- Copper-Catalyzed Cascade N-Dealkylation/N-Methyl Oxidation of Aromatic Amines by Using TEMPO and Oxygen as Oxidants
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A novel tandem N-dealkylation and N-methyl aerobic oxidation of tertiary aromatic amines to N-arylformamides using copper and TEMPO has been developed. This methodology suggested an alternative synthetic route from N-methylarylamines to N-arylformamides.
- Li, Dianjun,Wang, Shihaozhi,Yang, Jiale,Yang, Jinhui
-
supporting information
p. 6768 - 6772
(2021/12/31)
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- Acid-catalyzed chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines
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Chemodivergent reactions of 2,2-dimethoxyacetaldehyde and anilines were described, which were established on the basis of either a C[sbnd]C bond cleavage or a rearrangement process of a reaction intermediate. These reactions proceeded in a condition-determined manner with good functional group tolerance. In the first model, 2,2-dimethoxyacetaldehyde reacted with aniline to form a new C[sbnd]N bond, in the presence of O2, via a C[sbnd]C bond cleavage reaction. However, in the second model, by performing the reaction in the absence of O2, Heyns rearrangement occurred and generated a new C[sbnd]O bond to form methyl phenylglycinate. Such condition-determined reactions not only offered the new way for value-added conversion of biomass-derived platform molecule, 2, 2-dimethoxyacetaldehyde, but also provided efficient methods for the synthesis of N-arylformamides and methyl phenylglycinates.
- Guo, Luxia,Chen, Zihao,Zhu, Hongmei,Li, Minghao,Gu, Yanlong
-
supporting information
p. 1419 - 1422
(2020/11/12)
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- HCl-mediated transamidation of unactivated formamides using aromatic amines in aqueous media
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We report transamidation protocol to synthesize a range of secondary and tertiary amides from weakly nucleophilic aromatic and hetero-aryl amines with low reactive formamide derivatives, utilizing hydrochloric acid as catalyst. This current acid mediated strategy is beneficial because it eliminates the need for a metal catalyst, promoter or additives in the reaction, simplifies isolation and purification. Notably, this approach conventionally used to synthesize molecules on gram scales with excellent yields and a high tolerance for functional groups.
- Dhawan, Sanjeev,Girase, Pankaj Sanjay,Kumar, Vishal,Karpoormath, Rajshekhar
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p. 3729 - 3739
(2021/10/14)
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- Palladium-catalyzed secondary benzylic imidoylative reactions
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Reported herein is a palladium-catalyzed secondary benzylic imidoylative Negishi reaction leveraging the sterically bulky aromatic isocyanides as the imine source. This method allows the facile access of alkyl-, (hetero)aryl-, and alkynylzinc reagents to afford various α-substituted phenylacetone products under mild acidic hydrolysis, which are ubiquitous motifs in many pharmaceuticals and biologically active compounds. The diastereoselective reduction of imine can be accomplished to provide the expedient conversion of secondary benzylic halide into α-substituted phenethylamine derivatives with high atom economy.
- Wang, Chenglong,Wu, Licheng,Xu, Wentao,He, Feng,Qu, Jingping,Chen, Yifeng
-
supporting information
p. 6954 - 6959
(2020/09/15)
-
- A NHC-silyliumylidene cation for catalytic N?formylation of amines using carbon dioxide
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This study describes the use of a silicon(II) complex, namely, the NHC-silyliumylidene cation complex [(IMe)2SiH]I (1, IMe =:C{N(Me)C(Me)}2), to catalyze the chemoselective N-formylation of primary and secondary amines using CO2 and PhSiH3 under mild conditions to afford the corresponding formamides as a sole product (average reaction time: 4.5 h; primary amines, average yield: 95%, average TOF: 8 h?1; secondary amines, average yield: 98%, average TOF: 17 h?1). The activity of 1 and product yields outperform the currently available non-transition-metal catalysts used for this catalysis. Mechanistic studies show that the silicon(II) center in complex 1 catalyzes the C?N bond formation via a different pathway in comparison with non-transition-metal catalysts. It sequentially activates CO2, PhSiH3, and amines, which proceeds via a dihydrogen elimination mechanism, to form formamides, siloxanes, and dihydrogen gas.
- Leong, Bi-Xiang,Teo, Yeow-Chuan,Condamines, Cloe,Yang, Ming-Chung,Su, Ming-Der,So, Cheuk-Wai
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p. 14824 - 14833
(2020/12/21)
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- Tetracoordinate borates as catalysts for reductive formylation of amines with carbon dioxide
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We report sodium trihydroxyaryl borates as the first robust tetracoordinate organoboron catalysts for reductive functionalization of CO2. These catalysts, easily synthesized from condensing boronic acids with metal hydroxides, activate main group element-hydrogen (E-H) bonds efficiently. In contrast to BX3 type boranes, boronic acids and metal-BAr4 salts, under transition metal-free conditions, sodium trihydroxyaryl borates exhibit high reactivity of reductive N-formylation toward a variety of amines (106 examples), including those with functional groups such as ester, olefin, hydroxyl, cyano, nitro, halogen, MeS-, ether groups, etc. The over-performance to catalyze formylation of challenging pyridyl amines affords a promising alternative method to the use of traditional formylation reagents. Mechanistic investigation supports electrostatic interactions as the key for Si/B-H activation, enabling alkali metal borates as versatile catalysts for hydroborylation, hydrosilylation, and reductive formylation/methylation of CO2.
