- Direct para-Selective C-H Amination of Iodobenzenes: Highly Efficient Approach for the Synthesis of Diarylamines
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Iodine(III)-mediated synthesis of 4-iodo-N-phenylaniline from iodobenzene has been achieved, and the reaction can proceed under mild conditions. A variety of functional groups were well tolerated, providing the corresponding products in moderate to good yields. The remaining iodine group provides an effective platform for converting the products into several valuable asymmetric diphenylamines. Most importantly, this reaction can be easily scaled up to the ten-gram scale, highlighting its synthetic utility. The mechanistic study revealed that the in situ generated aryl hypervalent iodine intermediate is the key factor to realize this para-selective C-H amination reaction.
- Chen, Yujie,Huang, Zhibin,Jiang, Yaqiqi,Shu, Sai,Yang, Shan,Shi, Da-Qing,Zhao, Yingsheng
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p. 8226 - 8235
(2021/06/28)
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- Direct Superacid-Promoted Difluoroethylation of Aromatics
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Under superacid conditions, aromatic amines are directly and regioselectively 1,1-difluoroethylated. Low temperature in situ NMR studies confirmed the presence of benzylic α-fluoronium and α-chloronium ions as key intermediates in the reaction. This method has a wide substrate scope and can be applied to the late-stage functionalization of natural alkaloids and active pharmaceutical ingredients.
- Artault, Maxime,Martin-Mingot, Agnès,Thibaudeau, Sébastien,Vitse, Kassandra
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supporting information
(2021/12/22)
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- Method for catalyzing one-pot hydrogenation and amidation of nitroaromatic hydrocarbon and carboxylic acid by visible light
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The invention discloses a method for catalyzing one-pot hydrogenation and amidation reaction of nitroaromatic hydrocarbon and carboxylic acid by visible light. The method comprises the following steps: preparing Pt nanoparticles uniformly dispersed on an N-doped titanium dioxide/titanium carbide (MXene) heterojunction as a photocatalyst (3% Pt/N-TiO2/Ti3C2), and applying the catalyst to a cascade reaction of an aromatic nitro compound and carboxylic acid to prepare an amide product. The 3% Pt/N-TiO2/Ti3C2 has excellent tandem hydrogenation and amidation activity and chemical selectivity of an aromatic nitro compound and carboxylic acid under the irradiation of visible light. The excellent catalytic performance of 3% Pt/N-TiO2/Ti3C2 is attributed to the close contact of TiO2 and conductive Ti3C2, and the separation efficiency of photo-induced electrons and holes is improved through charge short-range directional transmission. The preparation method of the catalyst is simple and easy to operate, the catalyst can be used for photocatalytic efficient one-pot hydrogenation and amidation reactions, the reaction conditions are mild, and the catalyst is easy to recycle.
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Paragraph 0033
(2021/06/09)
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- Visible-light induced one-pot hydrogenation and amidation of nitroaromatics with carboxylic acids over 2D MXene-derived Pt/N-TiO2/Ti3C2
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Pt nanoparticles supported on N doped titanium dioxide/titanium carbide (MXene) heterojunctions were employed as photocatalysts for the tandem reactions between aromatic nitro compounds and carboxylic acids to produce amide products. The 3%Pt/N-TiO2/Ti3C2 heterojunction was prepared by in situ grew TiO2 on Ti3C2 nanosheets and then N doped TiO2 with melamine, Pt nanoparticles with 3.3 nm mean diameter well dispersed on N-TiO2/Ti3C2. 3%Pt/N-TiO2/Ti3C2 had excellent amidation activity and chemoselectivity under visible-light irradiation. The elevated catalytic performance of 3%Pt/N-TiO2/Ti3C2 was owing to the improvement in photogenerated electron and hole separation efficiency through charge short-range directional transmission caused by the intimate contact between the TiO2 and the conductive Ti3C2. This direct hydrogenation along with amidation between nitroaromatics and carboxylic acids own actual merits in the amides produce with no harmful byproducts. In situ DRIFTS spectra verified that the amidation activation with visible light irradiation at 25 °C was much faster than heating.
