- Synthesis of a photostable near-infrared-absorbing photosensitizer for selective photodamage to cancer cells
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A new class of near-infrared (NIR)-absorptive (>900 nm) photosensitizer based on a phenothiazinium scaffold is reported. The stable solid compound, o-DAP, the oxidative form of 3,7-bis(4-methylaminophenyl)-10H-phenothiazine, can generate reactive oxygen species (ROS, singlet oxygen and superoxide) under appropriate irradiation conditions. After biologically evaluating the intracellular uptake, localization, and phototoxicity of this compound, it was concluded that o-DAP is photostable and a potential selective photodynamic therapy (PDT) agent under either NIR or white light irradiation because its photodamage is more efficient in cancer cells than in normal cells and is without significant dark toxicity. This is very rare for photosensitizers in PDT applications. Selective PDT agent: A photostable near-infrared (NIR)-absorptive phenothiazinium derivative, o-DAP, has been successfully synthesized and demonstrated to be a potential tumor-specific NIR-absorptive (>900 nm) photosensitizer for photodynamic therapy (PDT; see figure). This compound is expected to become a PDT reagent in a solar environment.
- Hsieh, Tung-Sheng,Wu, Jhen-Yi,Chang, Cheng-Chung
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Read Online
- A practical and scalable process for the preparation of 4-aminophenylboronic acid pinacol ester
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A practical process has been developed for scalable preparation of 4-aminophenylboronic acid pinacol ester through facile two-step procedure. After boron trifluoride etherate efficiently activated the reaction of 4-bromoaniline with diphenyl ketone, metalation reaction of protected 4-bromoaniline with lithium trialkylmagnesiate readily proceeded under mild conditions (-20 °C), which was subsequently subjected to esterification and deprotection reaction to give the 4-aminophenylboronic acid pinacol ester. The improved synthetic route has been successfully scaled up to kilogram quantities in good yield and high quality.
- Xue, Feng,Li, Chang-Gong,Zhu, Yong,Lou, Tian-Jun,He, Guang-Jie
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Read Online
- Terphenyl based 'Turn On' fluorescent sensor for mercury
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New terphenyl-based derivative 4 with pyrene as a fluorophore has been synthesized and examined for its cation recognition abilities toward various cations by NMR and fluorescence spectroscopy. The results show that it has very high binding affinity (log
- Bhalla, Vandana,Tejpal, Ruchi,Kumar, Manoj,Puri, Rajiv Kumar,Mahajan, Rakesh K.
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Read Online
- Palladium-catalyzed borylation of aryl bromides and chlorides using phosphatrioxa-adamantane ligands
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Catalysts based on the combination of Pd(OAc)2 and the electron-deficient phosphatrioxa-adamantane ligands are described for borylation of aryl bromides and chlorides. Catalytic evaluation of a small library of phosphatrioxa-adamantane ligands provided some insights on the preferred ligand steric profile for borylation reactions. The corresponding aryl boronate esters were accessed under mild conditions (25–70 °C) and isolated in high yields (up to 96%).
- Christopher Maumela, Munaka,Holzapfel, Cedric W.,Lamola, Jairus L.,Moshapo, Paseka T.
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supporting information
(2021/12/13)
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- Catalytic Boration of Alkyl Halides with Borane without Hydrodehalogenation Enabled by Titanium Catalyst
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An unprecedented and general titanium-catalyzed boration of alkyl (pseudo)halides (alkyl-X, X=I, Br, Cl, OMs) with borane (HBpin, HBcat) is reported. The use of titanium catalyst can successfully suppress the undesired hydrodehalogenation products that prevail using other transition-metal catalysts. A series of synthetically useful alkyl boronate esters are readily obtained from various (primary, secondary, and tertiary) alkyl electrophiles, including unactivated alkyl chlorides, with tolerance of other reducing functional groups such as ester, alkene, and carbamate. Preliminary studies on the mechanism revealed a possible radical reaction pathway. Further extension of our strategy to aryl bromides is also demonstrated.
- Wang, Xianjin,Cui, Penglei,Xia, Chungu,Wu, Lipeng
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supporting information
p. 12298 - 12303
(2021/05/07)
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- Preparation method of aryl borate catalyzed by cesium neovalerate
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The preparation method comprises the following steps: dissolving a compound of formula (I) and a diboron compound in an organic solvent, then adding an organic solvent dissolved with cesium neovalerate, palladium acetate and triphenylphosphine, and carrying out reaction to obtain aryl boronic acid ester. In the formula (I) R1. R2, R3, R4 and R5 are each independently selected from H, C. 1 - C10 Alkyl group, C2 - C10 Alkenyl, C2 - C10 Alkynyl group, C1 - C10 Alkoxy, hydroxy, hydroxy-substituted C1 - C10 Alkyl, phenyl, C1 - C10 Alkylamino. X Is selected from F, Cl, Br, i. The preparation method has the advantages of low production cost, high product yield, high purity, simple operation and suitability for industrial mass production.
