- Catalyst and solvent-free alkylation of quinoline N-oxides with olefins: A direct access to quinoline-substituted α-hydroxy carboxylic derivatives
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A catalyst/solvent-free, one-pot and operationally simple method for the synthesis of quinoline-substituted α-hydroxy carboxylic derivatives by the hydroxyheteroarylation of olefins with quinoline N-oxides is reported. The reaction features a high atom-economy, mild and reagent/solvent-free conditions, broad substrate scope and good selectivity with high yields. A preliminary mechanistic study to shed light into the reaction pathway was also carried out.
- Kumar, Rakesh,Kumar, Inder,Sharma, Ritika,Sharma, Upendra
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- SO2F2-mediated oxidation of primary and tertiary amines with 30% aqueous H2O2 solution
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A highly efficient and selective oxidation of primary and tertiary amines employing SO2F2/H2O2/base system was described. Anilines were converted to the corresponding azoxybenzenes, while primary benzylamines were transformed into nitriles and secondary benzylamines were rearranged to amides. For tertiary amine substrates quinolines, isoquinolines and pyridines, their oxidation products were the corresponding N-oxides. The reaction conditions are very mild and just involve SO2F2, amines, 30% aqueous H2O2 solution, and inorganic base at room temperature. One unique advantage is that this oxidation system is just composed of inexpensive inorganic compounds without the use of any metal and organic compounds.
- Liao, Xudong,Zhou, Yi,Ai, Chengmei,Ye, Cuijiao,Chen, Guanghui,Yan, Zhaohua,Lin, Sen
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supporting information
(2021/11/01)
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- Method for preparing sulfone and N-oxygen compound by using green and efficient oxidation system
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The invention discloses a method for preparing sulfone and N-oxygen compound by using a green and efficient oxidation system. The method comprises the following steps of: by using a tertiary amine compound or aromatic thioether or fatty thioether compound as a raw material, H2O2 as an oxidant, methanol as a reaction solvent and potassium carbonate as an alkali, introducing sulfuryl fluoride 5O2F2gas as an accelerator; performing stirring at room temperature under a sealed condition for oxidation reaction; and after finishing the reaction, filtering to remove solid potassium carbonate, dryingto remove water, filtering to obtain a crude product, and finally carrying out column chromatography separation to obtain a pure product. Tertiary amine is oxidized into an N-oxygen compound, and thethioether is oxidized into sulfone. According to the method, the sulfuryl fluoride (SO2F2) which is very cheap and easy to obtain is used as the reaction promoter, green and environment-friendly hydrogen peroxide (H2O2) is used as an oxidizing agent, and so that the yield of the reaction is generally high; after the reaction, byproducts are only water and inorganic salts (SO4 and F) whichare easy to remove and free of pollution, and the green and efficient oxidation system can be realized, and therefore, the method is suitable for large-scale industrial production.
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Paragraph 0027-0029
(2021/01/29)
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- Efficient visible light mediated synthesis of quinolin-2(1H)-ones from quinolineN-oxides
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Quinolin-2(1H)-ones are one of the important classes of compounds due to their prevalence in natural products and in pharmacologically useful compounds. Here we present an unconventional and hitherto unknown photocatalytic approach to their synthesis from easily available quinoline-N-oxides. This reagent free highly atom economical photocatalytic method, with low catalyst loading, high yield and no undesirable by-product, provides an efficient greener alternative to all conventional synthesis reported to date. The robustness of the methodology has been successfully demonstrated with easy scaling up to the gram scale.
