- Cobalt-Catalyzed Deoxygenative Hydroboration of Nitro Compounds and Applications to One-Pot Synthesis of Aldimines and Amides
-
The commercially available and bench-stable Co(acac)2 ligated with bis[(2-diphenylphosphino)phenyl] ether (dpephos) was employed for selective room temperature hydroboration of nitro compounds with HBPin (TOF up to 4615 h?1), tolerating halide, hydroxy, amino, ether, ester, lactone, amide and heteroaromatic functionalities. These reactions offered a direct access to a variety of N-borylamines RN(H)BPin, which were in situ treated with aldehydes and carboxylic acids to produce a series of aldimines and secondary carboxamides without the need for dehydrating and/or coupling reagents. Combination of these transformations in a sequential one-pot manner allowed for direct and selective synthesis of aldimines and secondary carboxamides from readily available and inexpensive nitro compounds.
- Gudun, Kristina A.,Zakarina, Raikhan,Segizbayev, Medet,Hayrapetyan, Davit,Slamova, Ainur,Khalimon, Andrey Y.
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p. 601 - 611
(2021/11/30)
-
- Visible-Light Carbon Nitride-Catalyzed Aerobic Cyclization of Thiobenzanilides under Ambient Air Conditions
-
A metal-free heterogeneous photocatalysis has been developed for the synthesis of benzothiazoles via intramolecular C-H functionalization/C-S bond formation of thiobenzanilides by inexpensive graphitic carbon nitride (g-C3N4) under visible-light irradiation. This reaction provides access to a broad range of 2-substituted benzothiazoles in high yields under an air atmosphere at room temperature without addition of a strong base or organic oxidizing reagents. In addition, the catalyst was found to be stable and reusable after five reaction cycles.
- Bai, Jin,Yan, Sijia,Zhang, Zhuxia,Guo, Zhen,Zhou, Cong-Ying
-
supporting information
p. 4843 - 4848
(2021/06/28)
-
- Visible-Light-Promoted Iron-Catalyzed N-Arylation of Dioxazolones with Arylboronic Acids
-
A visible-light-promoted and simple iron salt-catalyzed N-arylation was achieved efficiently under external photosensitizer-free conditions. Arylboronic acids and bench-stable dioxazolones were used for this cross-coupling reaction. This reaction features high reactivity, wide substrate scope, good functional group tolerance, simple operation procedure, and mild reaction conditions. Preliminary mechanistic investigations were conducted to support a radical pathway. This method may contribute to shift the paradigm of iron-catalyzed C-N bond construction and nitrene transfer chemistry.
- Tang, Jing-Jing,Yu, Xiaoqiang,Yamamoto, Yoshinori,Bao, Ming
-
p. 13955 - 13961
(2021/11/20)
-
- Cu-catalyzed arylation of bromo-difluoro-acetamides by aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts: New entries to aromatic amides
-
We describe a mechanism-guided discovery of a synthetic methodology that enables the preparation of aromatic amides from 2-bromo-2, 2-difluoroacetamides utilizing a copper-catalyzed direct arylation. Readily available and structurally simple aryl precursors such as aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts were used as the source for the aryl substituents. The scope of the reactions was tested, and the reactions were insensitive to the electronic nature of the aryl groups, as both electron-rich and electron-deficient aryls were successfully introduced. A wide range of 2-bromo-2, 2-difluoroacetamides as either aliphatic or aromatic secondary or tertiary amides were also reactive under the developed conditions. The described synthetic protocols displayed excellent efficiency and were successfully utilized for the expeditious preparation of diverse aromatic amides in good-to-excellent yields. The reactions were scaled up to gram quantities.
- Iaroshenko, Viktor O.,Jakubczyk, Micha?,Lanka, Suneel,Mkrtchyan, Satenik,Pittelkow, Michael
-
-
- Practical one-pot amidation of N -Alloc-, N -Boc-, and N -Cbz protected amines under mild conditions
-
A facile one-pot synthesis of amides from N-Alloc-, N-Boc-, and N-Cbz-protected amines has been described. The reactions involve the use of isocyanate intermediates, which are generated in situ in the presence of 2-chloropyridine and trifluoromethanesulfonyl anhydride, to react with Grignard reagents to produce the corresponding amides. Using this reaction protocol, a variety of N-Alloc-, N-Boc-, and N-Cbz-protected aliphatic amines and aryl amines were efficiently converted to amides with high yields. This method is highly effective for the synthesis of amides and offers a promising approach for facile amidation.
