate yields by the reaction of aromatic aldehydes with aqueous dimethylamine in the presence of molecular iodine or 1,3-diiodo-5,5-dimethylhydantoin (DIH) at room temperature. Under the same conditions and using the same procedure, treatment of aromatic aldehydes and morpholine in the presence of DIH also provided the corresponding N-aroyl morpholines in good to moderate yields. Georg Thieme Verlag Stuttgart · New York.
- Baba, Haruka,Moriyama, Katsuhiko,Togo, Hideo
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- Direct oxidative amination of aromatic aldehydes with amines in a continuous flow system using a metal-free catalyst
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A novel method for metal-free oxidative amination of aromatic aldehydes and alcohols in the presence of H2O2/NaBr/H+ within 25 min in a continuous flow system has been developed. A series of different substrates were tested and the corresponding products were obtained in good yields .
- Gu, Jiajia,Fang, Zheng,Liu, Chengkou,Li, Xin,Wei, Ping,Guo, Kai
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Read Online
- Diverse functionalization of aryl halides mediated by bis(phenylsulfonyl)methane
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A palladium-catalyzed coupling reaction of bis(phenylsulfonyl)methane and aryl halides was developed. A variety of bis(phenylsulfonyl)methyl arenes were prepared in good yields. The transformations of bis(phenylsulfonyl)methyl to methyl, trideuteriomethyl, ethyl, carboxyl, and other functional groups were demonstrated. The results provided a new approach to diverse functionalization of aryl halides.
- Pan, Ping,Chen, Lei,Zhang, Xue-jing,Yan, Ming
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supporting information
(2021/08/13)
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- A facile and versatile electro-reductive system for hydrodefunctionalization under ambient conditions
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A general electrochemical system for reductive hydrodefunctionalization is described, employing the inexpensive and easily available triethylamine (Et3N) as a sacrificial reductant. This protocol is characterized by facile operation, sustainable conditions, and exceptionally wide substrate scope covering the cleavage of C-halogen, N-S, N-C, O-S, O-C, C-C and C-N bonds. Notably, the selectivity and capability of reduction can be conveniently switched by simple incorporation or removal of an alcohol as a co-solvent.
- Huang, Binbin,Guo, Lin,Xia, Wujiong
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supporting information
p. 2095 - 2103
(2021/03/26)
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- Method for preparing amide from carboxylic acid under irradiation of blue light by taking iridium and cobalt complexes as catalysts
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The invention relates to a method for preparing amide from carboxylic acid under the irradiation of blue light by taking iridium and cobalt complexes as catalysts, and belongs to the field of chemistry. The method comprises the following step of: by taking R substituted carboxylic acid and R1' and R2' substituted amines as raw materials, triphenylphosphine as a deoxidizing agent, [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as a photocatalyst and Co(dmgH)(dmgH2)Cl2 as a metal complex catalyst, reacting in dichloromethane in an inert atmosphere and under the irradiation of blue light to obtain an amide compound, wherein R is an aryl group, a heteroaryl group, a protected amino group, a substituted alkyl group, a substituted aryl group or a substituted protected amino group, R1' is a hydrogen group, a substituted alkyl group, a phenyl group or a substituted phenyl group, and R2' is a hydrogen group, a substituted alkyl group, a phenyl group or a substituted phenyl group.
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Paragraph 0039-0040
(2021/05/12)
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- N -Heterocyclic carbene (NHC) catalyzed amidation of aldehydes with amines via the tandem N -hydroxysuccinimide ester formation
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A facile method for the amidation of aldehydes by a cascade approach was developed. This methodology, reported for the first time, uses a N-heterocyclic carbene (NHC) as the catalyst, and N-hydroxysuccinimide (NHS) mediated synthesis of amides utilising TBHP as the oxidant. Various substituted aldehydes reacted smoothly with NHS giving the corresponding active esters in moderate to good yields, which facilely converted into amides in one pot. In addition, the drug moclobemide was synthesized to represent the practical utility of the developed methodology. This journal is
- Singh, Ashmita,Narula
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p. 7486 - 7490
(2021/05/13)
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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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- NaI-mediated oxidative amidation of benzyl alcohols/aromatic aldehydes to benzamides via electrochemical reaction
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In this research, we have developed a mild electrochemical process for oxidative amidation of benzyl alcohols/aromatic aldehydes with cyclic amines into the corresponding benzamides. This electroorganic synthetic method proceeds using NaI as a redox mediator under ambient temperature in undivided cell, providing more than 25 examples of amide products in moderate to good yields. The benefits of this reaction include one-pot synthesis, open air condition, proceed in aqueous media and no requirement of external conducting salt, base and oxidant.