- Jiang, Heyan,Hu, Zujie,Gan, Chuan,Sun, Bin,Kong, Shuzhen,Bian, Fengxia
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- Metal-Free Photoinduced Transformation of Aryl Halides and Diketones into Aryl Ketones
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The acylation of aryl halides to prepare aryl ketones without metal catalyst represents an important yet challenging topic towards more sustainable ketone synthesis. Herein, we describe a simple and efficient metal-free protocol for the acylation of aryl halides with diketone under the irradiation of light utilizing N-methylpiperidine as base under an air atmosphere. This reaction can tolerate a wide range of functional groups and the corresponding ketones can be obtained in modest to good yields.
- Yao, Qiuli,Liu, Wenbo,Liu, Peng,Ren, Linjing,Fang, Xuehong,Li, Chao-Jun
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supporting information
p. 2721 - 2724
(2019/01/14)
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- Rhodium(III)-Catalyzed Directed C-H Dienylation of Anilides with Allenes Leads to Highly Conjugated Systems
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Allenes are unique coupling partners in transition-metal-catalyzed C-H functionalization leading to a variety of products via alkenylation, allenylation, allylation, and annulation reactions. The outcome is governed by both the reactivity of the allene and the formation and stability of the organometallic intermediate. An efficient Rh(III)-catalyzed, weakly coordinating group-directed dienylation of electronically unbiased allenes is developed using an N-acyl amino acid as a ligand. Further elaboration of the dienylated products to construct polycyclic compounds is also described.
- Ghosh, Chiranjit,Nagtilak, Prajyot Jayadev,Kapur, Manmohan
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supporting information
(2019/05/08)
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- Method for synthesizing alkyne through catalytic asymmetric cross coupling (by machine translation)
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The invention belongs to the field of, asymmetric synthesis, and discloses a method for catalyzing asymmetric cross- coupling to synthesize: an alkyne, and the L method comprises, the following steps, of A: preparing B a cuprous, salt and C a: ligand; preparing a catalyst; adding a base; reacting the compound with the compound with the compound; and reacting the compound with the compound. Of these, one of them, X is selected from the group consisting of, R halogens. 1 Optionally substituted heteroarylsulfonylcyanamide groups selected from the, group consisting, of optionally substituted, phenyl groups In-flight vehicle, R6 Trialkyl silyl groups or alkyl radicals, R2 Cycloalkyl radicals optionally substituted with an, optionally substituted alkyl, (CH radical2 )n R4 Multi,layer chain, n=0-10,R saw blade4 A group selected, from, the group consisting of phenyl, alkenyl, aralkynyls, noonyloxy,and, noonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulfonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylsulphonylphenyl disiloxy-radicals. R3 A ligand, selected from hydrogen or any of the functional groups, is selected from the group consisting of, hydrogen and any L other functional group. The method, R disclosed by the, A invention has the, advantages of good catalytic, R ’ effect, wide application range. and high catalytic efficiency, and the, method disclosed by the, invention has the. advantages of good catalytic effect, wide application range and high catalytic efficiency. (by machine translation)
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Paragraph 0383
(2020/01/12)
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- Highly ortho-Selective Chlorination of Anilines Using a Secondary Ammonium Salt Organocatalyst
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An organocatalytic, highly facile, efficient, and regioselective ortho-chlorination of anilines is described. A secondary ammonium chloride salt has been employed as the catalyst and the reaction can be conducted at room temperature without protection from air and moisture. In addition, the reaction is readily scalable and the catalyst can be recycled and reused. This catalytic protocol has been applied to the efficient synthesis of a highly potent c-Met kinase inhibitor. Mechanistic studies revealed that unique structural features of the secondary ammonium chloride salt are important for both the catalysis and regioselectivity of the electrophilic ortho-chlorination.