- Hong, Wan Pyo,Tran, Van Hieu,Kim, Hee-Kwon
-
p. 15890 - 15895
(2021/05/19)
-
- Chromium-catalyzed ligand-free amidation of esters with anilines
-
Amides are important structural motifs in pharmaceutical and agrochemical chemistry because of the intriguing biological active properties. We report here the amidation of commercially available esters with anilines that was promoted by low-cost and air-stable chromium(III) pre-catalyst combined with magnesium, providing access to amides. This reaction occurs without the use of external ligands in a simple operation. Mechanistic studies indicate that a reactive aminated Cr species responsible for the amidation can be considered, which may be formed by reaction of low-valent Cr with aniline followed by reduction with hydrogen evolution.
- Chen, Changpeng,Ling, Liang,Luo, Meiming,Zeng, Xiaoming
-
supporting information
p. 762 - 766
(2021/04/14)
-
- Copper-catalyzed Goldberg-type C-N coupling in deep eutectic solvents (DESs) and water under aerobic conditions
-
An efficient and selectiveN-functionalization of amides is first reportedviaa CuI-catalyzed Goldberg-type C-N coupling reaction between aryl iodides and primary/secondary amides run either in Deep Eutectic Solvents (DESs) or water as sustainable reaction media, under mild and bench-type reaction conditions (absence of protecting atmosphere). Higher activities were observed in an aqueous medium, though the employment of DESs expanded and improved the scope of the reaction to include also aliphatic amides. Additional valuable features of the reported protocol include: (i) the possibility to scale up the reaction without any erosion of the yield/reaction time; (ii) the recyclability of both the catalyst and the eutectic solvent up to 4 consecutive runs; and (iii) the feasibility of the proposed catalytic system for the synthesis of biologically active molecules.
- Cicco, Luciana,Hernández-Fernández, Jose A.,Salomone, Antonio,Vitale, Paola,Ramos-Martín, Marina,González-Sabín, Javier,Presa Soto, Alejandro,Perna, Filippo M.,Capriati, Vito,García-álvarez, Joaquín
-
supporting information
p. 1773 - 1779
(2021/03/14)
-
- Copper-catalyzed aerobic oxidative C-C bond cleavage of simple ketones for the synthesis of amides
-
A Cu-catalyzed oxidative amidation of simple ketones with amines via carbon-carbon (C-C) bond cleavage has been developed. A number of aryl and alkyl ketones could be easily converted to amides using cheap copper salt as the catalyst and O2 as the oxidant with a wide range of amines, including primary and secondary amines. This method shows a notable advantage of the broad scope for the substrate, thus providing a practical approach to amides. A plausible mechanism is proposed based on the preliminary experiments.
- Li, Ke,Liu, Wei,Liu, Yu-Feng,Yang, Guo-Ping,Zeng, Kai
-
p. 6958 - 6964
(2020/10/02)
-
- N-Phenylbenzamide derivatives as alternative oxidase inhibitors: Synthesis, molecular properties, 1H-STD NMR, and QSAR
-
In the present work, 117 N-phenylbenzamides (NPDs) were prepared and evaluated against recombinant AOX from the fungal pathogen Moniliophthora perniciosa. 1H, 13C NMR, FTIR, and mass spectra provided structural information on NPDs. The library compounds were tested as Alternative Oxidase inhibitors in two different assays using the model yeast Pichia pastoris: cell growth and oxygen consumption assays. The most active compound, 3FH, was further characterized by DRX and 1H-NMR-STD. Single crystal X-ray diffraction showed intra- and intermolecular interactions of 3FH in solid-state and elucidated its 3D structural configuration. 1H-NMR-STD allowed us to derive protein-ligand interactions in a membrane-mimetic system and evidenced an outstanding interaction of 3FH with this enzyme. Results of both biological assays were used as input to Quantitative Structure-Activity Relationship models, which highlighted the more important molecular fragments contributions for protein-ligand interaction.
- Barsottini, Mario R. O.,Carazzolle, Marcelo F.,Costa, Paulo C. S.,Evangelista, Joel S.,Miranda, Paulo C. M. L.,Nascimento, Andrey F. Z.,Pereira, Gon?alo A. G.,Pires, Bárbara A.,Rocco, Silvana A.,Sfor?a, Maurício L.,Silva, Jaqueline S.,Vieira, Maria L. L.,Zeri, Ana C. M.
