- Transition-Metal-Free Acceptorless Decarbonylation of Formic Acid Enabled by a Liquid Chemical-Looping Strategy
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The selective decarbonylation of formic acid was achieved under transition-metal-free conditions. Using a liquid chemical-looping strategy, the thermodynamically favored dehydrogenation of formic acid was shut down, yielding a pure stream of CO with no H2 or CO2 contamination. The transformation involves a two-step sequence where methanol is used as a recyclable looping agent to yield methylformate, which is subsequently decomposed to carbon monoxide using alkoxides as catalysts.
- Imberdis, Arnaud,Lefèvre, Guillaume,Cantat, Thibault
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Read Online
- Engineering of Microcage Carbon Nanotube Architectures with Decoupled Multimodal Porosity and Amplified Catalytic Performance
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New approaches for the engineering of the 3D microstructure, pore modality, and chemical functionality of hierarchically porous nanocarbon assemblies are key to develop the next generation of functional aerogel and membrane materials. Here, interfacially driven assembly of carbon nanotubes (CNT) is exploited to fabricate structurally directed aerogels with highly controlled internal architectures, composed of pseudo-monolayer, CNT microcages. CNT Pickering emulsions enable engineering at fundamentally different length scales, whereby the microporosity, mesoporosity, and macroporosity are decoupled and individually controlled through CNT type, CNT number density, and process energy, respectively. In addition, metal nanocatalysts (Cu, Pd, and Ru) are embedded within the architectures through an elegant sublimation and shock-decomposition approach; introducing the first approach that enables through-volume functionalization of intricate, pre-designed aerogels without microstructural degradation. Catalytic structure–function relationships are explored in a pharma-important amidation reaction; providing insights on how the engineered frameworks enhance catalyst activity. A sophisticated array of advanced tomographic, spectroscopic, and microscopic techniques reveal an intricate 3D assembly of CNT building-blocks and their influence on the functional properties of the enhanced nanocatalysts. These advances set a basis to modulate structure and chemistry of functional aerogel materials independently in a controlled fashion for a variety of applications, including energy conversion and storage, smart electronics, and (electro)catalysis.
- Brydson, Rik,Cairns, Gareth A.,Chamberlain, Thomas W.,Flahaut, Emmanuel,Hondow, Nicole,Mannering, Jamie,Menzel, Robert,Stones, Rebecca,Sykes, Daniel,Xia, Dong
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- Conformational, vibrational, NMR and DFT studies of N-methylacetanilide
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A detailed conformational, vibrational, NMR and DFT studies of N-methylacetanilide have been carried out. In DFT, B3LYP method have been used with 6-31G(d,p), 6-311++G(d,p) and cc-pVTZ basis sets. The vibrational frequencies were calculated resulting in IR and Raman frequencies together with intensities and Raman depolarisation ratios. The dipole moment derivatives were computed analytically. Owing to the complexity of the molecule, the potential energy distributions of the vibrational modes of the compound are also calculated. Isoelectronic molecular electrostatic potential surface (MEP) and electron density surface were examined. 1H and 13C NMR isotropic chemical shifts were calculated and the assignments made are compared with the experimental values. The energies of important MO's of the compound were also determined from TD-DFT method.
- Arjunan,Santhanam,Rani,Rosi,Mohan
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- Preparation and catalytic evaluation of a palladium catalyst deposited over modified clinoptilolite (Pd&at;MCP) for chemoselective N-formylation and N-acylation of amines
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Novel palladium nanoparticles stabilized by clinoptilolite as a natural inexpensive zeolite prepared and used for N-formylation and N-acylation of amines at room temperature at environmentally benign reaction conditions in good to excellent yields. Pd (II) was immobilized on the surface of clinoptilolite via facile multi-step amine functionalization to obtain a sustainable, recoverable, and highly active nano-catalyst. The structural and morphological characterizations of the catalyst carried out using XRD, FT-IR, BET and TEM techniques. Moreover, the catalyst is easily recovered using simple filtration and reused for 7 consecutive runs without any loss in activity.
- Amirsoleimani, Mina,Khalilzadeh, Mohammad A.,Zareyee, Daryoush
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- An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides
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Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.
- Kumar, Vishal,Dhawan, Sanjeev,Girase, Pankaj Sanjay,Singh, Parvesh,Karpoormath, Rajshekhar
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p. 5627 - 5639
(2021/11/11)
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- Method for preparing aryl amide compound by catalyzing carbonylation of aryl tertiary amine through metal-free catalytic system
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The invention discloses a method for preparing aryl amide compounds by catalyzing aryl tertiary amine carbonylation through a metal-free catalytic system. The method is characterized in that in a reaction solvent, carbonyl molybdenum is used as a substitute carbonyl source, an organic base is used as a main catalyst, and methyl iodide is used as a catalyst promoter; and carbonylation of aryl tertiary amine is catalyzed under normal pressure to prepare the aryl amide compound. The reaction formula of synthesis is shown in the specification, wherein R is one of CH3, C2H5, pheyl, F, CL, Br or CN. According to the present invention, the organic base is adopted as the main catalyst, the iodomethane is adopted as the catalyst promoter, the carbonyl molybdenum is adopted as the substitute carbonyl source, and the aryl tertiary amine carbonylation can be efficiently catalyzed at the reaction temperature of 140 DEG C to prepare the aryl amide compound, so that the atom economy of the reaction is effectively improved, and a wide application prospect is provided; the molybdenum carbonyl is used as the substitute carbonyl source, so that the potential safety hazard of carbon monoxide is avoided; and the reaction can be carried out under normal pressure in the reaction process, and high-pressure reaction equipment is not needed.