- Xiong, Xiaodong,Yeung, Ying-Yeung
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supporting information
p. 16101 - 16105
(2016/12/26)
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- A new method for synthesizing zaleplon (by machine translation)
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The present invention provides a new method for synthesizing zaleplon. In particular, the method of the invention takes the acetophenone as raw materials, make N-ethyl-N-[ 3 - (3- dimethyl amine -1-oxo-2-propenyl) phenyl] acetamide, with 3-amino-4-cyano pyrazole reaction, forming N-[ 3 - (3-cyano-pyrazolo [1,5-α] pyrimidin-7-yl) phenyl]-N-ethyl acetamide. The synthetic route of the present invention of fewer steps, after treatment is simple, low cost, suitable for industrial production. (by machine translation)
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Paragraph 0120; 0121
(2016/10/10)
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- A kind of two-thiazoline ketone compounds and pharmaceutical compositions thereof and use thereof (by machine translation)
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The invention provides general formula (I) indicated by the thiazoline ketone compounds and pharmaceutical compositions thereof and use thereof. The compounds can be combined with the bromodomain domain of the protein, thereby adjusting the downstream signal path, to play a particular function, can be used for treating the relevant domain protein in the bromodomain of various diseases. Such compounds can be interference has Brd4 bromodomain domain with the acetylated histone binding, and then lower the oncogene c - the ventilating cabins and its related target gene transcription, so that it may be effective for treating the tumor. (by machine translation)
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Paragraph 0129; 0130; 0131; 0132
(2017/01/17)
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- Structure-based modification of 3-/4-aminoacetophenones giving a profound change of activity on tyrosinase: From potent activators to highly efficient inhibitors
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In this study, we developed 3-/4-aminoacetophenones and their structure-based 3-/4-aminophenylethylidenethiosemicarbazide derivatives, respectively, as novel tyrosinase activators and inhibitors. Notably, all the obtained thiosemicarbazones displayed more potent tyrosinase inhibitory activities than kojic acid. Especially, compound 7k was found to be the most active tyrosinase inhibitor with IC50 value of 0.291 1/4M. The structure-activity relationships (SARs) analysis showed that: (1) the amine group was absolutely necessarily for determining the tyrosinase activation activity; (2) the introduction of thiosemicarbazide group played a very vital role in transforming tyrosinase activators into tyrosinase inhibitors; (3) the phenylethylenethiosemicarbazide moiety was crucial for determining the tyrosinase inhibitory activity; (4) the type of acyl group had no obvious effect on the inhibitory activity; (5) the position of amide substituent on the phenyl ring influenced the tyrosinase inhibitory potency. Moreover, the inhibition mechanism and inhibition kinetics study revealed that compound 7k was reversible and non-competitive inhibitor, and compound 8h was reversible and competitive-uncompetitive mixed-II type inhibitor.
- You, Ao,Zhou, Jie,Song, Senchuan,Zhu, Guoxun,Song, Huacan,Yi, Wei
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p. 255 - 262
(2015/03/04)
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- Synthesis and structure-activity relationship of aminoarylthiazole derivatives as correctors of the chloride transport defect in cystic fibrosis
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Abstract The cystic fibrosis transmembrane conductance regulator (CFTR) is a chloride channel present in the membrane of epithelial cells. Mutations affecting the CFTR gene cause cystic fibrosis (CF), a multi-organ severe disease. The most common CF mutation, F508del, impairs the processing and activity (gating) of CFTR protein. Other mutations, like G551D, only cause a gating defect. Processing and gating defects can be targeted by small molecules called generically correctors and potentiators, respectively. Aminoarylthiazoles (AATs) represent an interesting class of compounds that includes molecules with dual activity, as correctors and potentiators. With the aim to improve the activity profile of AATs, we have now designed and synthesized a library of novel compounds in order to establish an initial SAR that may provide indications about the chemical groups that are beneficial or detrimental for rescue activity. The new compounds were tested as correctors and potentiators in CFBE41o-expressing F508del-CFTR using a functional assay. A dual active compound, AAT-4a, characterized by improved efficacy and marked synergy when combined with the corrector VX-809 has been identified. Moreover, by computational methods, a possible binding site for AATs in nucleotide binding domain NBD1 has been detected. These results will direct the synthesis of new analogues with possibly improved activity.
- Pesce, Emanuela,Bellotti, Marta,Liessi, Nara,Guariento, Sara,Damonte, Gianluca,Cichero, Elena,Galatini, Andrea,Salis, Annalisa,Gianotti, Ambra,Pedemonte, Nicoletta,Zegarra-Moran, Olga,Fossa, Paola,Galietta, Luis J.V.,Millo, Enrico
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- TETRAZOLINONE COMPOUND AND USE THEREOF
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The compound represented by formula (1): wherein R4 and R5 each represents a hydrogen atom, a halogen atom, or a C1-C3 alkyl group; R6 represents a C1-C4 alkyl group, a C3-C6 cycloalkyl group, or the like; R7, R8, and R9 each represents a hydrogen atom, a halogen atom, or the like; R10 represents a C1-C3 alkyl group, or the like; R13 represents a C1-C3 alkyl group, or the like; and Q represents a phenyl group, or the like; has an excellent control effect on pests.