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-
- Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
-
The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
- Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
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p. 4087 - 4101
(2019/04/30)
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- Iodine-mediated aryl transfer reaction from arylhydrazine hydrochlorides to nitriles
-
An iodine-promoted, metal-, base-, and solvent-free cross-coupling reaction was developed for the synthesis of various useful secondary amides via an aryl N-addition reaction of aryl groups to cyano groups. This aryl transfer reaction proceeds with arylhydrazine hydrochlorides serving as the aryl donors. A labelling experiment shows that the N atom in the product comes from the cyano group of the nitriles, which are low in cost. A plausible radical-driven mechanism is also proposed.
- Zhang, Zhiguo,Li, Xiang,Li, Yinghua,Guo, Yan,Zhao, Xunan,Yan, Yan,Sun, Kai,Zhang, Guisheng
-
supporting information
p. 3628 - 3635
(2019/05/29)
-
- Chromium-Catalyzed Activation of Acyl C-O Bonds with Magnesium for Amidation of Esters with Nitroarenes
-
Here, we report a chromium-catalyzed activation of acyl C-O bonds with magnesium for amidation of esters with nitroarenes. Low-cost chromium(III) chloride shows high reactivity in promoting amidation by using magnesium as reductant and chlorotrimethylsilane as additive. It provides a step-economic strategy to the synthesis of centrally important amide motifs using inexpensive and air-stable nitroarenes as amino sources.
- Ling, Liang,Chen, Changpeng,Luo, Meiming,Zeng, Xiaoming
-
supporting information
(2019/03/19)
-
- Synthesis of Amides by Mild Palladium-Catalyzed Aminocarbonylation of Arylsilanes with Amines Enabled by Copper(II) Fluoride
-
A general Pd-catalyzed synthesis of amides by oxidative aminocarbonylation of arylsilanes under mild conditions was accomplished for the first time. The reaction is promoted by a commercially available copper(II) fluoride, which acts as a dual silane activator and mild oxidant, enabling highly efficient aminocarbonylation of versatile arylsilanes at atmospheric CO pressure. The reaction is tolerant of a wide range of arylsilanes and various sensitive halide functional groups as well as a broad scope of amines are compatible with this oxidative process using cheap CO. A significant aspect involves the increased efficiency by the catalyst system. The reaction represents a segue into the powerful Pd-catalyzed oxidative transformations of organosilanes.
- Zhang, Jin,Hou, Yanyan,Ma, Yangmin,Szostak, Michal
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p. 338 - 345
(2019/01/10)
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- Secondary/tertiary amide compound and synthesis method thereof
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The invention discloses a secondary/tertiary amide compound and a synthesis method thereof. The method comprises the following steps: adding arylsilane and an amine compound, a catalyst and an additive to a solvent, introducing CO under a certain pressure, carrying out a carbonylation reaction, and carrying out separation and purification to obtain the secondary/tertiary amide. The method for preparing the secondary/tertiary amide by the carbonylation reaction has the advantages of concision, high efficiency, directness in the reaction, high atom economy, and wide sources and good stability ofa substrate. The reaction system of the invention does not require inert gas protection, and has mild conditions, and the target product is easy to separate and the yield reaches up to 92% under optimized reaction conditions.
- -
-
Paragraph 0136; 0137; 0138; 0139
(2019/01/21)
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- Method for synthesizing amide compound through photocatalysis in water phase
-
The invention discloses a method for synthesizing an amide compound through photocatalysis in a water phase. The method comprises the following steps: putting catalysis amounts of a free radical initiator, an amine derivative, a carboxylic acid derivative, a phase transfer catalyst, an inorganic base and water into a reaction container, carrying out a reaction in a photocatalysis reaction instrument at certain power under a room temperature condition, after a certain time, carrying out extraction by using a small amount of ethyl acetate, and carrying out recrystallization, so as to obtain theamide compound, wherein the free radical initiator is eosin, methyl orange, sodium persulfate, ammonium persulfate or potassium peroxodisulfate, the phase transfer catalyst is tetrabutylammonium bromide, and the power of the photocatalytic reaction instrument is 5W. By adopting the method disclosed by the invention, toxic thionyl chloride or phosphorus oxychloride is not needed for a chlorinationreaction, water is adopted as a solvent, a novel photocatalysis method is used, and the amide compound with a high yield can be prepared through a room-temperature reaction for 2-5 hours with an incandescent light bulb of 5W, and in addition, the method is simple in aftertreatment, and low in cost and is an ideal green synthesis method of amide compounds.