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Paragraph 0028-0043; 0050-0063; 0068-0069
(2021/08/19)
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- Method for promoting acylation of amine or alcohol by carbon dioxide
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The invention relates to a method for promoting acylation of amine or alcohol by carbon dioxide, which comprises the following steps of: mixing an amine compound, carboxylate or thiocarboxylate compound and a reaction solvent under the action of carbon dioxide, and reacting to obtain an amide compound, or under the action of carbon dioxide, mixing the alcohol compound, the thiocarboxylate compound and the reaction solvent [gamma]-valerolactone, and reacting to obtain the ester compound. According to the invention, under the promotion action of carbon dioxide, carboxylate or thiocarboxylate is used as an acylation reagent, and amine and alcohol are converted into amide and ester compounds in the absence of a transition metal catalyst, so that acylation reagents such as acyl chloride or anhydride with irritation and corrosivity are avoided; and the method has the advantages of simple operation, mild reaction conditions, high tolerance of substrate functional groups, strong applicability and high yield, and provides an efficient, reliable and economical preparation method for synthesis of amide and ester compounds.
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Paragraph 0036-0038
(2021/05/29)
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- Novel hybrid conjugates with dual estrogen receptor α degradation and histone deacetylase inhibitory activities for breast cancer therapy
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Hormone therapy targeting estrogen receptors is widely used clinically for the treatment of breast cancer, such as tamoxifen, but most of them are partial agonists, which can cause serious side effects after long-term use. The use of selective estrogen receptor down-regulators (SERDs) may be an effective alternative to breast cancer therapy by directly degrading ERα protein to shut down ERα signaling. However, the solely clinically used SERD fulvestrant, is low orally bioavailable and requires intravenous injection, which severely limits its clinical application. On the other hand, double- or multi-target conjugates, which are able to synergize antitumor activity by different pathways, thus may enhance therapeutic effect in comparison with single targeted therapy. In this study, we designed and synthesized a series of novel dual-functional conjugates targeting both ERα degradation and histone deacetylase inhibiton by combining a privileged SERD skeleton 7-oxabicyclo[2.2.1]heptane sulfonamide (OBHSA) with a histone deacetylase inhibitor side chain. We found that substituents on both the sulfonamide nitrogen and phenyl group of OBHSA unit had significant effect on biological activities. Among them, conjugate 16i with N-methyl and naphthyl groups exhibited potent antiproliferative activity against MCF-7 cells, and excellent ERα degradation activity and HDACs inhibitory ability. A further molecular docking study indicated the interaction patterns of these conjugates with ERα, which may provide guidance to design novel SERDs or PROTAC-like SERDs for breast cancer therapy.
- Zhao, Chenxi,Tang, Chu,Li, Changhao,Ning, Wentao,Hu, Zhiye,Xin, Lilan,Zhou, Hai-Bing,Huang, Jian
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- Z-Selective Fluoroalkenylation of (Hetero)Aromatic Systems by Iodonium Reagents in Palladium-Catalyzed Directed C?H Activation
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The direct and catalytic incorporation of fluorine containing molecular motifs into organic compounds resulting high-value added chemicals represents a rapidly evolving part of synthetic methodologies, thus this area is in the focus of pharmaceutical and agrochemical research. Herein we report a stereoselective procedure for direct fluorovinylation of aromatic and heteroaromatic scaffolds. This methodology development has been realized by palladium-catalyzed ortho C?H activation reaction of aniline derivatives featuring the regioselectivity via directing groups such as secondary of tertiary amides, ureas or ketones. The application of non-symmetrical aryl(fluoroalkenyl)-iodonium salts as fluoroalkenylating agents allowed mild reaction conditions in general for this transformation. The scope and limitations have been thoroughly investigated and the feasibility has been demonstrated by more than 50 examples.
- Bényei, Attila,Domján, Attila,Egyed, Orsolya,Gonda, Zsombor,Novák, Zoltán,Sályi, Gerg?,Tóth, Balázs L.
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- Asymmetric Transfer Hydrogenation of α-Keto Amides; Highly Enantioselective Formation of Malic Acid Diamides and α-Hydroxyamides
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The asymmetric transfer hydrogenation (ATH) of α-keto-1,4-diamides using a tethered Ru/TsDPEN catalyst was achieved in high ee. Studies on derivatives identified the structural elements which lead to the highest enantioselectivities in the products. The α-keto-amide reduction products have been converted to a range of synthetically valuable derivatives.
- Gediya, Shweta K.,Vyas, Vijyesh K.,Clarkson, Guy J.,Wills, Martin
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supporting information
p. 7803 - 7807
(2021/10/20)
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- An organocatalytic C-C bond cleavage approach: A metal-free and peroxide-free facile method for the synthesis of amide derivatives
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A facile organocatalytic approach has been devised towards the synthesis of amide derivatives using 1,3-dicarbonyls as easily available acyl-sources under peroxide-free reaction conditions. This transformation was accomplished by the cleavage of the C-C bond in the presence of TEMPO as an organocatalyst and excludes the use of transition-metals and harsh reaction conditions. A broad range of substrates with diverse functional groups were well tolerated and delivered the products in high yields.
- Vodnala, Nagaraju,Gujjarappa, Raghuram,Polina, Saibabu,Satheesh, Vanaparthi,Kaldhi, Dhananjaya,Kabi, Arup K.,Malakar, Chandi C.
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supporting information
p. 20940 - 20944
(2020/12/31)
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- N-Heterocyclic Carbene/Cobalt Cooperative Catalysis for the Chemo- and Regioselective C?N Bond Formation between Aldehyde and Amines/Amides
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A novel methodology for the construction of various secondary (4 examples), tertiary amides (31 examples), and imides (16 examples) by a Cobalt(II) catalyzed oxidative amide coupling in aqueous media. The Co(III)-TMC was reacted with N-Heteroatom Carbene to form active catalyst Co(II)NHC-TMC in situ which involves in the coordination with Breslow's intermediate and SET for the activation of aldehyde and amides. The mechanism for activation of amide and amine differs on the basis of SET based nucleophilic addition and ligand exchange respectively. The regeneration of the catalyst was achieved using Fe(III)(EDTA)-H2O2 as oxidant. The use of Co(II)TMC-O2 was also found equally efficient in the process. The method is found regioselective for N?H activation in the presence of equally susceptible ortho-C?H bond activation. And amines were found more susceptible then the corresponding amide for the reaction.