- Du, Chen-Xia,Huang, Zijun,Jiang, Xiaolin,Li, Yuehui,Makha, Mohamed,Wang, Fang,Zhao, Dongmei
-
supporting information
p. 5317 - 5324
(2020/09/17)
-
- Preparation method of 2-methoxy-4-nitroaniline
-
The invention discloses a preparation method of 2-methoxy-4-nitroaniline. The preparation method comprises the following steps of: carrying out acetylation reaction of o-methoxyaniline and acetic acid, discharging water generated in the acetylation reaction process from a reaction system, dropwisely adding fuming nitric acid into the prepared acetic acid solution of the o-methoxyacetanilide to carry out nitration reaction, adding deionized water after the nitration reaction is finished and then filtering, adding the prepared 2-methoxy-4-nitroaniline into an alkali solution to carry out hydrolysis reaction; after the hydrolysis reaction is finished, cooling the prepared reaction solution, and filtering to obtain 2-methoxy-4-nitroaniline. By adopting the method to synthesize 2-methoxy-4-nitroaniline, the acylation reaction cost is low, the nitration reaction selectivity is high, the discharge of three wastes is reduced, the production cost is reduced, the product purity is high, the yield is high, and the 2-methoxy-4-nitroaniline has a good industrial application value.
- -
-
Paragraph 0074; 0075
(2019/06/12)
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- Visible-light-induced radical cascade cyclization of oxime esters and aryl isonitriles: Synthesis of cyclopenta[: B] quinoxalines
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A visible-light-induced radical cascade cyclization of aryl isonitriles and cyclobutanone oxime esters for the synthesis of cyclopenta[b]quinoxalines has been accomplished for the first time. The key to the success of this process was the integration of the in situ-formed nitrile radical followed by the cascade radical isonitrile/nitrile insertion-cyclization. The easy introduction of substituents for both substrates and the high functional group tolerance of the reaction make it an efficient strategy to give various quinoxaline derivatives in moderate to good yields.
- Yuan, Yao,Dong, Wu-Heng,Gao, Xiao-Shuang,Xie, Xiao-Min,Zhang, Zhao-Guo
-
supporting information
p. 11900 - 11903
(2019/10/11)
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- An efficient method for the N-formylation of amines under catalyst- and additive-free conditions
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A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.
- Xu, Zhuo-Wei,Xu, Wen-Yi,Pei, Xiao-Jun,Tang, Fei,Feng, Yi-Si
-
supporting information
p. 1254 - 1258
(2019/04/10)
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- Mn-Catalyzed Selective Double and Mono-N-Formylation and N-Methylation of Amines by using CO2
-
Functionalization of amines by using CO2 is of fundamental importance considering the abundance of amines and CO2. In this context, the catalytic formylation and methylation of amines represent convenient and successful protocols for selective CO2 utilization as a C1 building block. This study represents the first example of selective catalytic double N-formylation of aryl amines by using a dinuclear Mn complex in the presence of phenylsilane. This robust system also allows for selective formylation and methylation of amines under a range of conditions.
- Huang, Zijun,Jiang, Xiaolin,Zhou, Shaofang,Yang, Peiju,Du, Chen-Xia,Li, Yuehui
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p. 3054 - 3059
(2019/04/10)
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- Visible-Light-Induced Radical Cascade Cyclization: Synthesis of the ABCD Ring Cores of Camptothecins
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A new strategy for constructing indolizino[1,2-b]quinolin-9(11H)-ones (ring cores of camptothecins) from readily available isocyanoarenes and N-(alkyl-2-yn-1-yl)pyridin-2(1H)-ones has been developed through a visible-light-induced radical cascade cyclization process. The reaction proceeds under mild conditions with fair to excellent yields. The easy introduction of substituents for both reactants and the broad functional group tolerance of the reaction make it a straightforward route to the cores of the marketed camptothecins and their derivatives.