- -
-
Paragraph 0018-0046
(2019/10/01)
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- Preparation method of N-aryl amide compounds
-
The invention belongs to the technical field of synthesis of compounds, and in particular relates to a preparation method of N-aryl amide compounds. The method comprises the following steps: dissolving amide, a copper catalyst and alkali in an organic solvent, and adding a halogenated aromatic hydrocarbon; then, irradiating with ultraviolet light for carrying out a reaction for 12-24h under nitrogen protection; after the reaction is completed, concentrating reaction liquid by using a rotary evaporator; separately and purifying by means of column chromatography silica gel to obtain the N-aryl amide. The method provided by the invention replaces heating with illumination, does not need to add a ligand, is simple in process, mild in conditions and lower in economic cost, and has higher functional group compatibility and universality.
- -
-
Paragraph 0035-0037
(2018/12/13)
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- Cobalt(III)-Catalyzed Construction of Benzofurans, Benzofuranones and One-Pot Orthogonal C?H Functionalizations to Access Polysubstituted Benzofurans
-
Benzofuran and benzofuranone derivatives have been synthesized through exclusive 5-exo-dig intramolecular hydroarylation using the amide-directed, cost-effective, high-valent Cp*CoIII-catalytic system. Challenging one-pot, orthogonal C?H functionalizations using two different electrophiles are also reported to afford polysubstituted benzofurans. Several valuable functional group interconversions along with removal of the amide directing group provide a route to access several diversely functionalized benzofurans. The mechanistic study suggests a reversible cobaltation step is operative here. (Figure presented.).
- Bera, Sourav Sekhar,Debbarma, Suvankar,Jana, Sripati,Maji, Modhu Sudan
-
supporting information
p. 2204 - 2210
(2018/06/07)
-
- Direct synthesis of N-arylamides via the coupling of aryl diazonium tetrafluoroborates and nitriles under transition-metal-free conditions
-
The direct synthesis of N-arylamides via the coupling of aryl diazonium tetrafluoroborates and nitriles under transition-metal-free conditions has been developed. The reported protocol is practical and represents an efficient method to produce functionalized amides in moderate to good yields.
- Xiong, Biquan,Wang, Gang,Xiong, Tao,Wan, Liming,Zhou, Congshan,Liu, Yu,Zhang, Panliang,Yang, Changan,Tang, Kewen
-
supporting information
p. 3139 - 3142
(2018/07/13)
-
- Copper-catalyzed synthesis of benzanilides from lignin model substrates 2-phenoxyacetophenones under an air atmosphere
-
The synthesis of chemicals from biomass-derived compounds is an interesting and challenging topic. In this work, using the lignin-derived 2-phenoxyacetophenones as the feedstock we present a novel approach for the synthesis of benzanilides via the reaction of 2-phenoxyacetophenones with anilines catalyzed by CuCl2 in DMSO at 120 °C under an air atmosphere. This approach has wide scope for 2-phenoxyacetophenones and anilines, and various benzanilides accompanied by the corresponding phenols could be obtained in high yields via changing the 2-phenoxyacetophenones and anilines. The reaction mechanism study indicated that the oxidative cleavage of the C-C bond in 2-phenoxyacetophenones and the formation of a C-N bond occurred simultaneously in the reaction process, resulting in the formation of benzanilides together with phenols.
- Liu, Xinwei,Zhang, Hongye,Wu, Cailing,Chen, Yu,Yu, Bo,Liu, Zhimin,Liu, Zhenghui
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p. 1223 - 1227
(2018/02/06)
-
- Hypervalent Iodine(III)-Promoted Phenyl Transfer Reaction from Phenyl Hydrazides to Nitriles
-
A useful transformation of nitriles to N-phenyl amides has been achieved through a novel intermolecular phenyl transfer reaction from phenyl hydrazides and N-addition to nitriles in the presence of PIFA under mild and solvent-free conditions. This cross-coupling reaction includes the oxidative cleavage of sp2 C-N bonds of phenyl hydrazides to form a phenyl radical and the subsequent N-addition to cyanos to form new sp2 C-N bonds and provides efficient access to various N-phenyl amides in moderate to good yields under mild reaction conditions.