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Paragraph 0853
(2015/11/16)
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- Antiobesity, antioxidant and cytotoxicity activities of newly synthesized chalcone derivatives and their metal complexes Dedicated to Professor R. R. Schmidt on the occasion of his 79th birthday.
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Four sets of rationally designed chalcones were prepared for evaluation of their antiobesity, antioxidant and cytotoxicity activities. These sets include nine oleoyl chalcones as mimics of oleoyl estrone, three monohydroxy chalcones (chalcone ligands), Schiff base-derived chalcones and four copper as well as zinc complexes. Oleoyl chalcones 4d, 4e and particularly 6a as an isosteric isomer of oleoyl estrone, were as active as Orlistat on weight loss and related metabolic parameters using male SD rats in vivo. Chalcone ligands 10a-c and Schiff base-derived chalcones 11 and 14a,b were weakly antioxidants, while, the copper and zinc complexes 15a-d were good antioxidants with zinc chelates 15b,d being more active than their copper analogues 15a,cin vitro. Compounds 10c and 14a showed good cytotoxicity activities as Doxorubicin against PC3 cancer cell line in vitro, while, the copper complex 15c showed promising activity with IC50 value of 5.95 μM. The estimated IC50 value for Doxorubicin was 8.7 μM. Chalcones 14a,b are bifunctional probes for potential investigations in cancer diagnosis and radiotherapy by complexation with Gd3+ or metal radioisotopes followed by posttranslation of Shiga toxin B-subunits that target globotriosyl ceramide expressing cancer cells.
- El Sayed Aly, Mohamed Ramadan,Abd El Razek Fodah, Hamadah Hamadah,Saleh, Sherif Yousef
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p. 517 - 530
(2014/03/21)
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- Green synthesis of benzamides in solvent- and activation-free conditions
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Herein, we describe a clean and ecocompatible pathway for both N-benzoylation and N-acetylation of anilines, amines, diamines, and aminoalcohols using three enol esters with good yields. We have improved the use of vinyl benzoate for the direct introduction of a benzamido-moiety under solvent- and activation-free conditions. The recovered amides are easily isolated by crystallization. Copyright
- Alalla, Affef,Merabet-Khelassi, Mounia,Aribi-Zouioueche, Louisa,Riant, Olivier
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supporting information
p. 2364 - 2376
(2014/07/22)
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- ZnAl2O4@SiO2 nanocomposite catalyst for the acetylation of alcohols, phenols and amines with acetic anhydride under solvent-free conditions
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A ZnAl2O4@SiO2 nanocomposite was prepared from metal nitrates and tetraethyl orthosilicate by the sol-gel process, and characterized by X-ray diffraction, Fourier transform infrared, transmission electron microscopy, and N2 adsorption-desorption measurements. The nanocomposite was tested as a heterogeneous catalyst for the acetylation of alcohols, phenols, and amines under solvent-free conditions. Under optimized conditions, efficient acetylation of these substrates with acetic anhydride over the ZnAl2O4@SiO2 nanocomposite was obtained. Acetylation of anilines and primary aliphatic amines proceeded rapidly at room temperature, while the reaction time was longer for the acetylation of alcohols and phenols, showing that an amine NH2 group can be selectively acetylated in the presence of alcoholic or phenolic OH groups. The catalyst can be reused without obvious loss of catalytic activity. The catalytic activity of the ZnAl2O4@SiO2 nanocomposite was higher than that of pure ZnAl2O4. The method gives high yields, and is clean, cost effective, compatible with substrates having other functional groups and it is suitable for practical organic synthesis.
- Farhadi, Saeed,Jahanara, Kosar
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p. 368 - 375
(2014/04/03)
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- Synthesis and biological evaluation of glucagon-like peptide-1 receptor agonists
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In this study, a series of fused-heterocyclic derivatives were systematically designed and synthesized using an efficient route, and evaluated in terms of GLP-1R agonist activity. We employed short synthetic steps and reactions that are tolerant of the presence of various functional groups and suitable for parallel operations to enable the rapid generation of libraries of diverse and structurally complex small molecules. Of the compounds synthesized, 3-(8-chloro-6-(trifluoromethyl)imidazo[1,2-a] pyridin-2-yl)phenyl methanesulfonate (8e) was the most potent agonist with an EC50 of 7.89 μM, and thus is the compound with the greatest potential for application. These findings represent a valuable starting point for the design and discovery of small-molecule GLP-1R agonists that can be administered orally.