- Bhuyan, Samuzal,Chhetri, Karan,Hossain, Jagir,Jana, Saibal,Mandal, Susanta,Roy, Biswajit Gopal
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supporting information
p. 5049 - 5055
(2021/07/29)
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- Metal-free C8-H functionalization of quinolineN-oxides with ynamides
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The metal-free C8-H functionalization of quinolineN-oxides with ynamides is unveiled for the first time by the intramolecular Friedel-Crafts-type reaction of quinolyl enolonium intermediates generated from Br?nsted acid-catalyzed addition of quinolineN-ox
- Hu, Weican,Zhang, Feiyang,Chen, Chen,Qi, Tianhang,Shen, Yanlong,Qian, Guoying,Rong, Zhouting
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supporting information
p. 6995 - 6998
(2021/07/21)
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- N-(4-acetamidophenyl)-5-acetylfuran-2-carboxamide as a novel orally available diuretic that targets urea transporters with improved PD and PK properties
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Urea transporters (UTs) have been identified as new targets for diuretics. Functional deletion of UTs led to urea-selective urinary concentrating defects with relative salt sparing. In our previous study, a UT inhibitor with a diarylamide scaffold, which is denoted as 11a, was demonstrated as the first orally available UT inhibitor. However, the oral bioavailability of 11a was only 4.38%, which obstructed its clinical application. In this work, by replacing the nitro group of 11a with an acetyl group, 25a was obtained. Compared with 11a, 25a showed a 10 times stronger inhibitory effect on UT-B (0.14 μM vs. 1.41 μM in rats, and 0.48 μM vs. 5.82 μM in mice) and a much higher inhibition rate on UT-A1. Moreover, the metabolic stability both in vitro and in vivo and the drug-like properties (permeability and solubility) of 25a were obviously improved compared with those of 11a. Moreover, the bioavailability of 25a was 15.18%, which was 3 times higher than that of 11a, thereby resulting in significant enhancement of the diuretic activities in rats and mice. 25a showed excellent potential for development as a promising clinical diuretic candidate for targeting UTs to treat diseases that require long-term usage of diuretics, such as hyponatremia.
- Wang, Shuyuan,Xu, Yue,Zhao, Yan,Zhang, Shun,Li, Min,Li, Xiaowei,He, Jinzhao,Zhou, Hong,Ge, Zemei,Li, Runtao,Yang, Baoxue
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- Copper/manganese oxide catalyzed regioselective amination of quinoline N-oxides: An example of synergistic cooperative catalysis
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An atom economical and efficient protocol for C-2 amination of quinoline N-oxides using our synthesized recyclable heterogeneous Cu–MnO catalyst has been reported here. Direct C[sbnd]H aminations of heterocyclic N-oxides with secondary amine were carried out under base, and ligand-free conditions in good to excellent yields. The major advantage is that air is used as a sole oxidant and our catalyst is recycled several times.
- Sahoo, Tapan,Thakur, Dinesh,Panda, Asit Baran,Ghosh, Subhash Chandra
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supporting information
(2021/09/29)
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- Cobalt-Catalyzed C8-Dienylation of Quinoline-N-Oxides
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An efficient Cp*CoIII-catalyzed C8-dienylation of quinoline-N-oxides was achieved by employing allenes bearing leaving groups at the α-position as the dienylating agents. The reaction proceeds by CoIII-catalyzed C?H activation of qui
- Khan, Salman,Nair, Akshay M.,Shukla, Rahul K.,Volla, Chandra M. R.
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supporting information
p. 17042 - 17048
(2020/08/05)
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- Cu-Catalyzed carbamoylation: Versus amination of quinoline N -oxide with formamides
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An efficient, direct carbamoylation and amination of quinoline N-oxides with formamides to access 2-carbamoyl and 2-amino quinolines has been developed through copper-catalyzed C-C and C-N bond formations via cross-dehydrogenative coupling reactions. The reaction proceeds smoothly over a broad range of substrates with excellent functional group tolerance under mild conditions. Mechanistic studies suggest that the reaction is initiated by formamide radical or decarbonylative aminyl radical formation in the presence of TBHP, according to the different substituent on the N atom of formamide.
- Zhang, Yan,Zhang, Shiwei,Xu, Guangxing,Li, Min,Tang, Chunlei,Fan, Weizheng
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supporting information
p. 309 - 314
(2019/01/10)
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- Visible-Light-Photocatalyzed Reductions of N-Heterocyclic Nitroaryls to Anilines Utilizing Ascorbic Acid Reductant
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A photoreductive protocol utilizing [Ru(bpy)3]2+ photocatalyst, blue light LEDs, and ascorbic acid (AscH2) has been developed to reduce nitro N-heteroaryls to the corresponding anilines. Based on experimental and computational results and previous studies, we propose that the reaction proceeds via proton-coupled electron transfer between AscH2, photocatalyst, and the nitro N-heteroaryl. The method offers a green catalytic procedure to reduce, e.g., 4-/8-nitroquinolines to the corresponding aminoquinolines, substructures present in important antimalarial drugs.