- Yan, Yan,Zhang, Zhiguo,Wan, Yameng,Zhang, Guisheng,Ma, Nana,Liu, Qingfeng
-
supporting information
p. 7957 - 7963
(2017/08/14)
-
- Interpositus substituted N-aryl benzoyl amines one-step synthesis method of the compound
-
The invention discloses a one-step synthetic method of meta-substituted N-arylbenzamide compounds. Transition metal ruthenium is used as a catalyst, and the meta-substituted N-arylbenzamide compounds are synthesized in one step through carboxy-based o-C-H functionalization/ decarboxylation coupling reaction of aromatic acid and phenyl isocyanate compounds. The method has the advantages that the raw materials are simple and readily available, the catalyst is cheap, the reaction operation is simple, the utilization rate of atoms is high, the method is environment-friendly and the like.
- -
-
Paragraph 0017-0020; 0052-0055
(2017/02/28)
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- Direct Access to Acylated Azobenzenes and Amide Compounds by Reaction of Azoarenes with Benzylic Ethers as Acyl Equivalents
-
Described herein is the use of N=N double bond of azobenzene as both directing group and radical acceptor in one-reaction protocol for the first time. An efficient pathway for the Pd-catalyzed regiospecific ortho-acylation of azoarenes using benzylic ethers as acyl equivalents has been achieved. In the absence of palladium catalyst, amide compounds were formed by the reaction of azoarenes with benzylic ethers under certain conditions. Various mono-acylazobenzene and amide compounds were obtained in good yields (35 examples). The mono-acylated products and amide products could be easily controlled by palladium catalyst.
- Hong, Gang,Aruma, Alfred Njasotapher,Zhu, Xiaoyan,Wu, Shengying,Wang, Limin
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p. 1147 - 1158
(2016/05/11)
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- Ru(II)-catalyzed ortho-amidation and decarboxylation of aromatic acids: A versatile route to meta-substituted N-aryl benzamides
-
Carboxylate as a promising and valuable directing group has attracted a great deal of attention. However, employing it as a traceless direction group has rarely been reported. We developed the ruthenium-catalyzed amidation of substituted benzoic acids wit
- Shi, Xian-Ying,Dong, Xue-Fen,Fan, Juan,Liu, Ke-Yan,Wei, Jun-Fa,Li, Chao-Jun
-
p. 1286 - 1291
(2015/03/31)
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- Palladium/copper tandem catalysis for carbon-carbon triple bond cleavage of diaryl acetylenes
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A method for carbon-carbon triple bond cleavage based on palladium/copper tandem catalysis is developed. In this chemistry, anilines and diaryl acetylenes were converted into benzamides through cascade transformations combining palladium-catalyzed hydroamination of alkyne with copper-catalyzed aerobic oxidative C-C bond cleavage.
- Wang, Zhiwei,Fan, Wenyou,Deng, Guo-Jun,Zhou, Wang
-
supporting information
p. 5449 - 5452
(2015/09/15)
-
- A convenient synthesis of N-aryl benzamides by rhodium-catalyzed ortho-amidation and decarboxylation of benzoic acids
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The rhodium-catalyzed amidation of substituted benzoic acids with isocyanates by directed C-H functionalization followed by decarboxylation to afford the corresponding N-aryl benzamides is demonstrated, in which the carboxylate serves as a unique, removable directing group. Notably, less common meta-substituted N-aryl benzamides are generated readily from more accessible paraor ortho-substituted groups by employing this strategy.
- Shi, Xian-Ying,Liu, Ke-Yan,Fan, Juan,Dong, Xue-Fen,Wei, Jun-Fa,Li, Chao-Jun
-
supporting information
p. 1900 - 1903
(2015/01/30)
-
- Efficient cobalt-catalyzed C-N cross-coupling reaction between benzamide and aryl iodide in water
-
A practical and efficient strategy for the N-arylation of benzamide catalysed by a Co(C2O4)·2H2O/dmeda system in water is reported. Under the optimized conditions, a wide variety of N-arylated products were obtained in good yields (up to 92%) using substituted aryl iodides.