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Paragraph 0054-0057
(2021/09/22)
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- Discovery of pyrrolo[2,3-d]pyrimidine derivatives as potent Axl inhibitors: Design, synthesis and biological evaluation
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Axl has emerged as an attractive target for cancer therapy due to its strong correlation with tumor growth, metastasis, poor survival, and drug resistance. Herein, we report the design, synthesis and structure-activity relationship (SAR) investigation of a series of pyrrolo[2,3-d]pyrimidine derivatives as new Axl inhibitors. Among them, the most promising compound 13b showed high enzymatic and cellular Axl potencies. Furthermore, 13b possessed preferable pharmacokinetic properties and displayed promising therapeutic effect in BaF3/TEL-Axl xenograft tumor model. Compound 13b may serve as a lead compound for new antitumor drug discovery.
- Xu, Dandan,Sun, Deqiao,Wang, Wei,Peng, Xia,Zhan, Zhengsheng,Ji, Yinchun,Shen, Yanyan,Geng, Meiyu,Ai, Jing,Duan, Wenhu
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- Photo-induced thiolate catalytic activation of inert Caryl-hetero bonds for radical borylation
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Substantial effort is currently being devoted to obtaining photoredox catalysts with high redox power. Yet, it remains challenging to apply the currently established methods to the activation of bonds with high bond dissociation energy and to substrates with high reduction potentials. Herein, we introduce a novel photocatalytic strategy for the activation of inert substituted arenes for aryl borylation by using thiolate as a catalyst. This catalytic system exhibits strong reducing ability and engages non-activated Caryl–F, Caryl–X, Caryl–O, Caryl–N, and Caryl–S bonds in productive radical borylation reactions, thus expanding the available aryl radical precursor scope. Despite its high reducing power, the method has a broad substrate scope and good functional-group tolerance. Spectroscopic investigations and control experiments suggest the formation of a charge-transfer complex as the key step to activate the substrates.
- K?nig, Burkhard,Wang, Hua,Wang, Shun
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supporting information
p. 1653 - 1665
(2021/06/17)
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- Recyclable Pd2dba3/XPhos/PEG-2000 System for Efficient Borylation of Aryl Chlorides: Practical Access to Aryl Boronates
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Pd2dba3/XPhos in poly(ethylene glycol) (PEG-2000) is shown to be a highly stable and efficient catalyst for the borylation of aryl chlorides with bis(pinacolato)diboron. The borylation reaction proceeds smoothly at 110 °C, delivering a wide variety of aryl boronates in good to excellent yields with high functional group tolerance. The crude products were easily isolated via simple extraction of the reaction mixture with cyclohexane. Moreover, both expensive Pd2dba3 and XPhos in PEG-2000 system could be readily recycled and reused more than six times without loss of catalytic efficiency.
- Cai, Mingzhong,Huang, Bin,Luo, Chengkai,Xu, Caifeng
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- Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
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Transition metal catalysis that utilizes N-heterocyclic carbenes as noninnocent ligands in promoting transformations has not been well studied. We report here a cyclic (alkyl)(amino)carbene (CAAC) ligand-promoted nitro deoxygenative hydroboration with cost-effective chromium catalysis. Using 1 mol % of CAAC-Cr precatalyst, the addition of HBpin to nitro scaffolds leads to deoxygenation, allowing for the retention of various reducible functionalities and the compatibility of sensitive groups toward hydroboration, thereby providing a mild, chemoselective, and facile strategy to form anilines, as well as heteroaryl and aliphatic amine derivatives, with broad scope and particularly high turnover numbers (up to 1.8 × 106). Mechanistic studies, based on theoretical calculations, indicate that the CAAC ligand plays an important role in promoting polarity reversal of hydride of HBpin; it serves as an H-shuttle to facilitate deoxygenative hydroboration. The preparation of several commercially available pharmaceuticals by means of this strategy highlights its potential application in medicinal chemistry.
- Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
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supporting information
p. 1618 - 1629
(2021/01/25)
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- Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis
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The development of chemoselective and heterogeneous earth-abundant metal catalysts is essential for environmentally friendly chemical synthesis. We report a highly efficient, chemoselective, and reusable single-site nickel(II) hydride catalyst based on robust and porous aluminum metal-organic frameworks (MOFs) (DUT-5) for hydrogenation of nitro and nitrile compounds to the corresponding amines and hydrogenolysis of aryl ethers under mild conditions. The nickel-hydride catalyst was prepared by the metalation of aluminum hydroxide secondary building units (SBUs) of DUT-5 having the formula of Al(μ2-OH)(bpdc) (bpdc = 4,4′-biphenyldicarboxylate) with NiBr2 followed by a reaction with NaEt3BH. DUT-5-NiH has a broad substrate scope with excellent functional group tolerance in the hydrogenation of aromatic and aliphatic nitro and nitrile compounds under 1 bar H2 and could be recycled and reused at least 10 times. By changing the reaction conditions of the hydrogenation of nitriles, symmetric or unsymmetric secondary amines were also afforded selectively. The experimental and computational studies suggested reversible nitrile coordination to nickel followed by 1,2-insertion of coordinated nitrile into the nickel-hydride bond occurring in the turnover-limiting step. In addition, DUT-5-NiH is also an active catalyst for chemoselective hydrogenolysis of carbon-oxygen bonds in aryl ethers to afford hydrocarbons under atmospheric hydrogen in the absence of any base, which is important for the generation of fuels from biomass. This work highlights the potential of MOF-based single-site earth-abundant metal catalysts for practical and eco-friendly production of chemical feedstocks and biofuels.
- Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Dwivedi, Ashutosh,Manna, Kuntal
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p. 3943 - 3957
(2021/04/12)
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- Synthesis, crystal structure and DFT study of a novel compound N-(4-(2,4-dimorpholinopyrido[2,3-d]pyrimidin-6-yl)phenyl)pyrrolidine-1-carboxamide
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In this paper, the compound N-(4-(2,4-dimorpholinopyrido[2,3-d]pyrimidin-6-yl)phenyl) pyrrolidine-1-carboxamide was synthesized and characterized using 13C NMR, 1H NMR, FT-IR and MS as well as by a single crystal X-ray structural analysis. Additionally, the structure of the single crystal was confirmed using X-ray diffraction. The packing of the molecules in the solid state is dominated by hydrogen bonds. The optimized structure of the compound was computed via DFT using the B3LYP functional with the 6-311G(2d, p) as basis set and compared with that determined using X-ray diffraction. The results show that the crystal structure confirmed using X-ray diffraction is consistent with the molecular structure optimized using DFT. In addition, the anti-proliferative activity of the title compound on A375 cells was studied, and the inhibition rate at a concentration of 5 μM was 12.89%. Furthermore, molecular docking was performed to analyze the binding mode of the title compound with PI3Kγ.
- Zhou, Zhixu,Liu, Ye,Ren, Qian,Yu, Dehou,Lu, Hongguang
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- Method for preparing amine through catalytic reduction of nitro compound by cyclic (alkyl) (amino) carbene chromium complex
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The cyclic (alkyl) (amino) carbene chromium complex is prepared from corresponding ligand salt, alkali and CrCl3 and used for catalyzing pinacol borane to reduce nitro compounds in an ether solvent under mild conditions to generate corresponding amine. The method for preparing amine has the advantages of cheap and accessible raw materials, mild reaction conditions, wide substrate application range, high selectivity and the like, and is simple to operate.
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Paragraph 0015
(2021/04/17)
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- PERK INHIBITING IMIDAZOLOPYRAZINE COMPOUNDS
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Provided herein are compounds of formula (I) as shown below, compositions, and methods useful for inhibiting PERK and for treating related conditions, diseases, and disorders.
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Paragraph 0142; 0143; 0144
(2021/03/05)
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- PERK INHIBITING PYRROLOPYRIMIDINE COMPOUNDS
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Provided herein are compounds of formula (I), compositions, and methods useful for inhibiting PERK and for treating related conditions diseases, and disorders.
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Paragraph 0136; 0137; 0138
(2021/03/05)
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- PERK INHIBITING COMPOUNDS
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Provided herein are compounds of formula (I), compositions, and methods useful for inhibiting PERK and for treating related conditions, diseases, and disorders.
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Paragraph 0135-0137
(2021/03/05)
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- PERK INHIBITING PYRROLOPYRIMIDINE COMPOUNDS TO TREAT VIRAL INFECTIONS
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Provided herein are methods for treating a viral infection in a patient, comprising administering to said patient a therapeutically effective amount of a PERK inhibitor selected from a compound having the structure (I):
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Page/Page column 54-56
(2021/11/20)
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- PERK INHIBITORS FOR TREATING VIRAL INFECTIONS
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Provided herein are methods for treating a viral infection in a patient, comprising administering to said patient a therapeutically effective amount of a PERK inhibitor selected from a compound having the structure (I):
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Page/Page column 66; 67
(2021/11/20)
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- PERK INHIBITING IMIDAZOLOPYRAZINE COMPOUNDS
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Provided herein are methods for treating a viral infection in a patient, comprising administering to said patient a therapeutically effective amount of a PERK inhibitor selected from a compound having the structure (I).