- Zhang, Yu-Juan,Shen, Liu-Lan,Cheon, Hyae-Gyeong,Xu, Yong-Nan,Jeong, Jin-Hyun
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p. 588 - 599
(2014/06/09)
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- Fragment-based drug discovery of 2-thiazolidinones as inhibitors of the histone reader BRD4 bromodomain
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Recognizing acetyllysine of histone is a vital process of epigenetic regulation that is mediated by a protein module called bromodomain. To contribute novel scaffolds for developing into bromodomain inhibitors, we utilize a fragment-based drug discovery approach. By successively applying docking and X-ray crystallography, we were able to identify 9 fragment hits from diffracting more than 60 crystals. In the present work, we described four of them and carried out the integrated lead optimization for fragment 8, which bears a 2-thiazolidinone core. After several rounds of structure guided modifications, we assessed the druggability of 2-thiazolidinone by modulating in vitro pharmacokinetic studies and cellular activity assay. The results showed that two potent compounds of 2-thiazolidinones have good metabolic stability. Also, the cellular assay confirmed the activities of 2-thiazolidinones. Together, we hope the identified 2-thiazolidinone chemotype and other fragment hits described herein can stimulate researchers to develop more diversified bromodomain inhibitors.
- Zhao, Lele,Cao, Danyan,Chen, Tiantian,Wang, Yingqing,Miao, Zehong,Xu, Yechun,Chen, Wuyan,Wang, Xin,Li, Yanlian,Du, Zhiyan,Xiong, Bing,Li, Jian,Xu, Chunyan,Zhang, Naixia,He, Jianhua,Shen, Jingkang
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p. 3833 - 3851
(2013/07/11)
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- Oxidative para- Triflation of acetanilides
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Direct triflation of acetanilide derivatives with silver triflate has been accomplished under mild iodine(III)-mediated oxidative conditions. The reaction shows excellent regioselectivity for the para position and tolerates a range of ortho and meta substituents on the aromatic ring. This method is also compatible with the preparation of arylnonaflates in synthetically useful yields.
- Pialat, Amelie,Liegault, Benoit,Taillefer, Marc
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supporting information
p. 1764 - 1767
(2013/06/26)
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- Design, synthesis and biological evaluation of new aryl thiosemicarbazone as antichagasic candidates
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The present work reports on the synthesis, biological assaying and docking studies of a series of 12 aryl thiosemicarbazones, which were planned to act over two main enzymes, cruzain and trypanothione reductase. These enzymes are used as targets of trypanocidal activity in Chagas disease control with a minimal mutagenic profile. Three p-nitroaromatic thiosemicarbazones showed high activity against Trypanosoma cruzi in in vitro assays (IC50 57 μM), and no mutagenic profile was observed in micronucleous tests. Although the in vitro inhibition test showed that 10-μM doses of eight compounds inhibited cruzain activity, no correlation was found between cruzain inhibition and trypanocidal activity.
- Blau, Lorena,Menegon, Renato Farina,Trossini, Gustavo H. G.,Molino, Jo?o Vitor Dutra,Vital, Drielli Gomes,Cicarelli, Regina Maria Barretto,Passerini, Gabriela Duó,Bosquesi, Priscila Longhin,Chin, Chung Man
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p. 142 - 151
(2013/10/01)
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- Direct exchange of a ketone methyl or aryl group to another aryl group through ciC bond activation assisted by rhodium chelation
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Swapped: Commercially available quinolinone derivatives (1 or 2, see scheme) were reacted with arylboronic acids in the presence of a RhI complex to give aryl(quinolin-8-yl)methanone products 3 in medium to good yields. A mechanism that involves the in situ oxidation of RhI to RhIII by O2 in the presence of CuI was proposed. Copyright
- Wang, Jingjing,Chen, Weiqiang,Zuo, Sujing,Liu, Lu,Zhang, Xinrui,Wang, Jianhui
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supporting information
p. 12334 - 12338
(2013/02/23)
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- Synthesis, biological evaluation, and molecular docking of N-{3-[3-(9-methyl-9H-carbazol-3-yl)-acryloyl]-phenyl}-benzamide/amide derivatives as xanthine oxidase and tyrosinase inhibitors
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Claisen-Schmidt condensation of 3-formyl-9-methylcarbazole with various amides of 3-aminoacetophenone afforded N-{3-[3-(9-methyl-9H-carbazol-3-yl)- acryloyl]-phenyl}-benzamide/amide derivatives. All compounds were investigated for their in vitro xanthine oxidase (XO), tyrosinase and melanin production inhibitory activity. Most of the target compounds had more potent XO inhibitory activity than the standard drug (IC50 = 4.3-5.6 μM). Interestingly, compound 7q bearing cyclopropyl ring was found to be the most potent inhibitor of XO (IC50 = 4.3 μM). Molecular modelling study gave an insight into its binding modes with XO. Compounds 7a, 7d, 7e, 7g, and 7k were found to be potent inhibitors of tyrosinase (IC50 = 14.01-17.52 μM). These results suggest the possible use of these compounds for the design and development of novel XO and tyrosinase inhibitors.