- Siddiqui, Asher M.,Khalid, Anam,Khan, Arif,Azad, Chandra S.,Samim, Mohd.,Khan, Imran A.
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p. 4281 - 4287
(2020/07/24)
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- Phenysilane and Silicon Tetraacetate: Versatile Promotors for Amide Synthesis
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Phenylsilane was reevaluated as a useful coupling reagent for amide synthesis. At room temperature, a wide range of amides and peptides were obtained in good to excellent yields (up to 99 %). For the first time, Weinreb amides synthesis mediated by a hydrosilane were also documented. Comparative experiments with various acetoxysilanes suggested the involvement of a phenyl-triacyloxysilane. From this mechanistic study, silicon tetraacetate was shown as an efficient amine acylating agent.
- Morisset, Eléonore,Chardon, Aurélien,Rouden, Jacques,Blanchet, Jér?me
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supporting information
p. 388 - 392
(2020/01/24)
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- Selective Methylation of Amides, N-Heterocycles, Thiols, and Alcohols with Tetramethylammonium Fluoride
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We herein disclose the use of tetramethylammonium fluoride (TMAF) as a direct and selective methylating agent of a variety of amides, indoles, pyrroles, imidazoles, alcohols, and thiols. The method is characterized by operational simplicity, wide scope, and ease of purification. Our computational studies suggest a concerted methylation-deprotonation as the preferred reaction pathway.
- Cheng, Hong-Gang,Pu, Maoping,Kundu, Gourab,Schoenebeck, Franziska
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supporting information
p. 331 - 334
(2019/12/30)
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- Carbonylation of C?N Bonds in Tertiary Amines Catalyzed by Low-Valent Iron Catalysts
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The first iron catalysts able to promote the formal insertion of CO into the C?N bond of amines are reported. Using low-valent iron complexes, including K2[Fe(CO)4], amides are formed from aromatic and aliphatic amines, in the presence of an iodoalkane promoter. Inorganic Lewis acids, such as AlCl3 and Nd(OTf)3, have a positive influence on the catalytic activity of the iron salts, enabling the carbonylation at a low pressure of CO (6 to 8 bars).
- Nasr Allah, Tawfiq,Savourey, Solène,Berthet, Jean-Claude,Nicolas, Emmanuel,Cantat, Thibault
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supporting information
p. 10884 - 10887
(2019/07/15)
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- Synthesis of diverse libraries of carboxamides via chemoselective N-acylation of amines by carboxylic acids employing Br?nsted acidic IL [BMIM(SO3H)][OTf]
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Chemoselective N-acylation of amines with carboxylic acids as acyl electrophiles and Br?nsted acidic IL [BMIM(SO3H)][OTf] as promoter is reported under both thermal and microwave irradiation to produce libraries of carboxamides in good to excellent yields after a simple workup. The protocol is compatible with structurally diverse 1° and 2° amines and works in the presence of sensitive functional groups such as thiols and phenols. The potential for recycling and reuse of the IL is also demonstrated.
- Savanur, Hemantkumar M.,Malunavar, Shruti S.,Prabhala, Pavankumar,Sutar, Suraj M.,Kalkhambkar, Rajesh G.,Laali, Kenneth K.
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supporting information
(2019/09/30)
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- An efficient synthesis of benzothiazole using tetrabromomethane as a halogen bond donor catalyst
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An efficient and mild protocol has been developed for the synthesis of 2-substituted benzothiazole under solvent- and metal-free conditions using CBr4 as the catalyst. This process involves the activation of a thioamide through halogen bond formation between the sulphur atom of the thioamide and bromine atom of the CBr4 molecule. The presence of halogen-bonding interaction between N-methylthioamides and tetrabromomethane has been demonstrated with several control experiments, spectroscopic analysis and density functional theory (DFT). This methodology has a wide substrate scope for the synthesis of both 2-alkyl and 2-aryl substituted benzothiazoles.
- Kazi, Imran,Sekar, Govindasamy
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p. 9743 - 9756
(2019/12/02)
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- Preparation method of N-methyl-4-bromoaniline
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The invention provides a preparation method of N-methyl-4-bromoaniline, belonging to the technical field of organic synthesis. The preparation method solves the technical problems that existing monomethylation reaction steps of aniline are tedious and the purity of prepared products is low. The method comprises the following steps: 1, adding dichloroethane and N-methylaniline into a first reactor,then dropwise adding acetic anhydride into the first reactor, and carrying out stirring; 2, dropwise adding a brominating agent into the formed reaction system, carrying out stirring, carrying out sampling analysis until the content of N-methyl acetanilide is less than 1%, adding sodium sulfite, carrying out stirring, and carrying out suction filtration; 3, adding the solid N-methyl-4-bromoacetanilide obtained through suction filtration in the step 2 into a second reactor, then adding hydrochloric acid with a mass concentration of 15%, carrying out heating reflux for 3 h, and carrying out sampling analysis until a reaction is completed; and 4, cooling, neutralizing and extracting the reaction system in the step 3, and recovering the solvent to obtain the colorless transparent liquid N-methyl-4-bromoaniline. The N-methyl-4-bromoaniline prepared by using the method is high in purity, and has a content of greater than 98%.
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Paragraph 0046-0048; 0053-0055; 0060-0062
(2019/12/25)
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- Amide Bond Formation Catalyzed by Recyclable Copper Nanoparticles Supported on Zeolite Y under Mild Conditions
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A series of catalysts based on supported copper nanoparticles have been prepared and tested in the amide bond formation from tertiary amines and acid anhydrides, in the presence of tert-butyl hydroperoxide as an oxidant. Copper nanoparticles on zeolite Y (CuNPs/ZY) was found to be the most efficient catalyst for the synthesis of amides, working in acetonitrile as solvent, under ligand- and base-free conditions in air. The products were obtained in good to excellent yields and in short reaction times. The CuNPs/ZY system also exhibited higher catalytic activity than some commercially available copper and iron sources and it was reused in ten reaction cycles without any further pre-treatment. This methodology has been successfully scaled-up to a gram scale with no detriment to the yield.