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Page/Page column 67-68
(2021/11/20)
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- Visible Light-Induced Borylation of C-O, C-N, and C-X Bonds
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Boronic acids are centrally important functional motifs and synthetic precursors. Visible light-induced borylation may provide access to structurally diverse boronates, but a broadly efficient photocatalytic borylation method that can effect borylation of a wide range of substrates, including strong C-O bonds, remains elusive. Herein, we report a general, metal-free visible light-induced photocatalytic borylation platform that enables borylation of electron-rich derivatives of phenols and anilines, chloroarenes, as well as other haloarenes. The reaction exhibits excellent functional group tolerance, as demonstrated by the borylation of a range of structurally complex substrates. Remarkably, the reaction is catalyzed by phenothiazine, a simple organic photocatalyst with MW 200 that mediates the previously unachievable visible light-induced single electron reduction of phenol derivatives with reduction potentials as negative as approximately - 3 V versus SCE by a proton-coupled electron transfer mechanism. Mechanistic studies point to the crucial role of the photocatalyst-base interaction.
- Arman, Hadi D.,Dang, Hang. T.,Haug, Graham C.,He, Ru,Jin, Shengfei,Larionov, Oleg V.,Nguyen, Viet D.,Nguyen, Vu T.,Schanze, Kirk S.
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supporting information
(2020/02/04)
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- WEE1 inhibitors as well as preparation and application thereof
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The invention relates to WEE1 inhibitors as well as preparation and application thereof. The present invention relates to compounds of formula (I), or pharmaceutically acceptable salts, solvates, polymorphs or isomers thereof, and their use in the preparation of medicaments for the treatment of diseases associated with WEE1 activity.
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Paragraph 0875-0881
(2020/10/14)
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- Photocatalytic C–X borylation of aryl halides by hierarchical SiC nanowire-supported Pd nanoparticles
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Hierarchical SiC nanowire-supported Pd nanoparticles showed high photocatalytic activity for the C-X (X = Br, I) borylation of aryl halides at 30 °C. The SiC/Pd Mott-Schottky contact enhances the rapid transfer of the photogenerated electrons from SiC to the Pd nanoparticles. As a result, the concentrated energetic electrons in the Pd nanoparticles can facilitate the cleavage of C-I or C-Br bonds, which normally requires high-temperature thermal processes. We show that the present Pd/SiC photocatalyst is capable of catalyzing the transformation of a large variety of aryl halides to their corresponding boronate esters under visible light irradiation, with excellent yields.
- Jiao, Zhi-Feng,Zhao, Ji-Xiao,Guo, Xiao-Ning,Guo, Xiang-Yun
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p. 357 - 363
(2019/12/28)
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- Novel 3-(substituted amino)-6-alkyl-pyrazine-2-carboxamide derivatives and use thereof
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A novel 3 -6 - alkyl-pyrazine -2 - carboxamide derivative or a pharmaceutically acceptable salt thereof. A pharmaceutical composition for preventing or treating MerTTK-related diseases and a method for preventing or treating MerTTK-related diseases contains the same as an active ingredient.
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Paragraph 0228-0233
(2021/01/08)
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- Visible-Light-Induced Organocatalytic Borylation of Aryl Chlorides
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The preparation of arylboronates from unactivated aryl chlorides in a transition-metal-free manner is rather challenging. There are only few examples to achieve this goal by using ultraviolet irradiation. Based on the mechanistic understanding of the diboron/methoxide/pyridine reaction system, we achieved photoactivation of the in situ generated super electron donor and developed a visible-light-induced organocatalytic method for efficient borylation of unactivated aryl chlorides.
- Zhang, Li,Jiao, Lei
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supporting information
p. 9124 - 9128
(2019/06/17)
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- Para-Selective C-H Borylation of Common Arene Building Blocks Enabled by Ion-Pairing with a Bulky Countercation
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The selective functionalization of C-H bonds at the arene para position is highly challenging using transition metal catalysis. Iridium-catalyzed borylation has emerged as a leading technique for arene functionalization, but there are only a handful of strategies for para-selective borylation, which operate on specific substrate classes and use bespoke ligands or catalysts. We describe a remarkably general protocol which results in para-selectivity on some of the most common arene building blocks (anilines, benzylamines, phenols, benzyl alcohols) and uses standard borylation ligands. Our strategy hinges upon the facile conversion of the substrates into sulfate or sulfamate salts, wherein the anionic arene component is paired with a tetrabutylammonium cation. We hypothesize that the bulk of this cation disfavors meta-C-H borylation, thereby promoting the challenging para-selective reaction.
- Mihai, Madalina T.,Williams, Benjamin D.,Phipps, Robert J.
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p. 15477 - 15482
(2019/10/11)
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- Copper-Photocatalyzed Borylation of Organic Halides under Batch and Continuous-Flow Conditions
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The copper-photocatalyzed borylation of aryl, heteroaryl, vinyl and alkyl halides (I and Br) was reported. The reaction proceeded using a new heteroleptic Cu complex under irradiation with blue LEDs, giving the corresponding boronic-acid esters in good to excellent yields. The reaction was extended to continuous-flow conditions to allow an easy scale-up. The mechanism of the reaction was studied and a mechanism based on a reductive quenching (CuI/CuI*/Cu0) was suggested.