- Bandgar, Babasaheb P.,Adsul, Laxman K.,Chavan, Hemant V.,Shringare, Sadanand N.,Korbad, Balaji L.,Jalde, Shivkumar S.,Lonikar, Shrikant V.,Nile, Shivraj H.,Shirfule, Amol L.
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p. 5649 - 5657
(2012/10/29)
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- Acceptorless and base-free dehydrogenation of alcohols and amines using ruthenium-hydride complexes
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An efficient, operatively simple, acceptorless, and base-free dehydrogenation of secondary alcohols and nitrogen-containing heterocyclic compounds was achieved by using readily available ruthenium hydride complexes as precatalysts. The complex RuH2(CO)(PPh3)3 (1) and Shvo's complex (2) showed excellent activities for the dehydrogenation of secondary alcohols and nitrogen containing heterocycles. In addition to complexes 1 and 2, the complex RuH2(PPh3)4 (3) also showed moderate to excellent activity for the acceptorless dehydrogenation of nitrogen-containing heterocyclic compounds. Kinetic studies on the oxidation reaction of 1-phenylethanol using complex 1 were carried out in the presence and the absence of external triphenylphosphine (PPh3). External addition of PPh3 had a negative influence on the rate of the reaction, which suggested that dissociation of PPh3 occurred during the course of the reaction. Hydrogen was evolved from the oxidation reaction of 1-phenylethanol by using 1 mol% of 1 (88%) and 2 (92%), which demonstrated the possible usage of the catalytic systems in hydrogen generation. Copyright
- Muthaiah, Senthilkumar,Hong, Soon Hyeok
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p. 3045 - 3053
(2013/01/15)
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- Candida tenuis xylose reductase catalysed reduction of acetophenones: The effect of ring-substituents on catalytic efficiency
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The catalytic efficiencies of Candida tenuis xylose reductase catalysed reductions of mono-substituted acetophenones are in reasonable correlation with the σ-Hammett coefficients of the substituted phenyl groups. Variations of the substrate transformation rates are hence mainly caused by mesomeric and inductive effects of the substituents, while differences in substrate binding have a secondary relevance. Some substrate 1H NMR chemical shifts and carbonyl IR absorption bands are in reasonable accordance with the catalytic activities and allow the estimation of the transformation rates with good accuracy. The resulting substituted (S)-1-phenyl ethanols are generated in very high enantiomeric excess.
- Vogl, Michael,Kratzer, Regina,Nidetzky, Bernd,Brecker, Lothar
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experimental part
p. 5863 - 5870
(2011/09/30)
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- Additive-free chemoselective acylation of amines
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Aliphatic and aromatic amines are efficiently acylated by acetic, pivalic, benzoic, phthalic, or maleic anhydrides in ethyl acetate at room temperature. Under the same experimental conditions, amino alcohols are chemoselectively acylated at the amino group.