- Moglie, Yanina,Buxaderas, Eduardo,Mancini, Agustina,Alonso, Francisco,Radivoy, Gabriel
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p. 1487 - 1494
(2019/02/16)
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- Method for selective N-methylation of secondary amide
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The invention relates to a method for selective N-methylation of secondary amide. The method is characterized in that the secondary amide is in an organic solvent N, N-dimethyl formamide or dimethyl sulfoxide, trifluoroacetic acid methyl ester serves as a methylation reagent, and reaction is performed in the presence of sodium hydride, potassium tert-butoxide or sodium methylate, so as to obtain aselective N-methylated product. The method has the characteristics that generally a trifluoroacetylation product is produced when the trifluoroacetic acid methyl ester is reacted with amine compounds, however a N-methylated product can be selectively obtained when the trifluoroacetic acid methyl ester is reacted with secondary amide; the method is simple to operate, low in cost, mild in reactionconditions and high in selectivity, and avoids the use of hypertoxic methylation reagents, such as dimethyl sulfate and methyl iodide.
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Paragraph 0011
(2019/03/08)
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- Synthesis of acetamides using CO2, methanol, H2 and amines
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Herein, we report the synthesis of acetamides from CO2, methanol, H2 and corresponding amines, which is a new route used to synthesize acetamides. It was found that the Rh catalyst with LiI/LiCl as promoters could effectively catalyze this reaction. Interestingly, no ligand was required and amine substrates played a role in accelerating the reaction.
- Zhang, Jingjing,Qian, Qingli,Wang, Ying,Asare Bediako, Bernard Baffour,Cui, Meng,Yang, Guanying,Han, Buxing
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supporting information
p. 233 - 237
(2019/01/28)
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- Amide Synthesis from Thiocarboxylic Acids and Amines by Spontaneous Reaction and Electrosynthesis
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Amide bond formation is one of the most important basic reactions in chemistry. A catalyst-free approach for constructing amide bonds from thiocarboxylic acids and amines was developed. The mechanistic studies showed that the disulfide was the key intermediate for this amide synthesis. Thiobenzoic acids could be automatically oxidized to disulfides in air, thioaliphatic acids could be electro-oxidized to disulfides, and the resulting disulfides reacted with amines to give the corresponding amides. By this method, various amides could be easily synthesized in excellent yields without using any catalyst or activator. The successful synthesis of bioactive compounds also highlights the synthetic utility of this strategy in medicinal chemistry.
- Tang, Li,Matuska, Jack H.,Huang, Yu-Han,He, Yan-Hong,Guan, Zhi
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p. 2570 - 2575
(2019/06/13)
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- Exploring the PROTAC degron candidates: OBHSA with different side chains as novel selective estrogen receptor degraders (SERDs)
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As the mutant estrogen receptor (ER) continues to be characterized, breast cancer is becoming increasingly difficult to cure when treated with hormone therapy. In this regard, a strategy to selectively and effectively degrade the ER might be an effective alternative to endocrine therapy for breast cancer. In a previous study, we identified a novel series of 7-oxabicyclo[2.2.1]heptene sulfonamide (OBHSA) compounds as full ER antagonists while lacking the prototypical ligand side chain that has been widely used to induce antagonism of ERα. Further crystal structure studies and phenotypic assays revealed that these compounds are selective estrogen receptor degraders (SERDs) with a new mechanism of action. However, from a drug discovery point of view, there still is room to improve the potency of these OBHSA compounds. In this study, we have developed new classes of SERDs that contain the OBHSA core structure and different side chains, e.g., basic side chains, long alkyl acid side chains, and glycerol ether side chains, to simply mimic the degrons of proteolysis targeting chimera (PROTAC) and then investigated the structure-activity relationships of these PROTAC-like hybrid compounds. These novel SERDs could effectively inhibit MCF-7 cell proliferation and demonstrated good ERα degradation efficacy. Among the SERDs, compounds 17d, 17e and 17g containing a basic side chain with a N-trifluoroethyl substituent and a para methoxyl group at the phenyl group of the sulfonamide turned out to be the best candidates for ER degraders. A further docking study of these compounds with ERα elucidates their structure-activity relationships, which provides guidance to design new PROTAC degrons targeting ER for breast cancer therapy. Lastly, easy modification of these PROTAC-like SERDs enables further fine-tuning of their pharmacokinetic properties, including oral availability.
- Li, Yuanyuan,Zhang, Silong,Zhang, Jing,Hu, Zhiye,Xiao, Yuan,Huang, Jian,Dong, Chune,Huang, Shengtang,Zhou, Hai-Bing
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- Flower-like AgNPs@m-MgO as an excellent catalyst for CO2 fixation and acylation reactions under ambient conditions
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Synthesis of fine chemicals from the chemical fixation of CO2 is one of the attractive research areas of today to utilise greenhouse gas CO2 in a greener pathway. A flower-like silver nanoparticle grafted mesoporous magnesium oxide (AgNPs@m-MgO) nanocomposite has been prepared by a facile in situ pathway. The materials are characterised by XRD, FTIR, UV-vis, TG-DTA, FESEM, HR-TEM and N2 adsorption-desorption studies. This AgNPs@m-MgO material showed a mesoporous nature with good surface area. It indicated brilliant catalytic activity for both the carboxylation of terminal alkynes by chemical fixation of CO2 (1 atm) and the acylation of various amines by utilizing acetic acid as a reagent in solvent-free conditions showing yields up to 98% and 99% of the propiolic acid and acetamide products, respectively. The reusability of this catalyst has also been verified and it showed high recycling efficiency for both the reactions together with no considerable catalyst deactivation.
- Chowdhury, Arpita Hazra,Ghosh, Swarbhanu,Islam, Sk. Manirul
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p. 14194 - 14202
(2018/08/28)
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- 1,1-Diacyloxy-1-phenylmethanes as versatile N-acylating agents for amines
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1,1-Diacyloxy-1-phenylmethanes and 1-pivaloxy-1-acyloxy-1-phenylmethanes have been used as bench stable N-acylating reagents for primary and secondary amines and anilines under solvent-free conditions to afford their corresponding amides in good yield.