- Todorov, Aleksandar R.,Aikonen, Santeri,Muuronen, Mikko,Helaja, Juho
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supporting information
p. 3764 - 3768
(2019/05/24)
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- Catalyst-Free Synthesis of 2-Anilinoquinolines and 3-Hydroxyquinolines via Three-Component Reaction of Quinoline N-Oxides, Aryldiazonium Salts, and Acetonitrile
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A rapid microwave-assisted, catalyst-free, three-component synthesis of various 2-anilinoquinolines from quinoline N-oxides and aryldiazonium salts in acetonitrile under microwave irradiation is reported. This reaction utilizes acetonitrile as a single nitrogen source and involves the formation of two new C-N bonds via the formal [3 + 2] cycloaddition reaction. In the case of 2-substituted quinolines, 3-hydroxyquinoline was observed as the main product via a 1,3 shift of the oxygen atom from N-oxide to the C3 position of quinolines.
- Dhiman, Ankit Kumar,Chandra, Devesh,Kumar, Rakesh,Sharma, Upendra
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p. 6962 - 6969
(2019/06/14)
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- Method for synthesizing quinoline oxynitride from quinoline compound by ultrasonic-assisted oxidation
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The invention discloses a method for synthesizing quinoline oxynitride from a quinoline compound by ultrasonic-assisted oxidation. The quinoline compound and hydrogen peroxide are subjected to nitrogen oxidation reaction under the ultrasonic-assisted condition and perfluorosulfonic acid resin (Nafion-H) catalytic action to obtain quinoline oxynitride. The method has the advantages that the raw materials are easy to obtain, reaction conditions are simple and mild, greenness and energy conservation are achieved, and reaction selectivity and yield are high; energy is saved and the compatibility of substrate functional groups is excellent; in particular, the perfluorosulfonic acid resin can be recycled as an acid catalyst, so that not only is the reaction cost reduce, but also the reaction yield is increased, also the pollution problem in traditional oxidation reaction is avoided and a relatively high application value is achieved.
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Paragraph 0067; 0068; 0069
(2018/06/21)
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- RhIII-Catalyzed Direct C8-Arylation of Quinoline N-Oxides using Diazonaphthalen-2(1H)-ones: A Practical Approach towards 8-aza BINOL
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An efficient RhIII-catalyzed redox-neutral method for the direct C8-arylation of quinoline N-oxides using diazonaphthalen-2(1H)-one as coupling partner has been demonstrated. The developed method is simple, scalable and straightforward with a w
- Ghosh, Bidhan,Biswas, Aniruddha,Chakraborty, Soumen,Samanta, Rajarshi
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supporting information
p. 2388 - 2392
(2018/05/30)
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- Rhodium-Catalyzed Remote C-8 Alkylation of Quinolines with Activated and Unactivated Olefins: Mechanistic Study and Total Synthesis of EP4 Agonist
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Reported herein is a rhodium(III)-catalyzed regioselective distal C(sp2)-H bond alkylation of quinoline N-oxides using olefins as alkyl source and N-oxide as the traceless directing group. The reaction exhibits broad substrate scope with excellent selectivity for C-8 position and good yields of alkylated products. The usefulness of the developed catalytic protocol is established by synthesis of EP4 agonist. In mechanistic study, C-8 olefinated quinoline was identified as the reaction intermediate, which gets reduced to desired C-8 alkylated product in the presence of a rhodium(I) species (produced from rhodium(III) during reaction) and formic acid. Formic acid is produced from dimethylformamide in the presence of silver tetrafluoroborate. (Figure presented.).
- Sharma, Ritika,Kumar, Inder,Kumar, Rakesh,Sharma, Upendra
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supporting information
p. 3022 - 3028
(2017/09/08)
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- Synthesis of 2-Alkenylquinoline by Reductive Olefination of Quinoline N-Oxide under Metal-Free Conditions
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Synthesis of 2-alkenylquinoline by reductive olefination of quinoline N-oxide under metal-free conditions is disclosed. Practically, the reaction could be performed with quinoline as starting material via a one-pot, two-step process. A possible mechanism is proposed that involves a sequential 1,3-dipolar cycloaddition and acid-assisted ring opening followed by a dehydration process.