- Temperini, Andrea,Terlizzi, Raffaella,Testaferri, Lorenzo,Tiecco, Marcello
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experimental part
p. 295 - 302
(2010/03/30)
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- Spinel-type zinc aluminate (ZnAl2O4) nanoparticles prepared by the co-precipitation method: A novel, green and recyclable heterogeneous catalyst for the acetylation of amines, alcohols and phenols under solvent-free conditions
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Zinc aluminate (ZnAl2O4) nanoparticles with an average particle size of about 8 nm were easily prepared by the co-precipitation method using aqueous ammonia solution as the precipitating agent. This nanosized spinel-type oxide was characterized by TGA, XRD, FT-IR, TEM, and surface area measurement and used as the heterogeneous catalyst for the acetylation reaction. Efficient acetylation of various amines, alcohols and phenols was carried out over ZnAl2O4 nanoparticles using acetic anhydride and/or acetyl chloride as the acetylating agents at room temperature without the use of a solvent. The method is highly selective, allowing the alcoholic hydroxyl group to be protected while the phenolic hydroxyl group remains intact, and the amine group can be acetylated in the presence of the hydroxyl group. This method is fast and has a high yield. It is also clean, safe, cost effective, compatible with substrates that have other functional groups and very suitable for practical organic synthesis. In addition, the catalyst can be reused without significant loss of activity. Indeed, the catalytic activity of the ZnAl2O4 nanoparticles is higher than that of bulk ZnAl2O4.
- Farhadi, Saeid,Panahandehjoo, Somayeh
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scheme or table
p. 293 - 302
(2010/09/04)
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- Synthesis of deuterium-labeled zaleplon-d5 as an internal standard
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Zaleplon is licensed for the short-term treatment of insomnia. Excessive usage causes side effects; hence, the drug is controlled. Identifying zaleplon in a drug abuser requires an isotope-labeled internal standard. This work presents a synthesis of stable isotope-labeled internal standard for zaleplon, zaleplon-d5, by a five-step synthetic sequence. Copyright
- Shaikh, Ajam C.,Chen, Chinpiao
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- Expedient synthesis of deuterium-labelled amides within micro-reactors
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The pharmaceutical industry relies heavily on the synthesis of small quantities (10-500 mg) of stable, isotopically labelled compounds in the evaluation of new drug candidates for metabolism studies. As a result of the phenomenal cost of labelled materials even the preparation of small quantities can be extremely expensive. In this paper, for the first time, we report that micro-reactor technology may be used to prepare stable deuterium-labelled compounds by conducting all optimization experiments using unlabelled precursors and simply substituting the labelled derivatives once the optimization is complete. Here, we wish to present a simple, general procedure for the synthesis of amides containing isotopic labels demonstrated using [C-2H 3]acetyl chloride 1. The reaction is carried out within a micro-reactor set-up which we believe offers superiority over other reported methods viz requiring stoichiometric quantities of reagents, high containment of the system and generality of the technique, obtaining products in high yields. Copyright
- Hooper, Julian,Watts, Paul
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p. 189 - 196
(2008/02/08)
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- Efficient tandem process for the catalytic deprotection of N-allyl amides and lactams in aqueous media: A novel application of the bis(allyl)- ruthenium(IV) catalysts [Ru(η3:η2: η3-C12H18)Cl2] and [Ru(η3:η3-C10H16)-(μ-Cl) Cl}2]
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An operationally simple and highly efficient methodology for the removal of the allyl protecting group in amides and lactams has been developed by using the commercially available bis(allyl)-ruthenium(IV) catalysts [Ru(η3:η2:η3-C12H 18)Cl2] (C12H18 = dodeca-2,6,10-triene-1,12-diyl) and [(Ru(η3:η3- C10H16)(μ-Cl)Cl}2] (C10H 16 = 2,7-dimethylocta-2,6-diene-1,8-diyl). The tandem process, which takes place in aqueous media and proceeds in a one-pot manner, involves the initial isomerization of the C=C bond of the allyl unit and subsequent oxidative cleavage of the resulting enamide.
- Cadierno, Victorio,Gimeno, Jose,Nebra, Noel
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p. 6590 - 6594
(2008/03/13)
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- Zinc oxide (ZnO) as a new, highly efficient, and reusable catalyst for acylation of alcohols, phenols and amines under solvent free conditions
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Zinc oxide (ZnO) is a highly efficient catalyst for the acylation of a variety of alcohols, phenols and amines with acid chlorides or acid anhydrides under solvent free conditions. Primary, secondary, tertiary, allylic and benzylic alcohols, diols and phenols with electron donating or withdrawing substituents can be easily acylated in good to excellent yield.