- Chapman, Robert. S.L.,Tibbetts, Joshua. D.,Bull, Steven. D.
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p. 5330 - 5339
(2018/06/15)
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- Protection of COOH and OH groups in acid, base and salt free reactions
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We report an iron-catalyzed general functional group protection method with inexpensive reagents. This environmentally benign process does not use acids or bases, and does not produce waste products. Further purification beyond filtration and evaporation is, in most cases, unnecessary. Free COOH and OH groups can be protected in a one-pot reaction.
- Zhu, Xiaotao,Qian, Bo,Wei, Rongbiao,Huang, Jian-Dong,Bao, Hongli
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supporting information
p. 1444 - 1447
(2018/04/12)
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- Copper-(II) Catalyzed N-Formylation and N-Acylation of Aromatic, Aliphatic, and Heterocyclic Amines and a Preventive Study in the C-N Cross Coupling of Amines with Aryl Halides
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A Cu-(II) catalyzed N-formylation and N-acylation of amines with moderate to excellent yields, using N, N-dimethyl formamide (DMF) and N, N-dimethyl acetamide (DMA) as a formyl and acylating sources in the presence of 1,2,4-triazole is reported. This novel, highly efficient and simple protocol shows broad substrate scope for aliphatic, aromatic, and heterocyclic amines. In addition, the conditions to prevent N-formylation and N-acylation impurities in the C?N cross coupling of amines and aryl halides are described typically when DMF and DMA are used as solvents, with various catalysts, ligands, and bases.
- Sonawane, Rahul B.,Rasal, Nishant K.,Bhange, Dattatraya S.,Jagtap, Sangeeta V.
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p. 3907 - 3913
(2018/09/12)
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- Amide Effects in C?H Activation: Noncovalent Interactions with L-Shaped Ligand for meta Borylation of Aromatic Amides
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A new concept for the meta-selective borylation of aromatic amides is described. It has been demonstrated that while esters gave para borylations, amides lead to meta borylations. For achieving high meta selectivity, an L-shaped bifunctional ligand has been employed and engages in an O???K noncovalent interaction with the oxygen atom of the moderately distorted amide carbonyl group. This interaction provides exceptional control for meta C?H activation/borylation.
- Bisht, Ranjana,Hoque, Md Emdadul,Chattopadhyay, Buddhadeb
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supporting information
p. 15762 - 15766
(2018/11/10)
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- Acceleration of Pd-Catalyzed Amide N-Arylations Using Cocatalytic Metal Triflates: Substrate Scope and Mechanistic Study
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The Pd/xantphos-catalyzed cross-coupling of amides and aryl halides is accelerated by cocatalytic metal triflate additives. A survey of nitrogen nucleophiles reveals improved yields for a variety of N-aryl amide products when Al(OTf)3 is employed as a catalytic additive, with some exceptions. Initial rates of catalysis indicate that the Lewis acid acceleration is more pronounced when bromobenzene (PhBr) is used in comparison with iodobenzene (PhI). The observation of an aryl halide dependence on rate and various qualitative kinetic experiments are consistent with a mechanism in which ligand exchange of halide for amide ("transmetalation") is turnover limiting. The mechanism may be different depending on whether PhBr or PhI is used as a coupling partner. Oxidative addition complexes (xantphos)Pd(Ph)(X) (X = Br, I; xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene), likely intermediates in catalysis, have been prepared; their differing interactions with Yb(OTf)3 in solution resemble the halide dependence of the catalytic mechanism, which we propose originates from a reversible Lewis acid mediated halide abstraction during catalysis.
- Becica, Joseph,Dobereiner, Graham E.
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p. 5862 - 5870
(2017/09/15)
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- Thermolysis and radiofluorination of diaryliodonium salts derived from anilines
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Aniline-derived diaryliodonium salts were synthesized and functionalized in good to excellent yields by judicious utilization of electron-withdrawing protecting groups. This simple approach opens another route to radiolabeling amino arenes in relatively complex molecules, such as flutemetamol.
- Linstad, Ethan J.,Vāvere, Amy L.,Hu, Bao,Kempinger, Jayson J.,Snyder, Scott E.,DiMagno, Stephen G.
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supporting information
p. 2246 - 2252
(2017/03/17)
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- Electron-Transfer and Hydride-Transfer Pathways in the Stoltz–Grubbs Reducing System (KOtBu/Et3SiH)
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Recent studies by Stoltz, Grubbs et al. have shown that triethylsilane and potassium tert-butoxide react to form a highly attractive and versatile system that shows (reversible) silylation of arenes and heteroarenes as well as reductive cleavage of C?O bonds in aryl ethers and C?S bonds in aryl thioethers. Their extensive mechanistic studies indicate a complex network of reactions with a number of possible intermediates and mechanisms, but their reactions likely feature silyl radicals undergoing addition reactions and SH2 reactions. This paper focuses on the same system, but through computational and experimental studies, reports complementary facets of its chemistry based on a) single-electron transfer (SET), and b) hydride delivery reactions to arenes.
- Smith, Andrew J.,Young, Allan,Rohrbach, Simon,O'Connor, Erin F.,Allison, Mark,Wang, Hong-Shuang,Poole, Darren L.,Tuttle, Tell,Murphy, John A.
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p. 13747 - 13751
(2017/10/12)
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- Electrophilic Amination with Nitroarenes
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An exceptionally general electrophilic amination, which directly transforms commercially available nitroarenes into alkylated aromatic aminoboranes with zinc organyl compounds was developed. The reaction starts with a two-step partial reduction of the nitro group to a nitrenoid, which is used in situ as the electrophilic amination reagent. To facilitate isolation, the resulting air- and moisture-sensitive aminoboranes were reacted with a range of electrophiles. The method not only represents a direct transformation of nitro compounds into electrophilic amination reagents but also provides an elegant alternative to dehydrocoupling methods for the generation of aminoboranes.