- Yuan, Yao,Dong, Wuheng,Gao, Xiaoshuang,Gao, Huang,Xie, Xiaomin,Zhang, Zhaoguo
-
supporting information
p. 2840 - 2846
(2018/03/09)
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- Mild Access to N-Formylation of Primary Amines using Ethers as C1 Synthons under Metal-Free Conditions
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A new synthetic protocol has been developed for the synthesis of N-formamide derivatives using ethers as a C1 synthon under metal-free reaction conditions. The reaction is proposed to proceed through C?H functionalization, C?O cleavage, and C?N bond formation. This protocol is applicable to a variety of primary amines resulting in N-formamides in moderate to good yields. 1,4-dioxane was chosen as best C1 synthon after screening with various ethers. Mechanistic studies disclosed that the reaction proceeds through a radical pathway. While using α-amino ketones a α-alkylation product was formed rather than formylation. By replacing dioxane with Tetramethylethylenediamine (TMEDA) under standard conditions also gave the N-formamide derivatives in moderate yields. (Figure presented.).
- Mutra, Mohana Reddy,Dhandabani, Ganesh Kumar,Wang, Jeh-Jeng
-
supporting information
p. 3960 - 3968
(2018/09/10)
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- One-pot selective N-formylation of nitroarenes to formamides catalyzed by core-shell structured cobalt nanoparticles
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One-pot direct N-formylation of readily available nitroarenes with ammonium formate catalyzed by core-shell structured cobalt nanoparticles has been developed. A broad set of nitroarenes was successfully converted to their corresponding formamides in good to high yields with various functional group tolerance. This heterogeneous catalyst can be easily removed from the reaction medium and can be reused several times without a significant loss of reaction efficiency.
- Dong, Xiaosu,Wang, Zhaozhan,Duan, Yanan,Yang, Yong
-
supporting information
p. 8913 - 8916
(2018/08/17)
-
- Consecutive Lossen rearrangement/transamidation reaction of hydroxamic acids under catalyst- and additive-free conditions
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The Lossen rearrangement is a classic process for transforming activated hydroxamic acids into isocyanate under basic or thermal conditions. In the current report we disclosed a consecutive Lossen rearrangement/transamidation reaction in which unactivated hydroxamic acids were converted into N-substituted formamides in a one-pot manner under catalyst- and additive-free conditions. One feature of this novel transformation is that the formamide plays triple roles in the reaction by acting as a readily available solvent, a promoter for additive-free Lossen rearrangement, and a source of the formyl group in the final products. Acyl groups other than formyl could also be introduced into the product when changing the solvent to other low molecular weight aliphatic amide derivatives. The solvent-promoted Lossen rearrangement was better understood by DFT calculations, and the intermediacy of isocyanate and amine was supported well by experiments, in which the desired products were obtained in excellent yields under similar conditions. Not only monosubstituted formamides were synthesized from hydroxamic acids, but also N,N-disubstituted formamides were obtained when secondary amines were used as precursors.
- Jia, Mengmeng,Zhang, Heng,Lin, Yongjia,Chen, Dimei,Chen, Yanmei,Xia, Yuanzhi
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p. 3615 - 3624
(2018/05/26)
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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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- Diverse catalytic reactivity of a dearomatized PN3P?-nickel hydride pincer complex towards CO2 reduction
-
A dearomatized PN3P?-nickel hydride complex has been prepared using an oxidative addition process. The first nickel-catalyzed hydrosilylation of CO2 to methanol has been achieved, with unprecedented turnover numbers. Selective methylation and formylation of amines with CO2 were demonstrated by such a PN3P?-nickel hydride complex, highlighting its versatile functions in CO2 reduction.
- Li, Huaifeng,Gon?alves, Théo P.,Zhao, Qianyi,Gong, Dirong,Lai, Zhiping,Wang, Zhixiang,Zheng, Junrong,Huang, Kuo-Wei
-
supporting information
p. 11395 - 11398
(2018/10/20)
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- Method of N-formylating amines with a phosphonic anhydride
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A method for N-formylating an amine that includes reacting the amine and a formamide compound in the presence of a phosphonic anhydride to form an N-formylated amine. The phosphonic anhydride is present in an amount of 5-100 mol % relative to a total number of moles of the amine, and the reacting is performed for 1-24 hours at a temperature of 45-100° C.
- -
-
Page/Page column 21; 22; 25; 26
(2018/02/28)
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- A fragrant amines for the preparation of compounds (by machine translation)
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The invention discloses a fragrant amines preparation method of the compound, the method in a certain amount of supported cobalt-containing catalyst and a certain amount of fragrant nitryl compounds added in the reactor, then adding ammonium formate, and tetrahydrofuran mixed solvent with water, under stirring, the reaction temperature is 80 - 200 °C, reaction 0.5 - 24 h, to get the corresponding sweet-smelling amines compound. According to the preparation method of this invention the use of inexpensive, renewable bamboo shoots as raw materials for preparing carbon precursor, environmental protection, simple and easy to obtain, without adding nitrogen source material; at the same time in order to triphenylphosphine as the phosphorus source, low price. The substituted ammonium hydrogen as the reducing agent, the operation is simple, mild reaction conditions, in particular to an easily reducible functional group containing fragrant nitryl compounds for chemical selectivity can be controlled more easily. (by machine translation)
- -
-
Paragraph 0062-0066
(2018/11/10)
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- Silver-Catalyzed Chemoselective [4+2] Annulation of Two Isocyanides: A General Route to Pyridone-Fused Carbo- and Heterocycles
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A silver-catalyzed chemoselective [4+2] annulation of aryl and heteroaryl isocyanides with α-substituted isocyanoacetamides was developed for the facile and efficient synthesis of 2-aminoquinolones, naphthyridines, and phenanthrolines. A mechanism for this multistep domino reaction is proposed on the basis of a13C-labeling experiment, according to which an unprecedented chemoselective heterodimerization of two different isocyanides generates an α-amidoketenimine intermediate, which undergoes 1,3-amino migration to form an α-imidoylketene, followed by 6 π electrocyclization.