- Xia, Hong,Liu, Yuanhong,Zhao, Peng,Gou, Shaohua,Wang, Jun
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supporting information
p. 1796 - 1799
(2016/05/19)
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- Copper-catalyzed direct amination of quinoline N-oxides via C-H bond activation under mild conditions
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A highly efficient and concise one-pot strategy for the direct amination of quinoline N-oxides via copper-catalyzed dehydrogenative C-N coupling has been developed. The desired products were obtained in good to excellent yields for 22 examples starting from the parent aliphatic amines. This methodology provides a practical pathway to 2-aminoquinolines and features a simple system, high efficiency, environmental friendliness, low reaction temperature, and ligand, additives, base, and external oxidant free conditions.
- Zhu, Chongwei,Yi, Meiling,Wei, Donghui,Chen, Xuan,Wu, Yangjie,Cui, Xiuling
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supporting information
p. 1840 - 1843
(2014/05/06)
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- Development of luciferin analogues bearing an amino group and their application as BRET donors
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We systematically synthesized bioluminogenic substrates bearing an amino group on benzothiazole, quinoline, naphthalene, and coumarin scaffolds. They emit bioluminescence in various colors: red, orange, yellow, and green. An amino-substituted cou-marylluciferin derivative, coumarylami-noluciferin (CAL), showed the shortest bioluminescence wavelength among substrates reported so far. Further, the fluorescence of CAL did not exhibit solvatochromism, which suggests that its bioluminescence is not susceptible to environmental factors. We applied CAL as an energy-donor substrate for a bioluminescence resonance energy transfer (BRET) system with click beetle red luciferase (CBRluc), a mutant of firefly luciferase, as the energy-donor enzyme and yellow fluorescent protein (YFP) as the energy-acceptor fluorophore, and obtained a clearly bimodal bioluminescence spectrum. Stable bioluminescence that is not influenced by environmental factors is highly desirable for reliable measurements in biological assays.
- Takakura, Hideo,Sasakura, Kiyoshi,Ueno, Tasuku,Urano, Yasuteru,Terai, Takuya,Hanaoka, Kenjiro,Tsuboi, Takashi,Nagano, Tetsuo
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experimental part
p. 2053 - 2061
(2011/04/23)
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- NOVEL NITROGENATED HETEROCYCLIC COMPOUND AND SALT THEREOF
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A nitrogen-containing heterocyclic compound represented by the general formula: wherein the dashed line represents a single bond or a double bond; R1, R2, R3, R4 and R5 independently represent a hydrogen atom, halogen atom, a lower alkyl, aryl, lower alkoxy or monocyclic heterocyclic group which may be substituted or the like; R6 represents a lower alkyl, aryl, monocyclic heterocyclic, bicyclic heterocyclic or tricyclic heterocyclic group which may be substituted; X1 represents a lower alkylene group or the like; X2 represents a lower alkylene, lower alkenylene or lower alkynylene group which may be substituted; X3 represents an oxygen atom, sulfur atom, a sulfinyl group, sulfonyl group or the like; Y1 represents a bivalent cyclic group, containing a nitrogen, which may be substituted or the like; and Z1 represents a nitrogen atom, a carbon atom which may be substituted or the like, or a salt thereof. The compound or salt has a potent antibacterial activity and a high safety, and is therefore useful as an excellent antibacterial agent.
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Page/Page column 104
(2010/11/30)
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- Bicyclic modulators of androgen receptor function
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The invention provides for a pharmaceutical composition capable of modulating the androgen receptor comprising a compound of formula I wherein the substitutents are as described herein. Further provided are methods of using such compounds for the treatment of nuclear hormone receptor-associated conditions, such as age related diseases, for example sarcopenia. Also provided are pharmaceutical compositions containing such compounds and processes for preparing some of the compounds of the invention.
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- BICYCLIC MODULATORS OF ANDROGEN RECEPTOR FUNCTION
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The invention provides compounds according to formula I wherein the substitutents are as described herein. Further provided are methods of using such compounds for the treatment of nuclear hormone receptor-associated conditions, such as age related diseases, for example sarcopenia. Also provided are pharmaceutical compositions containing such compounds and processes for preparing some of the compounds of the invention.
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