- Rauser, Marian,Ascheberg, Christoph,Niggemann, Meike
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supporting information
p. 11570 - 11574
(2017/09/11)
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- Nickel-(II)-Catalyzed N-Formylation and N-Acylation of Amines
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A highly efficient protocol of Ni(II) metal complex, [Ni(quin)2], catalyzing N-formylation and N-acylation of amines with moderate to excellent yields, using N,N-dimethylformamide and N,N-dimethylacetamide in the presence of imidazole, is described here. The protocol shows broad substrate scope for aliphatic, aromatic, and heterocyclic amines.
- Sonawane, Rahul B.,Rasal, Nishant K.,Jagtap, Sangeeta V.
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supporting information
p. 2078 - 2081
(2017/04/28)
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- Transfer Hydro-dehalogenation of Organic Halides Catalyzed by Ruthenium(II) Complex
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A simple and efficient Ru(II)-catalyzed transfer hydro-dehalogenation of organic halides using 2-propanol solvent as the hydride source was reported. This methodology is applicable for hydro-dehalogenation of a variety of aromatic halides and α-haloesters and amides without additional ligand, and quantitative yields were achieved in many cases. The potential synthetic application of this method was demonstrated by efficient gram-scale transformation with catalyst loading as low as 0.5 mol %.
- You, Tingjie,Wang, Zhenrong,Chen, Jiajia,Xia, Yuanzhi
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p. 1340 - 1346
(2017/02/10)
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- Reductive dehalogenation method of organic halide
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The invention discloses a reductive dehalogenation method of an organic halide. In the inert gas atmosphere, the organic halide shown as the formula I or the formula II is subjected to reductive dehalogenation to generate an organic compound shown as the formula III or the formula IV (the formulas are shown as the description) in the presence of a catalyst, alkali and a solvent, wherein the reaction temperature is controlled to 90-100 DEG C. The reductive dehalogenation method has the advantages that the range of substrates is widened; the solvent in use does not need extra phosphorous ligands, the price is relatively cheap, and the consumption can be greatly reduced to 0.1 mol%; the solvent in use serves as a hydrogen source and reacts, the operation is simple, a lot reactions can reach quantitative yields, and when the reactions are scaled up to gram level reactions, almost quantitative yields can still be achieved.
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Paragraph 0093; 0094; 0095; 0096; 0097; 0098
(2017/08/28)
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- Method for preparing N-aryl tertiary amide with substituted Meldrum's acid as acylating agent in water phase
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The invention discloses a method for preparing N-aryl tertiary in a water phase. According to the method, water is used as the solvent, and substituted Meldrum's acid and N-aryl secondary amine react at 80-100 DEG C for 1-10 h to obtain the N-aryl tertiary. The molar ratio of substituted Meldrum's acid to N-aryl secondary amine is 1:10-10:1. The reaction concentration of substituted Meldrum's acid or N-aryl secondary amine is 0.5-4 mol/L. The method overcomes the defect that in the prior art, acyl chloride, anhydride, dehydration coupling reagent, organic solvent, phase transfer catalyst or metal catalyst needs to be adopted, and has the advantages that by using substituted Meldrum's acid as an acylating agent, pre-activating of carboxylic acid or using of a dehydration coupling reagent is avoided; due to the fact that substituted Meldrum's acid is easy to prepare, using of certain carboxylic acid and activated derivatives which are hard to get or expensive is avoided; water is used as the solvent, so that using of toxic organic solvent is avoided; no acid, alkali or metal catalyst is adopted, so that influences of acid and alkali on sensitive groups and equipment and metal ion residues in products are avoided. The synthesis method can play an important role in industrial production of N-aryl tertiary, especially N-aryl tertiary of complex carboxylic acid.
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Paragraph 0014; 0033
(2017/04/22)
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- Interception of amide ylides with sulfonamides: Synthesis of (: E)- N -sulfonyl amidines catalyzed by Zn(OTf)2
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Through the interception of amide ylides with sulfonamides, we herein report the first general example of an intermolecular condensation reaction between sulfonamides and amides. Beyond formamides, this approach was successfully applied to a variety of lactams and linear amides, giving rise to a broad array of (E)-N-sulfonyl amidines.
- Chen, Jijun,Long, Wenhao,Fang, Shangwen,Yang, Yonggang,Wan, Xiaobing
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supporting information
p. 13256 - 13259
(2017/12/26)
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- Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings
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The copper-catalyzed arylation of nucleophiles has been established as an efficient methodology for the formation of C-C and C-heteroatom bonds. Considering the advances during the last two decades, the ligand choice plays a key role in such transformations and can strongly influence the catalytic efficiency. The applicability of these Ullmann-type coupling reactions regarding the orthogonal selectivity of different functional groups constitutes a challenging subject for current synthetic strategies. Herein, we report a useful toolkit of Cu-based catalysts for the chemoselective arylation of a wide-range of nucleophiles in competitive reactions using aryl iodides and bromides. We show in this work that the arylation of all kinds of amides can be orthogonal to that of amines (aliphatic or aromatic) and phenol derivatives. This high chemoselectivity can be governed by the use of different ligands, yielding the desired coupling products under mild conditions. The selectivity trends are maintained for electronically biased iodobenzene and bromobenzene electrophiles. Radical clock experiments discard the occurrence of radical-based mechanisms.
- Rovira, Mireia,Soler, Marta,Güell, Imma,Wang, Ming-Zheng,Gómez, Laura,Ribas, Xavi
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supporting information
p. 7315 - 7325
(2016/09/09)
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- Potassium Thioacids Mediated Selective Amide and Peptide Constructions Enabled by Visible Light Photoredox Catalysis
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A remarkable visible-light-promoted photoredox catalytic methodology involved with amines and eco-friendly potassium thioacids for amide formation was uncovered. This approach can mimic the natural coenzyme acetyl-CoA to selectively acylate amines without affecting other functional groups such as alcohols, phenols, esters, among others. The developed strategy may hold great potential for a comprehensive display of biologically interesting peptide synthesis and amino acid modification through a diacyl disulfide intermediate.