- Hu, Zhongyan,Dong, Jinhuan,Men, Yang,Lin, Zhichen,Cai, Jinxiong,Xu, Xianxiu
-
supporting information
p. 1805 - 1809
(2017/02/05)
-
- Process for preparing red-B preparation method
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The invention relates to a preparation method for a red base B. A formylation reaction is performed on o-aminoanisole and formic acid at 80-102 DEG C on the condition that acylation reaction solvent exists, and filtration is performed to obtain o-formamide anisole after the formylation reaction is completed; the o-formamide anisole is added into a sulfuric acid solution, nitric acid is added into a reaction system to perform a nitration reaction when the temperature of the reaction system is controlled at 0-70 DEG C, and filtration is performed to obtain methoxyl-4-nitroformanilide after the nitration reaction is completed; a hydrolysis reaction is performed on the methoxyl-4-nitroformanilide on the condition that the sulfuric acid and water exist at 80-120 DEG C, after the hydrolysis reaction is completed, separation is performed, the pH value is regulated to 6-7 with sodium carbonate, and then filtration is performed to obtain the red base B. According to the preparation method, the produce yield is high, the cost is low, the quality is good, by-products are less, waste water generated in the production process of the red base B is greatly reduced, the clean production requirement is met, operation is easy and convenient, and industrialization is facilitated.
- -
-
Paragraph 0037; 0040; 0041
(2017/12/02)
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- Sulfated polyborate-catalyzed N-formylation of amines: a rapid, green and efficient protocol
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Abstract: A rapid, green and efficient method for N-formylation reaction of various amines with formic acid in the presence of sulfated polyborate catalyst under solvent-free conditions has been described. The catalyst has the advantage of mild Bronsted as well as Lewis acid character. The catalyst is recyclable with no significant loss in catalytic activity. The present protocol is advantageous due to its solvent-free condition, short reaction time, high yields, easy workup and ability to tolerate a variety of functional groups.
- Khatri, Chetan K.,Chaturbhuj, Ganesh U.
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p. 2513 - 2519
(2017/11/06)
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- Discovery of New Selenoureido Analogues of 4-(4-Fluorophenylureido)benzenesulfonamide as Carbonic Anhydrase Inhibitors
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A series of benzenesulfonamides bearing selenourea moieties was obtained considering the ureido-sulfonamide SLC-0111, in Phase I clinical trials as antitumor agent, as a lead molecule. All compounds showed interesting inhibition potencies against the physiologically relevant human (h) carbonic anhydrase (hCAs, EC 4.2.1.1) isoforms I, II, IV, and IX. The most flexible analogues in the series 14-19 showed low nanomolar inhibition constants against hCA I, II, and IX. We assessed selected compounds on the in vitro antioxidant properties and binding modes and evaluated ex vivo human prostate (PC3), breast (MDA-MB-231), and colon-rectal (HT-29) cancer cell lines both in normoxic and hypoxic conditions.
- Angeli, Andrea,Tanini, Damiano,Peat, Thomas S.,Di Cesare Mannelli, Lorenzo,Bartolucci, Gianluca,Capperucci, Antonella,Ghelardini, Carla,Supuran, Claudiu T.,Carta, Fabrizio
-
supporting information
p. 963 - 968
(2017/09/22)
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- Solvent- and catalyst-free N-formylations of amines at ambient condition: Exploring the usability of aromatic formates as N-formylating agents
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A solvent- and catalyst-free N-formylation protocol has been developed for amines (1s–21s) where aromatic formates (1r–6r) were used as the N-formylating agents. The amine substrates include both primary and secondary aromatic amines (1s–19s) as well as aliphatic amine (20s) and a primary amide (21s). Structures of both the aromatic formate and amine components strongly influenced the rate of the reaction and yield of the N-formamide products. The reaction condition is mild and easy to operate. This protocol can be done smoothly under ambient conditions and gives high yield of formamide products. Furthermore, the present method cannot be applied for the formylation of thiol group (22s). This signifies its possible use for the chemoselective N-formylation of amine in the presence of thiol functionality.
