- A metal-free aerobic oxidative bromination of anilines and aryl ketones with 2-methylpyridinium nitrate as a reusable ionic liquid
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An aerobic oxidative bromination of anilines and aryl ketones catalyzed by recyclable 2-methylpyridinium nitrate ionic liquid is achieved in water using hydrobromic acid as the bromine source and molecular oxygen as the oxidant. The catalytic system shows good efficiency and atom economy.
- Li, Ming-Fang,Wang, Jian,Ke, Yong-Xin,Pan, Song-Cheng,Yin, Hong,Du, Wenting,Li, Jing-Hua
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p. 267 - 270
(2020/01/08)
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- Nitromethane as a reagent for the synthesis of 3-nitroindoles from 2-haloarylamine derivatives
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A new approach to the synthesis of 3-nitroindoles using palladium-catalyzed arylation of nitromethane with N-(2-bromoaryl)imidates was developed. A convenient and rapid method for cyclization of ethyl N-(2-nitromethylaryl)acetimidates to 2-methyl-3-nitro-1H-indoles was proposed.
- Chesnokov,Ageshina,Maryanova,Rzhevskiy,Gribanov,Topchiy,Nechaev,Asachenko
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p. 2370 - 2377
(2020/12/31)
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- Making endo-cyclizations favorable again: A conceptually new synthetic approach to benzotriazoles via azide group directed lithiation/cyclization of 2-azidoaryl bromides
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Although benzotriazoles are important and ubiquitous, currently there is only one conceptual approach to their synthesis: bridging the two ortho-amino groups with an electrophilic nitrogen atom. Herein, we disclose a new practical alternative-the endo-cyclization of 2-azidoaryl lithiums obtained in situ from 2-azido-aryl bromides. The scope of the reaction is illustrated using twenty-four examples with a variety of alkyl, alkoxy, perfluoroalkyl, and halogen substituents. We found that the directing effect of the azide group allows selective metal-halogen exchange in aryl azides containing several bromine atoms. Furthermore, (2-bromophenyl)diazomethane undergoes similar cyclization to give an indazole. Thus, cyclizations of aryl lithiums containing an ortho-X = Y = Z group emerge as a new general approach for the synthesis of aromatic heterocycles. DFT computations suggested that the observed endo-selectivity applies to the anionic cyclizations of other functionalities that undergo "1,1-additions" (i.e., azides, diazo compounds, and isonitriles). In contrast, cyclizations with the heteroatomic functionalities that follow the "1,2-addition" pattern (cyanates, thiocyanates, isocyanates, isothiocyanates, and nitriles) prefer the exo-cyclization path. Hence, such reactions expand the current understanding of stereoelectronic factors in anionic cyclizations.
- Ageshina, Alexandra A.,Chesnokov, Gleb A.,Topchiy, Maxim A.,Alabugin, Igor V.,Nechaev, Mikhail S.,Asachenko, Andrey F.
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supporting information
p. 4523 - 4534
(2019/05/17)
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- Direct Synthesis of Structurally Divergent Indole Alkaloids from Simple Chemicals
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A direct and structurally divergent synthesis of indole alkaloids from very simple 2-vinylanilines, alkynes and TBN via a novel substrate fragmentation/cycloaddition strategy has been developed, which provides an efficient noble-metal-free approach to access a library of highly valuable indole derivatives of tryptamines and tryptamine-related oximes, lactams, and lactones, as well as β-carbolines, spiroindolines, and hexa-hydropyrrolo[2,3-b]indoles.