- Hosseini Sarvari, Mona,Sharghi, Hashem
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p. 10903 - 10907
(2007/10/03)
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- PRODUCTION OF N-ALKYLAMIDE COMPOUNDS
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The present invention provides an efficient process for the production of N-acylaniline derivatives by selectively alkylating an amide group at the nitrogen atom. The process comprises reacting an amide compound of the formula (2): (wherein, R1 and R2 are each independently an alkyl group, a substituted alkyl group, an alkenyl group, a substituted alkenyl group, an aryl group or a substituted aryl group) with a sulfuric acid ester in the presence of a solid metal hydroxide to give an N-alkylamide compound of the formula (3): (wherein R3 is an alkyl group and R1 and R2 have each the same meaning as described above).
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- Preparation of m-acylaniline derivatives by the reaction of tricarbonyl(cyclohexadienone O-benzyloxime)iron complex and higher order cuprates
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Reaction of tricarbonyl[(2,3,4,5-η)-2,4-cyclohexadien-1-one O-benzyloxime]iron and organocuprates, followed by the treatment with acetic anhydride and carbon monoxide, affords [(1,2,3,4-η)-1-(N-acetoxy-N-benzyloxyamino)-5-endo-acyl-1,3-cyclohexadiene] tri
- Ban, Soo Ho,Hayashi, Yujiro,Narasaka, Koichi
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p. 393 - 394
(2007/10/03)
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- Reinvestigation of a 5H-Dibenzotriazonine Synthesis
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Treatment of 5-chloro-2-aminobenzophenone (1) with o-phenylenediamine, sodium acetate, and acetic acid gave 2-(acetyl)amino-5-chlorobenzophenone (5) rather than N--1,2-benzenediamine (3), as reported by Kulkarni et al.Authentic 3 was prepared and treated with chloroacetic acid and polyphosphoric acid (PPA) to give 1, recovered 3, 2,8-dichloro-6,12-diphenyldibenzodiazocine (9) and 2-chloro-6-(chloromethyl)-13-phenyl-5H-dibenzotriazonine (10).Treatment of 5 with PPA, with or without chloroacetic acid, gave phenyl> phenylmethanone (11) as the sole product in 90percent yield.Treatment of other benzophenones, acetophenones, and anilines with sodium acetate and acetic acid provided acetanilides in 78-96percent yield, with the exception of 2'-aminoacetophenone (20), wich gave a quantitative yield of 2--4-methylquinoline (21).The mechanism of acetanilide formation with sodium acetate and acetic acid is discussed.The structure of 21 was established using high resolution 1H nmr techniques.Attempts to prepare an authentic sample of 21 from 2-chlorolepidine (26) and (20) gave 4-methyl-N--2-quinolinamine (29) as the major product.
- Peet, Norton P.,Sunder, Shyam,Barbuch, Robert J.,Whalon, Michael R.,Huber, Edward W.,Huffman, John C.
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p. 1611 - 1618
(2007/10/02)
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- SOLVOLYSIS KINETICS AND MECHANISM OF SUBSTITUTED 3-ACETYL-1,3-DIPHENYLTRIAZENES IN ACID MEDIUM; KINETIC ACIDITY FUNCTION
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The decomposition kinetics has been measured of fourteen 3-acetyl-1,3-bis(subst.phenyl)triazines in 40percent (v/v) ethanol and sulphuric acid.The kinetic acidity function and catalytic rate constants have been determined from the rate constants observed.Mechanism has been suggested for the general acid-catalyzed solvolysis from comparison of the course of the kinetic acidity function and H0 function and from the reaction constant of the Hammett equation.
- Pytela, Oldrich,Kaska, Martin,Ludwig, Miroslav,Vecera, Miroslav
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p. 2212 - 2216
(2007/10/02)
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- 2-(4-BENZOYL-1-PIPERIDYL)-1-PHENYLALKANOL DERIVATIVES
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Compound of general formula I STR1 in which R is hydrogen, R 1 is unsubstituted phenyl, 4-methoxy-3,5-dimethylphenyl or phenyl substituted at one of the 2-, 3-or 4-positions by halogen, C 1-4 alkyl, C 1-4 alkoxy, hydroxy, benzyloxy, trifluoromethyl, cyano, nitro, amino, acetylamino, methylthio, methylsulphonyl or aminosulphonyl and R 2 is unsubstituted phenyl, 2,4,6-trimethoxyphenyl or phenyl substituted at either the 3-or the 4-positions by fluorine, chlorine, methyl or methoxy, or an acid addition salt thereof.
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