- Nitelet, Antoine,Thevenet, Damien,Schiavi, Bruno,Hardouin, Christophe,Fournier, Jean,Tamion, Rodolphe,Pannecoucke, Xavier,Jubault, Philippe,Poisson, Thomas
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supporting information
p. 3262 - 3266
(2019/02/13)
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- MECHANICALLY SHAPED 2-DIMENSIONAL COVALENT ORGANIC FRAMEWORKS
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Covalent organic frameworks (COFs) usually crystallize as insoluble powders and their processing for suitable devices has been thought to be limited. Here, it is demonstrated that COFs can be mechanically pressed into shaped objects having anisotropic ordering with preferred orientation between the hk0 and 00/ crystallographic planes. Pellets prepared from bulk COF powders impregnated with LiC1O4 displayed room temperature conductivity up to 0.26 mS cm-1 and stability up to 10.0 V (vs. Li+/Li0). This outcome portends use of COFs as solid-state electrolytes in batteries.
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Page/Page column 26-27
(2018/02/28)
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- Framework: Vs. side-chain amphidynamic behaviour in oligo-(ethylene oxide) functionalised covalent-organic frameworks
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We present a family of covalent organic frameworks that have been functionalized with oligo-(ethylene oxide) chains of varying lengths. Because of the open structure of the COFs, the side chains do not interfere with their crystallization obtaining materials with predictable crystal structure. The difference in length of the side-chains allowed for the determination of amphidynamic behaviour with the use of 13C solid-state NMR relaxation methods. Computational calculations further contribute to understanding the atomistic dynamic behaviour of the different atoms. This study demonstrates the ability to design complex behaviour in organic crystals.
- Vazquez-Molina, Demetrius A.,Pope, Giovanna M.,Ezazi, Andrew A.,Mendoza-Cortes, Jose L.,Harper, James K.,Uribe-Romo, Fernando J.
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supporting information
p. 6947 - 6950
(2018/06/26)
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- Gated photochromism in azobenzene-appended rhodamine cassette: Through-bond energy transfer-a universal strategy towards "lock and Unlock" system
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A dyad 1 comprising fluorescent rhodamine and photochromic azobenzene covalently linked through a phenylene bridge, which still retains their individual electronic properties, was synthesized. Gating between the fluorescent and photochromic properties of the dyad in the presence of external stimuli such as light or cations/anions or both paved the way for the development of new stimuli-responsive molecular materials. Among the several metal ions, Fe3+ ion was found to be selective in inducing the spirocyclic ring opening reaction of rhodamine, which can be witnessed through turn-on fluorescence. Fe3+-bound dyad 1 precluded the traditional trans → cis isomerization of remotely connected azobenzene and catalysed the spirocyclic ring opening reaction, which led to fluorescence enhancement by a factor of 640. The fluorescence enhancement originated from through-bond energy transfer upon excitation of azobenzene. Indeed, the turn-on fluorescence and optical changes upon UV irradiation indicated that this material can be used as a probe to monitor harmful UV radiation. The distinctly different responses of 1 concerning physical stimuli (light) and chemical stimuli (Fe3+ and F- ions) make this molecule a multi-addressable functional material.
- Raman, Arunachalam,Augustine, George,Ayyadurai, Niraikulam,Easwaramoorthi, Shanmugam
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supporting information
p. 10497 - 10501
(2018/10/24)
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- Pd II -Porphyrin Complexes - The First Use as Safer and Efficient Catalysts for Miyaura Borylation
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We have developed a simple and convenient procedure for the preparation of pinacol arylboronates from aryl/heteroaryl bromides and bis(pinacolato)diborane using a Pd II -porphyrin complex as a catalyst. Seven different Pd II -porphyrin complexes (Pd II -T m HPP, Pd II -T m CPP, Pd II -TPP, Pd II -TST p SPP, Pd II -T p CPP, Pd II -T p TP, and Pd II -T p AP) have been synthesized and investigated for their catalytic influence in the Miyaura borylation.
- Rao, Kanusu Umamaheswara,Venkateswarlu, Katta
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supporting information
p. 1055 - 1060
(2018/03/23)
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- Discovery and evaluation of 3,5-disubstituted indole derivatives as Pim kinase inhibitors
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Pim kinases are promising therapeutic targets for the treatment of hematological cancers. A potent Pim kinase inhibitor 7f, derived from meridianin C, was further optimized by the replacement of 2-aminopyrimidine with substituted benzene. The optimization of the C-3 and C-5 positions of indole yielded compound 43 with improved cellular potency and high selectivity against a panel of 14 different kinases.
- More, Kunal N.,Hong, Victor S.,Lee, Ahyeon,Park, Jongsung,Kim, Shin,Lee, Jinho
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supporting information
p. 2513 - 2517
(2018/06/06)
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- Cobalt-Catalyzed C-F Bond Borylation of Aryl Fluorides
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A mild and practical cobalt-catalyzed defluoroborylation of fluoroarenes is presented for the first time. The method permits straightforward functionalization of fluoroarenes, with high selectivity for borylation of C-F over C-H bonds, and a tolerance for aerobic conditions. Furthermore, two-step 18F-fluorination was achieved for expanding the scope of 18F-positron emission tomography probes.