- Rerkrachaneekorn, Tanawat,Tankam, Theeranon,Sukwattanasinitt, Mongkol,Wacharasindhu, Sumrit
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supporting information
(2021/04/15)
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- Photocatalytic aldehydes/alcohols/toluenes oxidative amidation over bifunctional Pd/MOFs: Effect of Fe-O clusters and Lewis acid sites
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Heterogeneous photocatalytic organic synthesis is fascinating because of the utilization of ubiquitous solar light for chemical transformations. Here, three Fe-MOFs with different Fe-O clusters, Lewis acid sites and morphologies were synthesized through coordination structure engineering. Pd/Fe-MOFs nanocomposites were used to challenge the amide bond green synthesis with visible light. Pd/MIL-101(Fe) exhibited the best photocatalytic performance due to the easily excited Fe3-μ3-oxo clusters for light absorption, the efficient photogenerated carriers separation and migration, the large amount of Lewis acid sites based aldehydes and amines condensation promotion and the efficient O2 reduction to superoxide radicals over photogenerated electron-rich Pd NPs. Various aldehydes, alcohols and toluenes could be transformed to amide compounds with amines over Pd/MIL-101(Fe) with just oxygen or air as the green oxidant and water as the by-product. One-pot C–C cross-coupling and photo-redox C–N coupling cascade reactions could also be achieved over Pd/MIL-101(Fe). This work shed light on the efficient and sustainable amide bonds synthesis.
- Bian, Fengxia,Cheng, Hongmei,Jiang, Heyan,Sun, Bin,Tan, Jiangwei,Zang, Cuicui
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p. 279 - 287
(2021/08/21)
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- Copper-catalyzed and additive free decarboxylative trifluoromethylation of aromatic and heteroaromatic iodides
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A copper-catalyzed decarboxylative trifluoromethylation of (hetero)aromatic iodides has been developed. Importantly, this new copper-catalyzed reaction operates in the absence of any ligands and metal additives. The protocol shows good functional group tolerance and is compatible with heteroaromatic systems. The reaction proved scalable to a 15 mmol scale with increased yield. Finally, late-stage installation of the trifluoromethyl functionality afforded the N-trifluoroacetamide variant of the antidepressant agent, Prozac, demonstrating the applicability of the developed method.
- Johansen, Martin B.,Lindhardt, Anders T.
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supporting information
p. 1417 - 1425
(2020/03/03)
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- AZAINDOLE INHIBITORS OF WILD-TYPE AND MUTANT FORMS OF LRRK2
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Disclosed are compounds that possess inhibitory activity against LRRK2. Also disclosed are pharmaceutical compositions containing the compounds and methods of using the compounds to treat diseases and disorders including neurodegenerative diseases and dis
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Paragraph 0218; 0220
(2020/05/21)
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- Double carbonylation of iodoarenes in the presence of a pyridinium SILP-Pd catalyst
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The efficiency of a palladium catalyst, immobilised on a supported ionic liquid phase (SILP) with adsorbed 1-butyl-4-methylpyridinium chloride, was investigated in aminocarbonylation reactions. Double carbonylation was found to be the main reaction using different iodoarenes and aliphatic amines as substrates. Application of aniline derivatives as nucleophiles led to the exclusive formation of substituted benzamides. The stabilisation effect of the adsorbed pyridinium ionic liquid was compared to that of imidazolium and phosphonium derivatives. It was proved that the pyridinium SILP-palladium catalyst could be reused in at least 10 cycles. Recyclability was tested in five successive runs for all of the substrates.