- Batuta, Shaikh,Begum, Naznin Ara
-
supporting information
p. 137 - 147
(2017/01/11)
-
- Design, synthesis and biological evaluation of novel 4-(2-fluorophenoxy)quinoline derivatives as selective c-Met inhibitors
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Two novel series of 6,7-disubstituted-4-(2-fluorophenoxy)quinoline derivatives bearing 1H-imidazole-4-carboxamido or (E)-3-hydrosulfonylacrylamido motifs (16–31 and 32–42) were designed, synthesized and evaluated for their in vitro cytotoxic activity. Most of the compounds exhibited moderate to excellent potency against tested three cell lines, and fifteen compounds were further examined for their inhibitory activity against c-Met kinase. The most promising compound 16 (c-Met kinase [IC50]?=?1.1?nM) demonstrated high selectivity and remarkable cytotoxicity against HT-29, MKN-45 and A549 cells with IC50values of 0.08, 0.22 and 0.07?μM, which were 3.1-, 1.4- and 2.1-fold more active than Foretinib. The preliminary structure-activity relationships as well as molecular docking disclosed that 1H-imidazole-4-carboxamido as a linker was of great importance for the antitumor activity.
- Wang, Xiaoqiang,Jiang, Nan,Zhao, Sijia,Xi, Shuancheng,Wang, Jiao,Jing, Tongfei,Zhang, Wenyu,Guo, Ming,Gong, Ping,Zhai, Xin
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p. 886 - 896
(2017/02/05)
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- Design and Synthesis of Novel 4-Phenoxyquinolines Bearing 3-Hydrosulfonylacrylamido or 1H-Imidazole-4-carboxamido Scaffolds as c-Met Kinase Inhibitors
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A series of novel 6,7-disubstituted-4-phenoxyquinoline derivatives bearing (E)-3-hydrosulfonylacrylamido or 1H-imidazole-4-carboxamido moieties were designed, synthesized and evaluated for their cytotoxicity against A549, MKN-45, and HT-29 cancer cell lines in vitro. All the target compounds showed moderate to significant cytotoxic activity against the tested cells with IC50 values ranging from 0.13 to 2.65 μM. Five of them were further examined for their inhibitory activity against c-Met kinase, which identified compound 30 as a promising agent (c-Met IC50 = 1.52 nM) with IC50 values of 0.24, 0.45, and 0.13 μM against HT-29, MKN-45, and A549 cells, respectively.
- Wang, Jiao,Xie, Lijun,Wang, Yu,Wang, Xiaoqiang,Xi, Shuancheng,Zeng, Tianfang,Gong, Ping,Zhai, Xin
-
-
- 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)
-
- A process for preparing N - aryl amide compound
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The method discloses a method used for preparing an N-aryl amide compound from amides and aniline compounds. According to the method, a palladium salt and a ligand are taken as catalysts; an N,N-dimethyl formamide compound, an aniline compound, a protonic acid, a Lewis acid, and an organic solvent are mixed; and an obtained mixture is subjected to heating reaction so as to obtain the N-aryl amide compound. Advantages of the method are that: preparation route is short, substrate universality is excellent, reaction conditions are mild, synthesis yield is high, and used raw materials and catalysts are simple and easily available.
- -
-
Paragraph 0079-0082
(2017/08/02)
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- Electrostatic Catalyst Generated from Diazadiborinine for Carbonyl Reduction
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Since the seminal discovery by van der Waals in the late 19th century that weak attractive forces exist between even electrically neutral atoms or molecules, a number of noncovalent interactions have been recognized. Among them, electrostatic interactions such as hydrogen bonds play pivotal roles in countless chemical processes and biochemical living systems. By mimicking biocatalysis, various organocatalysts equipped with hydrogen-bond functionality have been developed; however, a challenge has persisted in designing catalysts exploiting other types of noncovalent interactions. Here, we report metal-free hydroboration reactions of carbonyl compounds and CO2 catalyzed by aromatic diazadiborinine. A joint experimental and computational study on the reaction mechanism suggests that adducts of diazadiborinine with carbonyl and CO2 formed at the initial stage of the reactions serve as actual catalysts. The former stabilizes the transition state by using the electrostatic interaction between the hydride of borane and the polar, hole-shaped structure of the adduct.
- Wu, Di,Wang, Ruixing,Li, Yongxin,Ganguly, Rakesh,Hirao, Hajime,Kinjo, Rei
-
supporting information
p. 134 - 151
(2017/07/17)
-
- Biomass-derived γ-valerolactone as an efficient solvent and catalyst for the transformation of CO2 to formamides
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Efficient conversion of carbon dioxide (CO2) into valuable chemicals is a very attractive topic. Herein, we conducted the first work on the utilization of biomass-derived γ-valerolactone (GVL) as the solvent and catalyst for transformation of CO2 with various primary and secondary amines in the presence of phenylsilane (PhSiH3), and the corresponding desired formamides were produced with high yields without any additional catalyst. Systematic studies indicated that the lactone structure of GVL played a key role in the formation of the active silyl formates and the activation of N-H bonds in amines, thus leading to the excellent performance of GVL for the catalytic reactions.