- Shen, Tao,Zhu, Bencong,Lin, Fengguirong,Pan, Jun,Wei, Jialiang,Luo, Xiao,Liu, Jianzhong,Jiao, Ning
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supporting information
p. 815 - 818
(2018/07/31)
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- Method for preparing o-haloaromaticamine from C-H-based activated arylamines
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The invention belongs to the technical field of organic chemistry and particularly relates to a method for preparing o-haloaromaticamine from C-H-based activated arylamines. The method comprises the following steps: taking anhydrous copper acetate as a reaction catalyst and hydrogen peroxide as an oxidizing agent, adding aniline compounds and potassium bromide or potassium iodide into water for reaction at room temperature for 2 h, extracting with ethyl acetate and concentrating under reduced pressure, so as to obtain a corresponding arylamine halogenated compound crude product; and performing column chromatographic isolation and purification to obtain a corresponding purified product. The method has the characteristics that the operation is simple, reaction conditions are mild, the reaction time is short, and the method is environment-friendly.
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Paragraph 0044; 0045; 0046; 0047; 0048
(2017/07/22)
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- A Molybdenum(0) Isocyanide Analogue of Ru(2,2′-Bipyridine)32+: A Strong Reductant for Photoredox Catalysis
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We report the first homoleptic Mo0complex with bidentate isocyanide ligands, which exhibits metal-to-ligand charge transfer (3MLCT) luminescence with quantum yields and lifetimes similar to Ru(bpy)32+(bpy=2,2′-b
- Büldt, Laura A.,Guo, Xingwei,Prescimone, Alessandro,Wenger, Oliver S.
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supporting information
p. 11247 - 11250
(2016/10/13)
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- Direct Tryptophols Synthesis from 2-Vinylanilines and Alkynes via C - C Triple Bond Cleavage and Dioxygen Activation
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An unexpected metal-free C - C triple bond cleavage, dioxygen activation, and reassembly into tryptophol derivatives has been developed. This chemistry provides a novel, simple, and efficient approach to highly valuable tryptophol derivatives from simple substrates under mild conditions. The mechanistic studies may promote the discovery of new methodologies through C-C bond cleavage and dioxygen activation.
- Shen, Tao,Zhang, Yiqun,Liang, Yu-Feng,Jiao, Ning
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supporting information
p. 13147 - 13150
(2016/10/24)
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- Copper-Promoted Tandem Reaction of Azobenzenes with Allyl Bromides via N=N Bond Cleavage for the Regioselective Synthesis of Quinolines
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A copper-promoted tandem reaction of a variety of azobenzenes and allyl bromides via N=N bond cleavage to regioselectively construct quinoline derivatives has been developed. The azobenzenes act as not only construction units but also an oxidant for quinoline formation.
- Yi, Xiangli,Xi, Chanjuan
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supporting information
p. 5836 - 5839
(2015/12/11)
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- Efficient and Practical Oxidative Bromination and Iodination of Arenes and Heteroarenes with DMSO and Hydrogen Halide: A Mild Protocol for Late-Stage Functionalization
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An efficient and practical system for inexpensive bromination and iodination of arenes as well as heteroarenes by using readily available dimethyl sulfoxide (DMSO) and HX (X = Br, I) reagents is reported. This mild oxidative system demonstrates a versatile protocol for the synthesis of aryl halides. HX (X = Br, I) are employed as halogenating reagents when combined with DMSO which participates in the present chemistry as a mild and inexpensive oxidant. This oxidative system is amenable to late-stage bromination of natural products. The kilogram-scale experiment (>95% yield) shows great potential for industrial application.
- Song, Song,Sun, Xiang,Li, Xinwei,Yuan, Yizhi,Jiao, Ning
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supporting information
p. 2886 - 2889
(2015/06/30)
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- Synthesis of 6-carboxylated phenanthridines by oxidative alkoxycarbonylation-cyclization of 2-isocyanobiphenyls with carbazates
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An iron-catalyzed synthesis of 6-carboxylated phenanthridines starting with readily prepared isocyanides and carbazates was developed. Reactions occurred via addition of alkoxycarbonyl radicals to the isocyanide group and subsequent intramolecular cyclization.
- Wang, Gao,Chen, Shan-Yong,Yu, Xiao-Qi
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supporting information
p. 5338 - 5341
(2015/01/09)
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- 1,7-palladium migration via C-H activation, followed by intramolecular amination: Regioselective synthesis of benzotriazoles
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A novel 1,7-palladiummigration-cyclization-dealkylation sequence for the regioselective synthesis of benzotriazoles has been developed. These reactions proceed in excellent yields with high regioselectivities. The mechanism of the reaction has also been investigated.