- Nagy, Enik?,Nagy, Petra,Papp, Máté,Skoda-F?ldes, Rita,Urbán, Béla
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- Two-step continuous flow synthesis of amide via oxidative amidation of methylarene
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A green and efficient method for the synthesis of amides has been developed through oxidative amidation between methylarenes with amines in a two-step continuous flow system. This method integrates methylarene oxidation and amide formation into a single operation which is usually accomplished separately. Oxidation with tert-butyl hydroperoxide (TBHP) as “green” oxidant, the synthesis of amides under mild reaction conditions in continuous flow system and the utilization of methylarenes as starting material make this methodology novel and environment friendly. The practical value of this method is highlighted through the synthesis of high-profile pharmaceutical agents, acetylprocainamide.
- Fang, Zheng,Guo, Kai,He, Wei,Liu, Chengkou,Shi, Tingting,Yang, Yuhang,Yang, Zhao,Zhang, Zhimin
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supporting information
(2020/02/28)
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- Electrochemical Amide Bond Formation from Benzaldehydes and Amines: Oxidation by Cathodic-Generated Hydrogen Peroxide
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Although amide bond formation from aldehydes and amines is a popular synthetic tool, most of the previously reported reactions depend on transition-metal catalysts or expensive oxidants. We considered that a more environmentally benign and safer approach could be achieved by electrochemistry. Nineteen benzamide derivatives were obtained with this reaction. NMR studies, cyclic voltammetry (CV) investigations, and control experiments showed that the corresponding intermediate, a hemiaminal, was transformed into the amide by oxidation with hydrogen peroxide generated in situ by cathodic reduction of molecular oxygen.
- Kurose, Yuma,Imada, Yasushi,Okada, Yohei,Chiba, Kazuhiro
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supporting information
p. 3844 - 3846
(2020/06/23)
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- HISTONE METHYLTRANSFERASE EZH2 INHIBITOR, PREPARATION METHOD AND PHARMACEUTICAL USE THEREOF
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The invention relates to a histone methyltransferase EZH2 inhibitor, a preparation method and pharmaceutical use thereof. In particular, the invention relates to a compound represented by the general formula (I), a preparation method thereof, a pharmaceut
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Paragraph 0498-0499
(2019/11/22)
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- Derivatives with uracil-benzothiazole structure, preparation method of derivatives, and application of anti-HCV drugs
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According to the invention, a new series of uracil-benzothiazole NS5B RdRp inhibitors are designed and synthesized; the compounds have the structure shown in a general formula (1), wherein the uracil-benzothiazole NS5B RdRp inhibitor provided by the inven
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Paragraph 0073-0075
(2019/12/02)
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- Metal-Free Transamidation of Secondary Amides by N-C Cleavage
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Transamidation reactions represent a fundamental chemical process involving conversion of one amide functional group into another. Herein, we report a facile, highly chemoselective method for transamidation of N-tert-butoxycarbonylation (N-Boc) activated secondary amides that proceeds under exceedingly mild conditions in the absence of any additives. Because this reaction is performed in the absence of metals, oxidants, or reductants, the reaction tolerates a large number of useful functionalities. The reaction is compatible with diverse amides and nucleophilic amines, affording the transamidation products in excellent yields through direct nucleophilic addition to the amide bond. The utility of this methodology is highlighted in the synthesis of Tigan, a commercial antiemetic, directly from the amide bond. We expect that this new metal-free transamidation will have broad implications for the development of new transformations involving direct nucleophilic addition to the amide bond as a key step.
- Rahman, Md. Mahbubur,Li, Guangchen,Szostak, Michal
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p. 12091 - 12100
(2019/10/11)
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- Catalyst-Free, Metal-Free, and Chemoselective Transamidation of Activated Secondary Amides
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A simple protocol, which is catalyst-free, metal-free, and chemoselective, for transamidation of activated secondary amides in ethanol as solvent under mild conditions is reported. A wide range of amines, amino acids, amino alcohols, and the substituents, which are problematic in catalyzed transamidation, are tolerated in this methodology. The transamidation reaction was successfully extended to water as the medium as well. The present methodology appears to be better than the other catalyzed transamidations reported recently.
- Ramkumar, Rajagopal,Chandrasekaran, Srinivasan
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p. 921 - 932
(2019/02/10)
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- 5-Bromo-norborn-2-en-7-one derivatives as a carbon monoxide source for palladium catalyzed carbonylation reactions
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Norbornenone (5b), obtained from the reaction of 2,5-dimethyl-3,4-diphenylcyclopentadienone dimer (3) with bromomaleic anhydride (4b), provides an excellent base-triggered source of carbon monoxide for palladium-catalysed carbonylation reactions. Aminocarbonylation, ketoamide synthesis, and Suzuki-Miyaura reactions of aryl iodides carried out in a two-chamber reaction vessel gave good to excellent yields of carbonylated products.