- Lim, Soobin,Song, Dalnim,Jeon, Seungwon,Kim, Youngsuk,Kim, Hyunseok,Lee, Sanghee,Cho, Hyungdo,Lee, Byung Chul,Kim, Sang Eun,Kim, Kimoon,Lee, Eunsung
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supporting information
p. 7249 - 7252
(2018/11/23)
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- LiHMDS-Promoted Palladium or Iron-Catalyzed ipso-Defluoroborylation of Aryl Fluorides
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A novel and efficient method for the synthesis of arylboronic acid pinacol esters via a palladium- or iron-catalyzed cross-coupling reaction of aryl fluorides with bis(pinacolato)diboron (B2pin2) in the presence of LiHMDS was developed. The Pd-catalyzed defluoroborylation of fluoroarenes is compatible with a variety of functional groups such as primary and secondary amine, ketone, trifluoromethyl, alkoxy, and boryl. Remarkably, no external ligand is required for enhanced conversion efficiency.
- Zhao, Xianghu,Wu, Mingsheng,Liu, Yisen,Cao, Song
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supporting information
p. 5564 - 5568
(2018/09/12)
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- Achieving High Ortho Selectivity in Aniline C-H Borylations by Modifying Boron Substituents
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High ortho selectivity for Ir-catalyzed C-H borylations (CHBs) of anilines results when B2eg2 (eg = ethylene glycolate) is used as the borylating reagent in lieu of B2pin2, which is known to give isomeric mixtures with anilines lacking a blocking group at the 4-position. With this modification, high selectivities and good yields are now possible for various anilines, including those with groups at the 2- and 3-positions. Experiments indicate that ArylN(H)Beg species are generated prior to CHB and support the improved ortho selectivity relative to B2pin2 reactions arising from smaller Beg ligands on the Ir catalyst. The lowest-energy transition states (TSs) from density functional theory computational analyses have N-H···O hydrogen-bonding interactions between PhN(H)Beg and O atoms in Beg ligands. Ir-catalyzed CHB of PhN(H)Me with B2eg2 is also highly ortho-selective. 1H NMR experiments show that N-borylation fully generates PhN(Me)Beg prior to CHB. The TS with the lowest Gibbs energy was the ortho TS, in which the Beg unit is oriented anti to the bipyridine ligand.
- Smith, Milton R.,Bisht, Ranjana,Haldar, Chabush,Pandey, Gajanan,Dannatt, Jonathan E.,Ghaffari, Behnaz,Maleczka, Robert E.,Chattopadhyay, Buddhadeb
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p. 6216 - 6223
(2018/05/23)
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- Simple Nickel Salts for the Amination of (Hetero)aryl Bromides and Iodides with Lithium Bis(trimethylsilyl)amide
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Recent developments in the chemistry of C-N bond formation and the synthesis of anilines have allowed for the use of first-row transition metals to catalyze these transformations. Much of the progress in this area has been driven by comprehensive screening for privileged/tailored ligands, which can be costly and not readily available in a research laboratory setting. In this communication we report a protocol in which simple nickel salts catalyze the C-N cross-coupling reaction between (hetero)aryl bromides and iodides with lithium bis(trimethylsilyl)amide without the need for any additive ligand. This method is amenable to low nickel catalyst loadings (1%) as well as gram-scale reactions. Because of the good functional group tolerance and compatibility with heterocyclic moieties, this method is useful for academic laboratory settings where access to tailored ligands and noble-metal catalysts could be challenging.
- Martinez, Gabriel Espinosa,Nugent, Joseph W.,Fout, Alison R.
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supporting information
p. 2941 - 2944
(2018/09/21)
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- Efficient Synthesis of Aryl Boronates via Cobalt-Catalyzed Borylation of Aryl Chlorides and Bromides
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An efficient catalytic system based on a Co(II)-NHC precursor has been developed for the cross coupling of bis(pinacolato)diboron with aryl halides including aryl chlorides, affording the aryl boronates in good to excellent yields. A wide range of functional groups are tolerated under mild reaction conditions. The reaction shows excellent chemoselectivity for bromide over chloride. Preliminary mechanistic investigations show that the catalytic cycle may rely on a cobalt(I)-(III) redox couple.