- Tan, Bryan Yong-Hao,Teo, Yong-Chua
-
supporting information
p. 7478 - 7481
(2014/12/11)
-
- An efficient synthesis of amides from alcohols and azides catalyzed by a bifunctional catalyst Au/DNA under mild conditions
-
A novel Au/DNA-catalyzed amidation from alcohols and azides was developed under mild conditions. Taking advantage of the water-soluble reversibility of this catalyst, the transformation could be carried out smoothly in water and the catalyst could be recovered and reused by a simple phase separation. This amidation reaction unitized the hydrogen transfer process and the oxidative coupling process synergistically in an atom economical and environmentally benign synthesis. the Partner Organisations 2014.
- Guo, Xuefeng,Tang, Lin,Yang, Yu,Zha, Zhenggen,Wang, Zhiyong
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supporting information
p. 2443 - 2447
(2014/05/06)
-
- Copper-catalyzed regioselective synthesis of N-aryl amides from aldoximes and aryl halides
-
Ligand-assisted copper-catalyzed reaction of aldoximes with aryl halides is described for the regioselective synthesis of N-aryl amides. This protocol is simple and compatible with a wide range of functional groups attached to the aryl ring of the halides as well as aldoximes. Copyright
- Panda, Niranjan,Mothkuri, Raghavender,Nayak, Dinesh Kumar
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supporting information
p. 1602 - 1605
(2014/03/21)
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- Copper-Catalyzed Regioselective Synthesis of N-Aryl Amides from Aldoximes and Aryl Halides
-
Ligand-assisted copper-catalyzed reaction of aldoximes with aryl halides is described for the regioselective synthesis of N-aryl amides. This protocol is simple and compatible with a wide range of functional groups attached to the aryl ring of the halides as well as aldoximes.
- Panda, Niranjan,Mothkuri, Raghavender,Nayak, Dinesh Kumar
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supporting information
p. 1602 - 1605
(2015/10/05)
-
- Aerobic oxidative transformation of primary alcohols and amines to amides promoted by a hydroxyapatite-supported gold catalyst in water
-
In the presence of an easily prepared hydroxyapatite-supported gold catalyst, namely Au/HAP, various kinds of structurally diverse primary alcohols including benzylic and aliphatic ones, and amines involving aromatic and secondary ones could be converted into the corresponding amides in water with up to 99% yield. Meanwhile, on the basis of experimental observations and literatures, a plausible reaction pathway was described to elucidate the reaction mechanism.
- Wang, Wentao,Cong, Yu,Zhang, Leilei,Huang, Yanqiang,Wang, Xiaodong,Zhang, Tao
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supporting information
p. 124 - 127
(2014/01/06)
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- Synthesis, antileishmanial activity and structure-activity relationship of 1-N-X-phenyl-3-N′-Y-phenyl-benzamidines
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Two series of N,N′-diphenyl-benzamidines were synthesized as part of a study to search potential new drugs with antileishmanial activity. These compounds were obtained by anilides in PCl5 halogenation reaction with generation in situ of the cor
- Rodrigues-Santos, Cláudio Eduardo,Leon, Leonor L.,Bortoluzzi, Adailton J.,Canto-Cavalheiro, Marilene Marcuzzo,Machado, Gérzia C.,Echevarria, Aurea
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p. 166 - 174
(2013/10/01)
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- Use of molecular oxygen as a reoxidant in the synthesis of 2-substituted benzothiazoles via palladium-catalyzed C-H functionalization/intramolecular C-S bond formation
-
Molecular oxygen (O2) was successfully employed as a reoxidant in cyclizations of thiobenzanilides 1a-s through a palladium-catalyzed C-H functionalization/intramolecular C-S bond formation process, leading to an efficient, green method for the synthesis of 2-arylbenzothiazoles 2a-s. Addition of cesium fluoride (CsF) greatly enhanced the reactions, which produced variously substituted 2-arylbenzothiazoles with good functional group tolerance. Thioureas 4a-j were also found to be suitable substrates for the cyclization process using a palladium/O2 catalyst system, thus generating 2-aminobenzothiazoles 5a-j. One-pot syntheses of 2-aminobenzothiazoles 5a-j from aryl isothiocyanates 6 and amines 7 were also successful.