- Payne, China M.,Cho, Kyulee,Larsen, David S.
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p. 30736 - 30740
(2019/10/19)
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- Ruthenium(II)-NNN-Pincer-Complex-Catalyzed Reactions Between Various Alcohols and Amines for Sustainable C?N and C?C Bond Formation
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An air and moisture stable 2-hydroxypyridine based bifunctional ruthenium NNN-pincer complex catalyzed efficient (TON=42840) N-alkylation of amines under mild conditions. Surprisingly, with cyclic secondary amines this methodology selectively produced only amides. Notably, N-methylation of several amines was achieved by using methanol as a green methylating agent. Furthermore, with lower catalyst loading (0.2 mol%) and shorter reaction time (6 h) numerous substituted quinolines were synthesized from 2-aminobenzyl alcohols and secondary alcohols. The effectiveness of this protocol was further extended by successfully synthesizing 2-alkylaminoquinolines in a one-pot fashion from amino alcohol, aliphatic nitriles, and alcohols. Gram scale synthesis of various compounds was also investigated to demonstrate the synthetic applicability of this methodology. (Figure presented.).
- Maji, Milan,Chakrabarti, Kaushik,Paul, Bhaskar,Roy, Bivas Chandra,Kundu, Sabuj
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supporting information
p. 722 - 729
(2018/01/01)
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- NOVEL COMPOUND HAVING BLT INHIBITORY ACTIVITY AND COMPOSITION, FOR PREVENTING OR TREATING INFLAMMATORY DISEASES, COMPRISING SAME AS ACTIVE INGREDIENT
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The present invention relates to a novel compound showing leukotriene B4 receptor 2 (BLT2) inhibitory activity and a pharmaceutical composition, for preventing or treating inflammatory diseases, comprising same as an active ingredient. The inventors identified a novel compound containing BTL2 inhibitory activity, and experimentally confirmed that the present novel compound had an excellent effect on the enhancement of the cancer cell death, on the inhibition of the metastasis and chemotactic mobility, and on the anti-asthma activity. Therefore, the present novel compound can be used as a very effective pharmaceutical component for treating the inflammatory-related diseases.
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Paragraph 0044; 0067
(2018/06/07)
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- Ligand- and Solvent-Tuned Chemoselective Carbonylation of Bromoaryl Triflates
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The palladium-catalyzed chemoselective carbonylation of bromoaryl triflates is reported. The selective C?Br bond versus C?OTf (OTf=triflate) bond functionalization can be remarkably tuned by the combination of the ligand [4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos) vs. 1,1′-bis(diphenylphosphino)ferrocene (DPPF)] and the solvent (toluene vs. DMSO). The respective ligand and solvent effects are rationalized by DFT calculations. In contrast, the monodentate ligands BuPAd2 and tBu3P prefer the selective C?Br bond activation and are solvent insensitive.
- Shen, Chaoren,Wei, Zhihong,Jiao, Haijun,Wu, Xiao-Feng
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p. 13369 - 1337
(2017/09/06)
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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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- Ortho lithiation-in situ borylation of substituted morpholine benzamides
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Morpholine amides are cheap and safe alternative to Weinreb amides as acylating agents of organometallic species. Herein, the in-situ lithiation/borylation of 18 ortho- meta- and para-substituted morpholine benzamides has been investigated. 10 of the 18 substrates provided the desired boronic esters as the major isomer (>90% regioselectivity) in crude isolated yields ranging from 68 to 93%. The synthetic usability of such building blocks was subsequently illustrated via the synthesis of a kinase inhibitor.
- Cederbalk, Anna,Lysén, Morten,Kehler, Jan,Kristensen, Jesper L.