- Verma, Piyush Kumar,Mandal, Souvik,Geetharani
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p. 4049 - 4054
(2018/05/22)
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- Photoinitiated long-lived charge separation with near-unity quantum yield in donor-acceptor1-acceptor2 systems for artificial photosynthesis
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We report the synthesis and photophysical characterization of isomeric donor-acceptor1-acceptor2 (D-A1-A2) triads each comprising a perylene donor (D) connected by a xylene bridge to a naphthalene-1,8-dicarboximide primary acceptor (NMI, A1) that is, in turn, covalently linked to a naphthalene-1,4:5,8-bis(dicarboximide) secondary acceptor (NDI, A2) through a benzene ring at its ortho, meta or para positions (Per-Xy-NMI-x-NDI). Selective photoexcitation of Per produces both Per+? and NDI?? simultaneously with time constants of ~50 ps in benzonitrile and ~80 ps in toluene with a >98% yield. This is much faster than expected for single-step electron transfer from 1*Per to NDI and is consistent with a two-step mechanism, 1*Per-Xy-NMI-x-NDI → Per+?-Xy-NMI??-x-NDI → Per+?-Xy-NMI-x-NDI??, in which the second step is much faster than the first step. In addition, preserving long-lived charge separation in these systems is found to depend on inhibiting charge recombination by a triplet radical ion pair recombination pathway.
- Han, Won-Sik,Veldkamp, Brad S.,Dyar, Scott M.,Eaton, Samuel W.,Wasielewski, Michael R.
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p. 4925 - 4935
(2017/07/27)
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- BIARYL DERIVATIVE AS GPR120 AGONIST
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The present invention relates to a biaryl derivative expressed by the chemical formula 1, a method for producing the biaryl derivative, a pharmaceutical composition comprising same, and use of same, the biaryl derivative expressed by the chemical formula 1, as a GPR120 agonist, promoting GLP-1 generation in the gastro-intestinal tract, reducing insulin resistance in the liver, muscles and the like from anti-inflammatory activity in the macrophage, pancreatic cells and the like, and allowing effective use in prevention or treatment of inflammation or metabolic diseases such as diabetes, complications from diabetes, obesity, non-alcoholic fatty liver disease, fatty liver disease, and osteoporosis.
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Paragraph 0536
(2017/11/17)
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- NOVEL COMPOUNDS AS GPR119 AGONISTS
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The present invention relates to novel compounds of formula (I) as GPR119 agonist, composition compositions containing such compounds and method of preparation thereof.
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Paragraph 0445-0447
(2017/10/26)
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- Highly solvatochromic fluorescence of anthraquinone dyes based on triphenylamines
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Five donor-acceptor anthraquinone dyes based on phenylamine/triphenylamines with different substituted groups were synthesized by Suzuki reaction in good yields, and the photophysical properties were studied in organic solvents with different polarity. The title dyes exhibited remarkable solvatochromic fluorescence (>190 nm emission shift in polar media), which was derived from intramolecular charge transfer (ICT) character that revealed by DFT/TD-DFT calculation. And large Stokes shifts (210–306 nm) were observed in different organic solvents, along with rich color changes from blue to green, yellow, orange and even purple-red. The Stokes shifts were linearly dependent on the solvent polarity function ET(30). Interestingly, it was found from the single-crystal X-ray diffraction analysis that dye 3 displayed two different interleaved channel structures, which was seldom seen in organic compounds and could be used as host for complexation potentially. Electrochemical characterization suggested that the different substituted phenylamine groups attached to anthraquinone unit could lead to tunable potentials and energy levels.
- Li, Yanxia,Tan, Tingfeng,Wang, Shirong,Xiao, Yin,Li, Xianggao
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p. 262 - 270
(2017/06/05)
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- A synthetic amino acid frequency that alcohol ester
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The invention relates to a method of synthesizing aminophenylboronic acid pinacol ester. The method includes subjecting bromoaniline having different substitute positions to silanization protection, reacting with magnesium metal or butyl lithium, and performing boronization/deprotection/esterification to obtain a product. Raw materials and agents, which are adopted in the method, are cheap and easily available. Reaction conditions are mild. Only simple treatment is needed after a reaction in each step is finished. The method is capable of continuous operation. The total yield is 40-55%. The purity of the product is high. The method is suitable for large-scale amplification production.
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Paragraph 0046; 0047; 0048; 0049
(2017/08/25)
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- Rhodium-Catalyzed Decarbonylative Borylation of Aromatic Thioesters for Facile Diversification of Aromatic Carboxylic Acids
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Transformation of aromatic thioesters into arylboronic esters was achieved efficiently using a rhodium catalyst. The broad functional-group tolerance and mild conditions of the method have allowed for the two-step decarboxylative borylation of a wide range of aromatic carboxylic acids, including commercially available drugs.
- Ochiai, Hidenori,Uetake, Yuta,Niwa, Takashi,Hosoya, Takamitsu
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p. 2482 - 2486
(2017/02/23)
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- Radical Metal-Free Borylation of Aryl Iodides
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A simple metal-free borylation of aryl iodides mediated by a fluoride sp 2 -sp 3 diboron adduct is described. The reaction conditions are compatible with various functional groups. Electronic effects of substituents do not affect the borylation while steric hindrance does. The reaction proceeds via a radical mechanism in which pyridine serves to stabilize the boryl radicals, generated in situ.