- Liu, Hongxin,Zhao, Liyun,Yuan, Yunfei,Xu, Zhifang,Chen, Kai,Qiu, Shengxiang,Tan, Haibo
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p. 1732 - 1736
(2016/03/15)
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- Boron trifluoride-methanol complex. Mild and powerful reagent for deprotection of acetylated amines. Scope and selectivity
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A boron trifluoride-methanol complex demonstrated remarkable deprotection selectivity against commonly used amino-protecting groups in the deacetylation of acetanilides and high sensitivity to the steric hindrance of substrates. The scope and limitations of the reaction were explored.
- Miltsov, Sergey,Karavan, Vladimir,Misharev, Alexandr,Alonso-Chamarro, Julian,Puyol, Mar
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supporting information
p. 641 - 644
(2016/01/26)
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- The copper-catalyzed aerobic oxidative amidation of tertiary amines
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A general and efficient method for the synthesis of tertiary amides has been developed via the copper-catalyzed aerobic oxidative amidation of tertiary amines. Due to the use of the O2 oxidant, various functional groups were well tolerated under the present conditions. Extensive substrates studies demonstrated its potential as a practical approach for the synthesis of tertiary amides.
- Cheng, Hui-Cheng,Hou, Wen-Jun,Li, Zeng-Wen,Liu, Ming-Yu,Guan, Bing-Tao
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supporting information
p. 17596 - 17599
(2015/12/08)
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- Iron-catalyzed aerobic oxidative amidation of tertiary amines with carboxylic acids
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An oxidative amidation of tertiary amines with carboxylic acids has been developed in the presence of FeCl3·6H2O as catalyst and oxygen as oxidant. A variety of tertiary amides were obtained in good to excellent yields from inexpensive and readily available reagents. The possible reaction pathways were investigated.
- Ma, Lina,Li, Yuanming,Li, Zhiping
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p. 1310 - 1315
(2015/03/18)
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- Convenient N-acetylation of amines in N,N-dimethylacetamide with N,N-carbonyldiimidazole
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Dimethylacetamide (DMAc) acts as an efficient source of acetyl and dimethylamine gas in the presence of N,N-carbonyldiimidazole (CDI). Addition of amines to the reaction mixture delivers the corresponding amides in good to excellent yields. The acetylation of amines reported herein, which relies on the in situ generation of N-acetylimidazole on warming of DMAc with CDI at 120-125 °C, serves as a convenient alternative to other acetylation methods.
- Chikkulapalli, Anil,Aavula, Sanjeev Kumar,Mona Np, Rifahath,Karthikeyan, Karthikeyan,Kumar C.H., Vinodh,Sulur G., Manjunatha,Sumathi, Shanmugam
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supporting information
p. 3799 - 3803
(2015/06/08)
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- Branch-selective alkene hydroarylation by cooperative destabilization: Iridium-catalyzed ortho-alkylation of acetanilides
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An iridium(I) catalyst system, modified with the wide-bite-angle and electron-deficient bisphosphine dFppb (1,4-bis(di(pentafluorophenyl)phosphino)butane) promotes highly branch-selective hydroarylation reactions between diverse acetanilides and aryl- or alkyl-substituted alkenes. This provides direct and ortho-selective access to synthetically challenging anilines, and addresses long-standing issues associated with related Friedel-Crafts alkylations. An iridium(I) catalyst system modified with the wide-bite-angle and electron-deficient bisphosphine dFppb (1,4-bis(di(pentafluorophenyl)phosphino)butane) promotes highly branch-selective hydroarylation reactions between diverse acetanilides and aryl- or alkyl-substituted alkenes. This provides direct and ortho-selective access to synthetically challenging anilines.
- Crisenza, Giacomo E. M.,Sokolova, Olga O.,Bower, John F.
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supporting information
p. 14866 - 14870
(2016/02/09)
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- Copper/N,N-dimethylglycine catalyzed Goldberg reactions between aryl bromides and amides, aryl iodides and secondary acyclic amides
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An efficient and general copper-catalyzed Goldberg reaction at 90-110 °C between aryl bromides and amides providing the desired products in good to excellent yields has been developed using N,N-dimethylglycine as the ligand. The reaction is tolerant toward a wide range of amides and a variety of functional group substituted aryl bromides. In addition, hindered, unreactive aromatic and aliphatic secondary acyclic amides, known to be poor nucleophiles, are efficiently coupled with aryl iodides through this simple and cheap copper/N,N-dimethylglycine catalytic system.