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p. 1576 - 1582
(2017/03/08)
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- Palladium-Catalyzed Oxidative Carbonylation of Aryl Hydrazines with CO and O2 at Atmospheric Pressure
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Palladium-catalyzed aerobic oxidative aminocarbonylation and alkoxycarbonylation reactions with aryl hydrazines as coupling partners have been developed. The oxidative carbonylation of aryl hydrazines proceeded smoothly at atmospheric pressure CO, employi
- Tu, Yongliang,Yuan, Lin,Wang, Tao,Wang, Changliu,Ke, Jiamei,Zhao, Junfeng
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p. 4970 - 4976
(2017/05/12)
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- Copper-catalyzed and iodide-promoted aerobic C-C bond cleavage/C-N bond formation toward the synthesis of amides
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A copper-catalyzed and iodide-promoted aerobic C-C bond cleavage/C-N bond formation reaction between ketone and simple amine was developed toward the synthesis of amides, which are useful synthetic intermediates in organic synthesis and important skeletons of biologically active molecules. Notably, the reaction conditions are very mild, and preliminary mechanistic investigations indicate that molecular oxygen might be involved in the C-C bond cleavage process.
- Wu, Kun,Huang, Zhiliang,Ma, Yiyang,Lei, Aiwen
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p. 24349 - 24352
(2016/03/15)
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- Copper-catalyzed one-pot oxidative amidation of alcohol to amide via C-H activation
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A one-pot oxidative amidation of both aliphatic and aromatic alcohols with N-chloramines, prepared in situ from many types of primary and secondary amines, was developed. This cross-coupling reaction integrates alcohol oxidation and amide bond formation, which are usually accomplished separately, into a single operation. And it was green, simple and convenient, which has a wide substrate scope and makes use of cheap, abundant, and easily available reagents. The practical value of this method is highlighted through the synthesis of a high-profile pharmaceutical agent, acetylprocainamide.
- Gu, Jiajia,Fang, Zheng,Yang, Yuhang,Yang, Zhao,Wan, Li,Li, Xin,Wei, Ping,Guo, Kai
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p. 89413 - 89416
(2016/10/03)
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- Covalent triazine framework-supported palladium as a ligand-free catalyst for the selective double carbonylation of aryl iodides under ambient pressure of CO
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Carbonylation of aryl iodides with amines under atmospheric pressure of CO, catalyzed by Pd/CTFs (covalent triazine frameworks) without any specific additives, leads to the highly selective synthesis of α-ketoamides.
- Wang, Zhifang,Liu, Cuibo,Huang, Yi,Hu, Yuchen,Zhang, Bin
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supporting information
p. 2960 - 2963
(2016/02/19)
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- CuCl/TBHP catalyzed synthesis of amides from aldehydes and amines in water
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A CuCl/TBHP catalyzed amidation of aldehydes with amine under aqueous media is described. Both aliphatic and aromatic aldehydes coupled with a variety of amines under the reaction conditions employed.
- Lu, Shao-Yi,Badsara, Satpal Singh,Wu, Yi-Chun,Reddy, Daggula Mallikarjuna,Lee, Chin-Fa
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supporting information
p. 633 - 636
(2016/01/26)
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- Synthesis of Ag/g-C3N4Composite as Highly Efficient Visible-Light Photocatalyst for Oxidative Amidation of Aromatic Aldehydes
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In this contribution, an Ag/g-C3N4nanocomposite was synthesized and utilized as highly efficient and green photocatalyst for organic reactions under visible light irradiation. A layered, porous g-C3N4was synthes
- Wang, Lingling,Yu, Min,Wu, Chaolong,Deng, Nan,Wang, Chao,Yao, Xiaoquan
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p. 2631 - 2641
(2016/08/31)
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- Chloroform as a Carbon Monoxide Precursor: In or Ex Situ Generation of CO for Pd-Catalyzed Aminocarbonylations
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Conditions for the rapid hydrolysis of chloroform to carbon monoxide (CO) using heterogeneous CsOH·H2O are described. CO and 13CO can be generated cleanly and rapidly under mild conditions and can be captured either in or ex situ in palladium-catalyzed aminocarbonylation reactions. Utilizing only 1-3 equiv of CO allows for the aminocarbonylation of aryl, vinyl, and benzyl halides with a wide variety of primary and secondary amines giving amide products in good to excellent yields. (Chemical Equation Presented).
- Gockel, Samuel N.,Hull, Kami L.