- Zhou, Jun,He, Jianjun,Wang, Binjie,Yang, Weijun,Ren, Hongjun
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supporting information; experimental part
p. 6868 - 6870
(2011/06/21)
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- Halogen substituted heteroatom-containing metallocene compounds for olefin polymerization
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Halogen substituted metallocene compounds are described and comprise one or more monocyclic or polycyclic ligands that are pi-bonded to the metal atom and include at least one halogen substituent directly bonded to an sp2 carbon atom at a bondable ring position of the ligand, wherein the or at least one ligand has one or more ring heteroatoms in its cyclic structure. When combined with a suitable activator, these compounds show activity in the polymerization of olefins, such as ethylene and propylene.
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Page/Page column 52-53; 54-55
(2010/11/27)
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- HALOGEN SUBSTITUTED METALLOCENE COMPOUNDS FOR OLEFIN POLYMERIZATION
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A metallocene compound is represented by the formula (1): AMXn-1 wherein M is a transition metal atom having a coordination number of n selected from Group 3, 4, 5 or 6 of the Periodic Table of Elements, or a lanthanide metal atom, or actinide metal atom; A is a substituted monocyclic or polycyclic arenyl ligand pi-bonded to M, wherein said arenyl ligand includes at least one halogen substituent directly bonded to any sp2 carbon atom at a bondable ring position of the ligand; and the or each X is a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.
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Page/Page column 123-124
(2010/11/27)
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- Halogen substituted metallocene compounds for olefin polymerization
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A metallocene compound is represented by the formula (1): [in-line-formulae]AMXn-1 [/in-line-formulae]wherein M is a transition metal atom having a coordination number of n selected from Group 3, 4, 5 or 6 of the Periodic Table of Elements, or a lanthanide metal atom, or actinide metal atom; A is a substituted monocyclic or polycyclic arenyl ligand pi-bonded to M, wherein said arenyl ligand includes at least one halogen substituent directly bonded to any sp2 carbon atom at a bondable ring position of the ligand; and the or each X is a univalent anionic ligand, or two X are joined and bound to the metal atom to form a metallocycle ring, or two X are joined to form a chelating ligand, a diene ligand, or an alkylidene ligand.
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- Discovery, Modeling, and Human Pharmacokinetics of N-(2-Acetyl-4,6-dimethylphenyl)-3-(3,4-dimethylisoxazol-5-ylsulfamoyl) -thiophene-2-carboxamide (TBC3711), a Second Generation, ETA Selective, and Orally Bioavailable Endothelin Antagonist
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Sitaxsentan (1) (Wu et al. J. Med. Chem. 1997, 40, 1690) is our first endothelin antagonist being evaluated in clinical trials. It has demonstrated biological effects in an acute hemodynamic study in CHF (Givertz et al. Circulation 2000, 101, 2922), an op
- Wu, Chengde,Decker, E. Radford,Blok, Natalie,Bui, Huong,You, Tony J.,Wang, Junmei,Bourgoyne, Andree R.,Knowles, Vippra,Berens, Kurt L.,Holland, George W.,Brock, Tommy A.,Dixon, Richard A. F.
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p. 1969 - 1986
(2007/10/03)
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- Halogenation Using Quaternary Ammonium Polyhalides. VI. Bromination of Aromatic Amines by Use of Benzyltrimethylammonium Tribromide
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The reaction of aromatic amines with benzyltrimethylammonium tribromide in dichloromethane-methanol containing calcium carbonate powder for 0.5 h at room temperature gave bromo-substituted aromatic amines in good yields.
- Kajigaeshi, Shoji,Kakinami, Takaaki,Inoue, Kazuhisa,Kondo, Manabu,Nakamura, Hiroko,et al.
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p. 597 - 599
(2007/10/02)
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