- Inamoto, Kiyofumi,Hasegawa, Chisa,Kawasaki, Junpei,Hiroya, Kou,Doi, Takayuki
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experimental part
p. 2643 - 2655
(2010/12/25)
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- Heterobimetallic complexes of lanthanide and lithium metals with dianionic guanidinate ligands: Syntheses, structures and catalytic activity for amidation of aldehydes with amines
-
Reactions of triguanidinate lanthanide complexes Ln[(iPrN)(NC6H4p-Cl)C(NHiPr)]3 (Ln = Nd, Y) with 3 equiv. of n-BuLi gave [Li(THF)(DME)]3Ln[μ-η2η1 (iPrN)2C(NC6H4p-Cl)]3, which represents the first structurally characterized complexes of lanthanide and lithium metals with dianionic guanidinate ligands. The Nd complex was found to be an effective catalyst for amidation of aldehydes with amines under mild conditions with a wide scope of substrates.
- Qian, Cunwei,Zhang, Xingmin,Zhang, Yong,Shen, Qi
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experimental part
p. 747 - 752
(2010/04/27)
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- Rhodium-catalysed addition reaction of aryl- and alkenylboronic acids to isocyanates
-
The addition reaction of aryl- and alkenylboronic acids to isocyanates is catalysed by a rhodium(i) complex, affording secondary amides under mild conditions. The Royal Society of Chemistry.
- Miura, Tomoya,Takahashi, Yusuke,Murakami, Masahiro
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p. 3577 - 3579
(2008/03/12)
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- N-arylbenzonitrilium ions. Photochemical generation and effect of substituents in the phenyl rings on lifetimes in water and reactivity with azide ion
-
Nitrilium ions Ar-C≡N+-Ar′ have been studied by laser flash photolysis in aqueous solutions containing 20% acetonitrile. The cations were generated by photoheterolysis of benzimidate esters Ar-CZ=N-Ar′ (Z = -OC6H4-4-CN) with 4-cyanophenoxide as the photochemical leaving group. Rate constants for the reaction with water (kw), azide ion (kaz) and hydroxide (kOH) were measured. The cation Ph-C≡N+-Ph is only 50-fold shorter lived in water compared to Ph-C≡N+-iPr (2); thus the effect of replacing an N-alkyl group with N-phenyl is modest. These two cations are also shown to have similar lifetimes to iminium analogs, e.g. Ph-CH=N+ (Me)-Ph. Thus, addition of water to analogous sp and sp2 hybridized systems occurs at a similar rate, and the increased steric access to the nitrilium plays at most a modest role. For the series where substituents in Ar′ were varied with Ar equal to phenyl, the Hammett plot for log kw correlated with σ, with ρ = - 1.4. For the series where Ar was varied, the data correlated much better with σ+, although ρ+ was only -0.6. This remarkably small effect of substituents in Ar constrasts with the effects seen in benzylic carbocations, but is consistent with the nitrilium structure, with most of the positive charge located on the nitrogen. Rate constant ratios kaz:kw, including the N-alkylnitrilium ion 2, are constant at ~104, with values of kaz well below the diffusion limit, even for the most reactive nitrilium ions. This is very different behaviour from that of carbocations and arylnitrenium ions of similar lifetimes in water. For these cations the rate constants kaz would be at or at least approaching the diffusion limit.
- Ruane, Patrick H.,Ahmed, Abid R.,McClelland, Robert A.
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p. 312 - 317
(2007/10/03)
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- Reactions of aniline with unsymmetrical acid anhydrides
-
Reaction of aniline with some mixed/unsymmetrical acid anhydrides to give exclusively one of the anilides is described.
- Dubey,Vinod Kumar
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p. 265 - 266
(2007/10/03)
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- HIV protease inhibitors
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HIV protease inhibitors, obtainable by chemical synthesis, inhibit or block the biological activity of the HIV protease enzyme, causing the replication of the HIV virus to terminate. These compounds, as well as pharmaceutical compositions that contain these compounds and optionally other anti-viral agents as active ingredients, are suitable for treating patients or hosts infected with the HIV virus, which is known to cause AIDS.
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- Synthesis and platelet aggregation inhibitory effects of harman and phthalide derivatives related to ligusticum chuanxiong (Hort.) constituents
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The Chinese drug plant Ligusticum chuanxiong (Hort.) has platelet aggregation inhibiting effects, and also protects against sub-lethal radiation doses that cause capillary hypercoagulation. Two types of derivatives of known constituents of this plant have been synthesized and tested for inhibition of hypercoagulation. These include harman and phthalide derivatives. The harman derivatives showed good inhibitory effects against platelet aggregation in rabbit heart blood ranging from 39-96%. The phthalides gave 0-19% inhibitions.