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supporting information
p. 3236 - 3239
(2015/07/15)
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- Iodine-catalyzed efficient amide formation from aldehydes and amines
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An efficient iodine-catalyzed radical oxidative amidation of aldehydes with amines has been developed. This methodology was employed to prepare amides in good to excellent yields with the advantages of wide functional group tolerance and operational simplicity.
- Wang, Peng,Xia, Jiaxuan,Gu, Yueqing
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supporting information
p. 7120 - 7123
(2015/12/01)
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- Photoinduced Aminocarbonylation of Aryl Iodides
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Transition metal-catalyzed aminocarbonylation of aryl halides with CO and amines, pioneered by Heck and co-workers in the 1970s, is among the most commonly employed reactions to make aromatic amides. A catalyst-free aminocarbonylation of aryl iodides with CO and amines, which simply uses photoirradiation conditions by Xe-lamp, has now been developed. This methodology shows broad functional-group tolerance, including that of heteroaromatic amides. A hybrid radical/ionic chain mechanism, involving electron transfer from zwitterionic radical intermediates generated by nucleophilic attack of amines to aroyl radicals, is proposed.
- Kawamoto, Takuji,Sato, Aoi,Ryu, Ilhyong
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supporting information
p. 14764 - 14767
(2015/10/19)
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- Direct oxidative amidation between methylarenes and amines in water
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An environmentally friendly direct oxidative amidation between methylarenes and free amines was developed. The aromatic amide could be prepared efficiently from raw chemicals by employing TBHP as a "green" oxidant with co-catalysis of TBAI and FeCl3 in water.
- Wang, Tao,Yuan, Lin,Zhao, Zhenguang,Shao, Ailong,Gao, Meng,Huang, Yangfei,Xiong, Fei,Zhang, Huali,Zhao, Junfeng
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supporting information
p. 2741 - 2744
(2015/05/27)
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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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- Mild and direct conversion of esters to morpholine amides using diisobutyl(morpholino)aluminum: Application to efficient one-pot synthesis of ketones and aldehydes from esters
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Morpholine amide intermediates, which are easily prepared by aminolysis of various esters with diisobutyl(morpholino)aluminum, react with organolithium and reducing agents (DIBALH or LDBMA) without isolation of the aminolysis intermediates to give ketones in 83-95% yields and aldehydes quantitatively.
- Jeon, Ah Ram,Kim, Min Eai,Park, Jae Kyo,Shin, Won Kyu,An, Duk Keun
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p. 4420 - 4424
(2014/06/10)
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- Multistep synthesis of amides from alcohols and amines in continuous flow microreactor systems using oxygen and urea hydrogen peroxide as oxidants
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By integrating a heterogeneous oxidation step, gas-liquid separation, and an oxidative amidation reaction to form a continuous system, a multistep synthetic protocol has been demonstrated to produce amides under mild conditions using alcohols and amines as the starting materials. The use of inexpensive oxygen and urea hydrogen peroxide as the only oxidants affords an economical and adaptable synthetic route for amides.
- Liu, Xiaoying,Jensen, Klavs F.
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p. 1538 - 1541
(2013/09/24)
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- Palladium nanoparticles supported on ZIF-8 as an efficient heterogeneous catalyst for aminocarbonylation
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Pd nanoparticles supported on ZIF-8 (PdNPs/ZIF-8) are described as an efficient heterogeneous catalyst for the aminocarbonylation of bromoarenes in the presence of phosphines and iodoarenes under phosphine-free conditions. The catalyst can be readily prepared and is air-stable. The palladium loading can be as low as 1 wt %, and the catalyst was recycled four times with negligible change in catalytic performance. A variety of pharmaceutically important amides was readily synthesized. A TON of 2540 was easily achieved in a batch reaction by scaling up to a gram scale. The catalyst reported can also be applied to the synthesis of cyclic and primary amides as well as an alkoxycarbonylation reaction to form an ester.
- Dang, Tuan T.,Zhu, Yinghuai,Ngiam, Joyce S. Y.,Ghosh, Subhash C.,Chen, Anqi,Seayad, Abdul M.
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p. 1406 - 1410
(2013/07/26)
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- Highly efficient aminocarbonylation of iodoarenes at atmospheric pressure catalyzed by a robust acenaphthoimidazolyidene allylic palladium complex
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A robust allylic palladium-NHC complex was developed and exhibited extremely high catalytic activity toward aminocarbonylation of various (hetero)aryl iodides under atmospheric carbon monoxide pressure, in which a broad range of secondary and primary amines were well tolerated. In addition, the concise synthesis of an anticancer drug tamibarotene was accomplished even in a gram scale, further highlighting the practical applicability of the protocol.