- Song, Jinliang,Zhou, Baowen,Liu, Huizhen,Xie, Chao,Meng, Qinglei,Zhang, Zhanrong,Han, Buxing
-
supporting information
p. 3956 - 3961
(2016/07/21)
-
- C-F Activation in Perfluorinated Arenes with Isonitriles under UV-Light Irradiation
-
Due to the great value of fluorinated arenes in agrochemistry, medicinal chemistry and materials science, development of methods for preparation of fluorinated arenes is of high importance. They can be either accessed by arene fluorination or by partial arene defluorination. However, the carbon-fluorine bond belongs to the strongest σ-bonds, which renders C-F activation highly challenging. Here it is shown that aryl and alkyl isonitriles efficiently activate the strong C-F bond in perfluoroarenes by simple UV irradiation under mild conditions. Reactions proceed by formal direct insertion of the isonitrile into the C-F bond without any transition metal. Activation occurs at arene C-F bonds whereas aliphatic C-F bonds remain unreacted. For selected perfluoroarenes C-F activation occurs with high regioselectivity and resulting imidoyl fluorides are transformed into other valuable compounds. Theoretical studies give insights into the reaction mechanism.
- Dewanji, Abhishek,Mück-Lichtenfeld, Christian,Bergander, Klaus,Daniliuc, Constantin G.,Studer, Armido
-
supporting information
p. 12295 - 12298
(2015/08/25)
-
- A metal-free approach for transamidation of amides with amines in aqueous media
-
An efficient, environmentally benign and a mild protocol for transamidation of amides with a variety of amines in the presence of K2S2O8 using stoichiometric quantity in aqueous conditions has been established. This method works under conventional thermal conditions and in microwave irradiation as well. A series of amides have been prepared using this reaction and this is a greener protocol for transamidation, which offers a diverse kind of substrate scope with exclusive product formation (yields 90-98%).
- Srinivas, Mahesuni,Hudwekar, Abhinandan D.,Venkateswarlu, Vunnam,Reddy, G. Lakshma,Kumar, K. A. Aravinda,Vishwakarma, Ram A.,Sawant, Sanghapal D.
-
supporting information
p. 4775 - 4779
(2015/07/20)
-
- The ortho effect on the acidic and alkaline hydrolysis of substituted formanilides
-
The kinetics of formanilides hydrolysis were determined under first-order conditions in hydrochloric acid (0.01-8 M, 20-60°C) and in hydroxide solutions (0.01-3 M, 25 and 40°C). Under acidic conditions, second-order specific acid catalytic constants were used to construct Hammett plots. The ortho effect was analyzed using the Fujita-Nishioka method. In alkaline solutions, hydrolysis displayed both first- and second-order dependence in the hydroxide concentration. The specific base catalytic constants were used to construct Hammett plots. Ortho effects were evaluated for the first-order dependence on the hydroxide concentration. Formanilide hydrolyzes in acidic solutions by specific acid catalysis, and the kinetic study results were consistent with the AAC2 mechanism. Ortho substitution led to a decrease in the rates of reaction due to steric inhibition of resonance, retardation due to steric bulk, and through space interactions. The primary hydrolytic pathway in alkaline solutions was consistent with a modified BAC2 mechanism. The Hammett plots for hydrolysis of meta- and para-substituted formanilides in 0.10 M sodium hydroxide solutions did not show substituent effects; however, ortho substitution led to a decrease in rate constants proportional to the steric bulk of the substituent.
- Desai, Salil Dileep,Kirsch, Lee E.
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p. 471 - 488
(2015/06/30)
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- Noble pyrene derivatives and organic light-emitting diode including the same
-
The present invention relates to a pyrene derivative represented by chemical formula A or chemical formula B, and an organic light-emitting device comprising the same. In the chemical formulas, Z, Ar1 to Ar4, Y1, and Y2 substituents and p, q and m are as
- -
-
Paragraph 0231-0237
(2016/10/08)
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- Synthesis of N-arylcarboxamides by the efficient transamidation of DMF and derivatives with anilines
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A novel protocol for the transamidation of DMF and derivatives with weakly nucleophilic anilines has been developed, utilizing a catalytic amount of Pd(OAc)2 and 2,2′-bipyridine, and with PivOH and BF3·Et2O as additives. This methodology has a broad substrate scope, and various corresponding transamidation products were prepared in good to excellent yields from commercially available DMF derivatives and anilines. The synthetic utility of the reported protocol was further demonstrated with a gram-scale experiment. Control experiments suggested the efficient transformation of DMF and derivatives with anilines might owe to the synergistic effect of palladium complex, PivOH, and BF3·Et2O.