- Foye, William O.,Wang, Xiping,Hongfu, Wang
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p. 180 - 191
(2007/10/03)
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- HIV protease inhibitors
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HIV protease inhibitors, obtainable by chemical synthesis, inhibit or block the biological activity of the HIV protease enzyme, causing the replication of the HIV virus to terminate. These compounds, as well as pharmaceutical compositions that contain these compounds and optionally other anti-viral agents as active ingredients, are suitable for treating patients or hosts infected with the HIV virus, which is known to cause AIDS.
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- Intermediate and process for making
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The present invention provides novel HIV protease inhibitors, pharmaceutical formulations containing those compounds and methods of treating and/or preventing HIV infection and/or AIDS.
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- Efficient Synthesis of Hydroxyphthalides
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Naturally occurring hydroxyphthalides were synthesized via migration of double bond regio- and stereoselectively.Isomerization of E-isomer to Z-isomer easily occurred under acidic or basic conditions.
- Ogawa, Yoshimitsu,Maruno, Masao,Wakamatsu, Takeshi
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- Facile and Effective Synthesis of Unusually Substituted Aromatic N-Phenylamides
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A mild and effective new method for the preparation of a variety of arylamides 3a-i as well as heterocyclic 5a, b and 6 and olefinic amides 7, 9 is described.The reaction of trialkylstannyl-substituted aromatic, heterocyclic or vinylic hydrocarbons with aryl isocyanates in the presence of aluminium trichloride provides the corresponding N-aryl-substituted amides in good to excellent yields.The stannyl group serves as a powerful leaving group superior to hydrogen by several powers of ten which allows, via ipso substitution, to obtain isomer patterns not accessible by normal electrophilic substitution reactions, e. g. substitution in meta position with respect to a methoxy group.
- Kobs, Uwe,Neumann, Wilhelm P.
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p. 2191 - 2194
(2007/10/02)
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- Diazotisation Rearrangement of Tosylhydrazones of ortho- and meta-Substituted-benzophenones and α-Substituted-acetophenones (Synthesis of Anilides)
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Ortho and meta-substituted-benzophenones (1a-g) and substituted-acetophenones (1h-i) were converted into tosylhydrazones (2a-i) by reacting with p-toluenesulphonyl-hydrazide.Conversion of 2a-i to the anilides (3a-i) was effected with the reagents H2SO4 and NaNO2, and was found to be as facile as in case of the para-substituted-benzophenone hydrozones.
- Joshi, Vidya,Sharma, R. K.
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p. 564 - 566
(2007/10/02)
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- REACTIONS OF IMIDIC ACID DERIVATIVES WITH NUCLEOPHILIC REAGENTS. ALKALINE HYDROLYSIS OF N-PHENYLBENZIMIDOYL-4-DIMETHYLAMINOPYRIDINIUM SALTS IN A WATER-DIOXANE MIXTURE
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First order in each of the reagents is characteristic of the alkaline hydrolysis of N-phenylbenzimidoylpyridinium salts +C5H4N(CH3)2>=NC6H5>.Cl- (R=3-CH3, H, 3-OCH3, 3-Br, 3-NO2> in aqueous dioxane (1:1) at 25 deg C with constant ionic strenght μ 0.2 (sodium chloride).On the basis of the proximity of the Hammett ρ parameters a common mechanism, involving the formation of an intermediate addition product in the rate-controlling stage, is proposed for the bimolecular reaction of these compounds (ρR 1.7) and 4-nitrophenyl N-phenylbenzimidates RC6H4C(OC6H4NO2)=NC6H5 (ρR 2.0) with the hydroxide ion.The salt effect of sodium perchlorate, sodium bromide, and sodium chloride in the process, due to the participation of ion pairs in the reaction, are discussed.
- Prudchenko, A. P.,Drizhd, L. P.,Savelova, V. A.
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p. 742 - 746
(2007/10/02)
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- Reaction of Sulphuryl Chloride with Some Schiff Bases
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The reaction of sulphuryl chloride with schiff bases has been studied.In each case, pure crystalline products have been isolated, and their structures elucidated on the basis of IR, PMR and mass spectral data.A plausible mechanism is advanced for the formation of observed products.
- Dhar, Durga N.,Gupta, Sudha R.
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p. 533 - 535
(2007/10/02)
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