- Fang, Weiwei,Deng, Qinyue,Xu, Mizhi,Tu, Tao
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supporting information
p. 3678 - 3681
(2013/08/23)
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- Preparation of tertiary amides via aryl, heteroaryl, and benzyl organozinc reagents; Scope and limitations
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A facile synthetic protocol for the preparation of tertiary amides has been developed. The title compounds have been successfully obtained by the Pd-catalyzed cross-coupling reactions of readily available aryl and benzyl organozinc reagents with the appropriate carbamoyl chlorides.
- Rieke, Reuben D.,Kim, Seung-Hoi
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experimental part
p. 3478 - 3481
(2012/08/13)
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- Direct oxidative amidation of aromatic aldehydes using aqueous hydrogen peroxide in continuous flow microreactor systems
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A practical and economical protocol has been developed for the direct oxidative amidation of aromatic aldehydes with secondary amines to synthesize amides in a single operation under mild conditions within 15-40 min. The utilization of aqueous hydrogen peroxide affords a clean synthetic route. No catalysts or promoting reagents are required.
- Liu, Xiaoying,Jensen, Klavs F.
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supporting information; experimental part
p. 1471 - 1474
(2012/06/04)
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- Mild conversion of esters lacking acidic α-hydrogens into amides via samarium(III) tris[hexamethyldisilazide] and amines
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Samarium(III) tris[hexamethyldisilazide] (Sm[(Me3Si) 2N]3 = Sm[HMDS]3) promotes the direct conversion of an ester admixed with an amine into the corresponding carboxamide under exceptionally mild conditions (≤0°) and in high yields. Only a slight excess of amine and the lanthanide complex are required to effect complete conversion of the ester into the amide. Esters with acidic α-hydrogens undergo a competing Claisen-like condensation along with the desired conversion into amides. Georg Thieme Verlag Stuttgart New York.
- Campbell, James B.,Sparks, Richard B.,Dedinas, Robert F.
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experimental part
p. 357 - 360
(2011/03/22)
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- Synthesis of isotopically labelled SGLT inhibitors and their metabolites
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Isotopically labelled analogues of two structurally very similar SGLT inhibitors AVE2268 (1a) and AVE8887 (1b) have been synthesized by various routes. The radioactive labelled [14C]-AVE2268 was prepared in five steps including a Friedel-Crafts acylation as the key step for the 14C-label introduction. For [14C]-AVE8887 the same synthetic approach was not successful and therefore an alternative thiophene metallation/Weinreb amide sequence was developed. This pathway was also applied to obtain stable isotopically labelled analogues of both AVE2268 and AVE8887. Finally, the synthesis of two metabolites, sulfate 12 and glucuronide 13 were achieved by applying interesting protecting group and oxidation strategies.
- Derdau, Volker,Fey, Thorsten,Atzrodt, Jens
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scheme or table
p. 1472 - 1482
(2010/04/02)
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- INHIBITORS OF JANUS KINASES
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The instant invention provides for compounds that inhibit the four known mammalian JAK kinases (JAK1, JAK2, JAK3 and TYK2). The invention also provides for compositions comprising such inhibitory compounds and methods of inhibiting the activity of JAK1, JAK2, JAK3 and TYK2 by administering the compound to a patient in need of treatment for myeloproliferative disorders or cancer
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Page/Page column 49
(2010/04/03)
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- PHENOXY ACETIC ACID DERIVATIVES
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The present invention provides phenoxyacetic acid derivatives of Formula (I) for the treatment of CRTH2 related disorders and disease selected from asthma, atopic dermatitis and inflammatory dermatoses.
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Page/Page column 133
(2010/09/03)
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- INHIBITORS OF JANUS KINASES
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The instant invention provides for compounds that inhibit the four known mammalian JAK kinases (JAK1, JAK2, JAK3 and TYK2). The invention also provides for compositions comprising such inhibitory compounds and methods of inhibiting the activity of JAK1, J
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Page/Page column 35-36
(2010/04/03)
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