- Gu, Da-Wei,Guo, Xun-Xiang
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p. 9117 - 9122
(2015/11/09)
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- Hydrophosphination of CO2 and Subsequent Formate Transfer in the 1,3,2-Diazaphospholene-Catalyzed N-Formylation of Amines
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Hydrophosphination of CO2 with 1,3,2-Diazaphospholene (NHP-H; 1) afforded phosphorus formate (NHP-OCOH; 2) through the formation of a bond between the electrophilic phosphorus atom in 1 and the oxygen atom from CO2, along with hydride transfer to the carbon atom of CO2. Transfer of the formate from 2 to Ph2SiH2 produced Ph2Si(OCHO)2 (3) in a reaction that could be carried out in a catalytic manner by using 5 mol % of 1. These elementary reactions were applied to the metal-free catalytic N-formylation of amine derivatives with CO2 in one pot under ambient conditions.
- Chong, Che Chang,Kinjo, Rei
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supporting information
p. 12116 - 12120
(2015/10/12)
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- Ligand free open air copper(II) mediated aryl formamidation and amination of aryl halides
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A simple synthetic procedure for direct formamidation and amination of aryl halides mediated by copper(II) salts was developed in open air, without an external ligand in formamide with potassium carbonate as a base. This approach is particularly efficient when electron active aryl halides are used as substrates. In these cases almost quantitative formamidation was observed.
- Komati, Rajesh,Jursic, Branko S.
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p. 1523 - 1527
(2014/03/21)
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- Highly efficient rhodium-catalyzed transfer hydrogenation of nitroarenes into amines and formanilides
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An efficient and selective rhodium-catalyzed transfer hydrogenation of nitroarenes with formic acid as the hydrogen source to give amines or formanilides has been developed. The addition of iodide ion accelerates the reaction, which can take place at room temperature. Georg Thieme Verlag Stuttgart New York.
- Wei, Yawen,Wu, Jianjun,Xue, Dong,Wang, Chao,Liu, Zhaotie,Zhang, Zhuozhuo,Chen, Guangfu,Xiao, Jianliang
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supporting information
p. 1295 - 1298
(2014/06/10)
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- Hypervalent iodine catalyzed transamidation of carboxamides with amines
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This protocol describes the catalytic use of diacetoxyiodobenzene (DIB) for the efficient transamidation of carboxamides with amines under mild conditions.
- Vanjari, Rajeshwer,Kumar Allam, Bharat,Nand Singh, Krishna
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p. 1691 - 1694
(2013/03/28)
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- A novel and simple transamidation of carboxamides in 1,4-dioxane without a catalyst
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An easy acylation and formylation of amines has been achieved via transamidation using 1,4-dioxane. The investigation works efficiently without an added catalyst and completes within short time under microwave irradiation.
- Vanjari, Rajeshwer,Allam, Bharat Kumar,Singh, Krishna Nand
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p. 2553 - 2555
(2013/06/05)
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- Nanoceria-catalyzed highly efficient procedure for N-formylation of amines at room temperature under solvent-free conditions
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Nanoceria-catalyzed simple and efficient protocol for the N-formylation of amines using formic acid at room temperature under solvent-free conditions shows high yield of desired product chemoselectivity and improvement in reaction time.
- Patil, Umakant B.,Singh, Abhilash S.,Nagarkar, Jayashree M.
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supporting information
p. 524 - 526
(2013/06/05)
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- A simple method for preparation of ZnO nanoparticles as a highly efficient nanocatalyst for N-formylation of primary and secondary amines under solvent-free condition
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A convenient reaction between alky, aryl, and heteroalkyl amines and formic acid as a formylating agent in the presence of catalytic amount of mechanochemically synthesized zinc oxide nanoparticles under solvent-free condition for the synthesis of corresponding N-formyl derivatives is described. Copyright Taylor and Francis Group, LLC.
- Alinezhad, Heshmatollah,Salehian, Fatemeh
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p. 532 - 538
(2013/07/19)
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- Copper-catalyzed formamidation of arylboronic acids: Direct access to formanilides
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A new approach for direct synthesis of formanilides starting from structurally varied arylboronic acids is reported. The protocol involves a copper-catalyzed Chan-Lam coupling reaction between arylboronic acids and formamide in the presence of a base at room temperature. The strategy offers a valid and practical alternative to existing transformations of amino, nitro, and azido arenes to formanilides, especially in terms of executing arylboronic acids as easily accessible, stable, and diversified substrates, under mild reaction conditions, and in a simple operation with high efficiency. Georg Thieme Verlag Stuttgart · New York.
- Srivastava, Vishnu P.,Yadav, Deepak K.,Yadav, Arvind K.,Watal, Geeta,Yadav, Lal Dhar S.