- Jiang, Liqin
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supporting information
p. 13448 - 13460
(2015/02/19)
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- Ligand-free Ullmann-type C-heteroatom couplings under practical conditions
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A new practical ligand-free protocol for copper-catalyzed C-heteroatom cross-coupling reactions (Ullmann-type) is described. The use of dimethyl sulfoxide (DMSO) as the solvent overcomes the need to use organic auxiliary ligands; thus, DMSO is revealed as a nontoxic and superior solvent for Ullmann-type coupling reactions. This method allows the arylation of a wide range of amides, alcohols, and amines under practical conditions with bromobenzene and iodobenzene derivatives and will likely find direct application in current organic synthesis. The competitive reactivity among different functional groups is reported and rationalized, and the possibility to achieve selective arylation reactions is demonstrated. Copyright
- Gueell, Imma,Ribas, Xavi
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p. 3188 - 3195
(2014/06/09)
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- A novel silver nanoparticle embedded mesoporous polyaniline (mPANI/Ag) nanocomposite as a recyclable catalyst in the acylation of amines and alcohols under solvent free conditions
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A mesoporous polyaniline/silver (mPANI/Ag) nanocomposite has been prepared using mesoporous organic polymer polyaniline with silver nitrate via radical polymerization of aniline monomer in the presence of hydrochloric acid. The mPANI/Ag nanocomposite has been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive X-ray spectra (EDX), Fourier transform infrared spectroscopy (FT-IR), and ultraviolet-visible absorption spectra (UV-vis). The XRD patterns indicated that the crystalline phase of Ag is cubic. TEM images show that the Ag nanoparticles are well dispersed in the mesoporous polyaniline matrix. The mPANI/Ag acts as an efficient heterogeneous nanocatalyst in the acylation of substituted amines and alcohols using acetic acid. The catalyst is air-stable, inexpensive, easy to prepare and can be reused several times without a significant decrease in activity and selectivity. This journal is
- Mandi, Usha,Roy, Anupam Singha,Banerjee, Biplab,Islam, Sk. Manirul
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p. 42670 - 42681
(2015/02/19)
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- Direct oxidative amidation between N,N-dimethylanilines and anhydrides using metal-organic framework [Cu2(EDB)2(BPY)] as an efficient heterogeneous catalyst
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A crystalline porous metal-organic framework [Cu2(EDB) 2(BPY)] was synthesized and used as a heterogeneous catalyst for the direct oxidative amidation between N,N-dimethylanilines and anhydrides to form tertiary amides as the principal products. The [Cu2(EDB) 2(BPY)] exhibited similar activity as compared to that of [Cu 2(BDC)2(BPY)], [Cu2(BDC)2(DABCO)], MOF-143, and other common homogeneous salt catalysts. The optimal reaction conditions employed were [Cu2(EDB)2(BPY)] (10 % mol), TBHP (2 equiv), pyridine (1 equiv) in CH3CN at 80 °C over 2 h. The Cu2(EDB)2(BPY) could be separated from the reaction mixture by filtration, and could be recovered and reused several times without a significant degradation in catalytic activity and selectivity. Furthermore, generality of the optimal conditions was confirmed by employing various N,N-dimethylaniline and anhydride derivatives. Copyright
- Dang, Giao H.,Nguyen, Thanh D.,Le, Dung T.,Truong, Thanh,Phan, Nam T.S.
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p. 1129 - 1137
(2014/11/12)
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- A 2,6-bis(phenylamino)pyridinato titanium catalyst for the highly regioselective hydroaminoalkylation of styrenes and 1,3-butadienes
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The C-C bond forming catalytic hydroaminoalkylation of terminal alkenes, 1,3-dienes, or styrenes allows a direct and highly atom efficient (100 %) synthesis of amines which can result in the formation of two regioisomers, the linear and the branched product. We present a new titanium catalyst with 2,6-bis(phenylamino)pyridinato ligands for intermolecular hydroaminoalkylation reactions of styrenes and 1-phenyl-1,3-butadienes that delivers the corresponding linear hydroaminoalkylation products with excellent regioselectivities. Linear progress: A new Ti complex with 2,6-bis(phenylamino) pyridinato ligands catalyzes highly regioselective hydroaminoalkylation reactions of styrenes. The process that directly gives access to the corresponding linear hydroaminoalkylation products offers a new and flexible synthetic approach towards pharmaceutically important 3-arylpropylamines. It is also possible to convert (E)-1-phenyl-1,3-butadienes into the corresponding linear products.
- Doerfler, Jaika,Preuss, Till,Schischko, Alexandra,Schmidtmann, Marc,Doye, Sven
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p. 7918 - 7922
(2014/08/05)
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- Electrochemical reduction of 2-chloro-N-phenylacetamides at carbon and silver cathodes in dimethylformamide
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Cyclic voltammetry and controlled-potential (bulk) electrolysis have been employed to investigate the direct electrochemical reduction of 2-chloro-N-methyl-N-phenylacetamide (1a), 2-chloro-N-ethyl-N-phenylacetamide (1b), and 2-chloro-N-phenylacetamide (1c) at carbon and silver cathodes, as well as the catalytic reduction of these compounds by electrogenerated nickel(I) salen, in dimethylformamide (DMF) containing 0.050 M tetramethylammonium tetrafluoroborate (TMABF4). Cyclic voltammograms for reduction of 1a and 1b show a single irreversible cathodic peak for cleavage of the carbon-chlorine bond, but two irreversible cathodic peaks are observed in cyclic voltammograms for reduction of 1c. Controlled-potential reduction of 1a and 1b gives mixtures of dechlorinated amide and N-alkyl-N-phenylaniline, whereas bulk electrolyses of 1c afford N-phenylacetamide in almost quantitative yield. In addition, bulk electrolyses of 1a and 1b result in the formation of very small amounts of dimeric species that arise from coupling of the radical intermediate formed by one-electron cleavage of the carbon-chlorine bond. On the basis of the coulometric n values and product distributions, together with computations based on density functional theory, we propose mechanistic pictures for the reduction of 1a and 1b that involve radical intermediates, whereas reduction of 1c involves carbanion intermediates.
- Pasciak, Erick M.,Sengupta, Arkajyoti,Mubarak, Mohammad S.,Raghavachari, Krishnan,Peters, Dennis G.
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p. 159 - 166
(2014/04/03)
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- Carbonylation of quaternary ammonium salts to tertiary amides using NaCo(CO)4 catalyst
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We reported here the catalytic carbonylation of quaternary ammonium salts under anhydrous condition. Quaternary ammonium salts, a kind of versatile reagents that were widely used in organometallic chemistry, can be carbonylated to tertiary amides by an in situ prepared NaCo(CO)4 catalyst. It was found that the counterions (Cl-, Br-, I-, OTf-) in the quaternary ammonium salts played a significant role in the reaction and tetramethylammonium iodide could give high yield (96%) of N,N-dimethylacetamide (DMAc) with only 0.5 mol% cobalt catalyst. Under optimum conditions, several other quaternary ammonium iodides were also carbonylated to corresponding tertiary amides in moderate to excellent yields. Obviously, these results also give us a special apprehension that Me4NI and other quaternary ammonium salts could be possibly carbonylated to tertiary amides in the carbonylation reaction where they are used as promoters or solvents in most cases. Considering the high activity and moderate to excellent selectivity, this process could be a potential method for the synthesis of certain tertiary amides. Moreover, the cleaving mechanism of CN bonds and the possible catalytic intermediates were discussed in detail.
- Lei, Yizhu,Zhang, Rui,Wu, Qing,Mei, Hui,Xiao, Bo,Li, Guangxing
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p. 120 - 125
(2013/12/04)
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