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p. 1423 - 1427
(2013/07/26)
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- Deep eutectic solvent promoted highly efficient synthesis of N, N'-diarylamidines and formamides
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A deep eutectic solvent was used as a dual catalyst and reaction medium for the efficient N-formylation of aromatic amines without hazardous organic solvent and catalyst. Treatment of aromatic amines with trimethyl orthoformate and formic acid in deep eutectic solvent at 70 °C gives the corresponding N-formyl derivatives in good to excellent yields. This simple ammonium deep eutectic solvent, easily synthesized from choline chloride and SnCl2, with 100% atom economy and making it applicable to industry and laboratory. Furthermore, heating the trimethyl orthoformate and aromatic primary amines in the deep eutectic solvent results in formation of the corresponding N,N'-diarylamidines in high yields.
- Azizi, Najmadin,Gholibeglo, Elham,Babapour, Mahbobe,Ghafuri, Hossein,Bolourtchian, Seyed Mohammad
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p. 768 - 773
(2012/10/30)
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- 2-(Sulfooxy)propane-1,2,3-tricarboxylic acid as novel and versatile catalyst for the formylation of alcohols and amines using ethyl formate under neat conditions
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2-(Sulfooxy)propane-1,2,3-tricarboxylic acid (supported on silica gel) has been introduced as novel and green catalyst for the formylation of alcohols and amines with ethyl formate, as mild formylation agent, under neat conditions at room temperature.. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
- Ghorbani-Choghamarani, Arash,Akbaripanah, Ziba
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experimental part
p. 450 - 453
(2012/06/04)
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- Efficient one-pot synthesis of unsymmetrical gold(I) N-heterocyclic carbene complexes and their use as catalysts
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Eleven different gold(I) complexes of new NHC ligands were prepared in excellent yield, demonstrating the versatility of the new route to NHC complexes. While the influence of electronically different ligands on the synthesis of the catalysts was small, the catalytic activities of the products differed significantly.
- Hashmi, A. Stephen K.,Yu, Yang,Rominger, Frank
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experimental part
p. 895 - 904
(2012/04/04)
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- A very simple and highly efficient procedure for N-formylation of primary and secondary amines at room temperature under solvent-free conditions
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N-Formylation of primary and secondary amines has efficiently been carried out at room temperature in excellent yields by using catalytic amount of sodium formate in formic acid under solvent-free conditions. The process is remarkably simple and environmentally benign.
- Brahmachari, Goutam,Laskar, Sujay
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experimental part
p. 2319 - 2322
(2010/05/19)
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- PROCESS FOR THE PREPARATION OF N-SUBSTITUTED FORMAMIDES
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N-Aryl- or N-heteroarylformamides are prepared by hydrogenating a corresponding nitroarene or nitroheteroarene with formic acid and/or ammonium formate as hydrogen donor and formylating agent in the presence of at least one noble metal-based hydrogenation catalyst and a vanadium or molybdenum compound as co-catalyst.
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- 10-Aminomethylene-1,8-dihydroxy-9(10H)-anthracenones: Inhibitory action against 5-lipoxygenase and the growth of HaCaT cells
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A novel series of 10-aminomethylene substituted 1,8-dihydroxy-9(10H)-anthracenones was synthesized and evaluated both in the bovine polymorphonuclear leukocyte 5-lipoxygenase (5-LO) and in the HaCaT keratinocyte proliferation assay for their enzyme inhibitory and antiproliferative activity, respectively. The synthesis required readily available formanilides as starting materials and a modified Vilsmeier type reaction with the parent anthracenone. The most potent inhibitor of 5-LO was a 4-hydroxyphenyl analog, whereas a 4-nitrophenyl substituent was essential for potent antiproliferative activity. The results of this study indicate that an activated double bond at C-10 of phenylalkylidene-substituted anthracenones is required for potency.
- Mueller,Sellmer,Prinz
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p. 895 - 900
(2007/10/03)
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- DECOMPOSITION OF ARYLAZIDES BY THF/n-BUTYLLITHIUM-II- -ISOLATION OF 1-ARYL-4,5-DIHYDRO-5-HYDROXY-1H-1,2,3-TRIAZOLES
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By reaction of arylazides having no electron-withdrawing groups with the enolate ion of the acetaldehyde (formed by cycloreversion of THF in the presence of n-buthyllithium), 1-aryl-4,5-dihydro-5-hydroxy-1H-1,2,3-triazoles could be isolated and then characterized.Further reaction of such hydroxytriazolines with the same enolate ion afforded substantial amounts of the corresponding N-formylanilines , confirming their intermediacy in the previously reported decomposition of arylazides by THF/n-butyllithium.On the other hand, using alkoxides as bases, the preferred scheme of conversion of the hydroxytriazolines was found to be the known dehydration to 1-aryl-1H-1,2,3-triazoles.
- Nunno, L. Di,Scilimati, A.
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p. 3913 - 3920
(2007/10/02)
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