- Pinet, Sandra,Liautard, Virginie,Debiais, Mégane,Pucheault, Mathieu
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p. 4759 - 4768
(2017/10/03)
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- Under the mellow promotion aromatic amine boronise produced by the reaction of an aryl boronic acid and aryl borate method
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The invention discloses a method for preparation of aryl boronic acid and aryl borate by alcohol-promoted boronation reaction of aromatic amine, the aromatic amine which is easy to get and cheap is used as a raw material, a diboron compound is used as a boron source, a nitrite is used as a diazotization reagent, and the aryl boronic acid and aryl borate are obtained by alcohol-promoted reaction at room temperature in no presence of a catalyst. The method has the advantages of simple operation, mild reaction conditions, no presence of a metal catalyst, reduction of the production cost, high product yield, tolerance to different functional groups on aryl, and a wide adaptive range.
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Paragraph 0028; 0045-0048
(2017/08/25)
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- Cobalt-catalyzed borylation of aryl halides and pseudohalides
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We report the first Co-catalyzed borylation of aryl halides and pseudohalides with bis(pinacolato)diboron (B2pin2). The synthesis of two new Co(II) complexes of oxazolinylferrocenylphosphine ligands is described. Upon activation with LiMe, the Co complex catalyzes the borylation reactions of aryl bromides, iodides, sulfonates, arenediazonium salts, and even aryl chlorides under mild conditions, providing the borylated products in excellent to moderate yields and with high functional group tolerance.
- Yao, Wubing,Fang, Huaquan,Peng, Sihan,Wen, Huanan,Zhang, Lei,Hu, Aiguo,Huang, Zheng
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supporting information
p. 1559 - 1564
(2016/06/09)
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- 2-Aryl-indenylphosphine ligands: Design, synthesis and application in Pd-catalyzed Suzuki-Miyaura coupling reactions
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A focused library of phosphine ligands was constructed for structural optimization. The catalyst can be used to perform the Suzuki-Miyaura cross-coupling reaction of aryl and heteroaryl chlorides.
- Lian, Ze-Yu,Yuan, Jia,Yan, Meng-Qi,Liu, Yan,Luo, Xue,Wu, Qing-Guo,Liu, Sheng-Hua,Chen, Jian,Zhu, Xiao-Lei,Yu, Guang-Ao
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supporting information
p. 10090 - 10094
(2016/11/06)
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- Diarylurea compound with antitumor activity, and preparation method and application thereof
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The invention provides a diarylurea compound with antitumor activity, and a preparation method and application thereof. The compound has a structural formula as described in the specification. In the structural formula, R1 and R2 are selected from the group consisting of hydrogen, alkane groups or halogen groups. The compound provided by the invention has good inhibitory activity to VEGFR-2 kinase, so a signal channel induced by the VEGFR-2 kinase can be blocked through inhibition of the activity of the VEGFR-2 kinase, and proliferation and migration of tumor cells are inhibited; thus, the compound can be applied in preparation of antitumor drugs. Meanwhile, the preparation method for the compound has the following advantages: raw materials are easily available; reaction conditions are mild; the process of reaction is simple to operate; and used reagents are cheap.
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Paragraph 0033-0036
(2017/07/19)
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- Nickel-Catalyzed Borylation of Aryl- and Benzyltrimethylammonium Salts via C-N Bond Cleavage
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By developing a mild Ni-catalyzed system, a method for direct borylation of sp2 and sp3 C-N bonds has been established. The key to this hightly efficient C-N bond borylative cleavage depends on the appropriate choice of the nickel catalyst Ni(COD)2, ICy·HCl as a ligand, and the use of 2-ethoxyethanol as the cosolvent. This transformation shows good functional group compatibility and can serve as a powerful synthetic tool for gram-scale synthesis and late-stage C-N borylation of complex compounds.
- Hu, Jiefeng,Sun, Heqing,Cai, Wangshui,Pu, Xinghui,Zhang, Yemin,Shi, Zhuangzhi
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- Efficient metal-free photochemical borylation of aryl halides under batch and continuous-flow conditions
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A rapid, chemoselective and metal-free C-B bond-forming reaction of aryl iodides and bromides in aqueous solution at low temperatures was discovered. This reaction is amenable to batch and continuous-flow conditions and shows exceptional functional group tolerance and broad substrate scope regarding both the aryl halide and the borylating reagent. Initial mechanistic experiments indicated a photolytically generated aryl radical as the key intermediate.
- Chen, Kai,Zhang, Shuai,He, Pei,Li, Pengfei
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p. 3676 - 3680
(2016/06/09)
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- ORGANIC COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
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The present invention refers to organic compound and relates to search including organic electroluminescent device, of the present invention organic compounds are organic layer for organic electroluminescence device, preferably light-emitting layer according to be used in the organic electroluminescent the P-type semiconductor layer,, driving voltage, the objective compound. longevity, etc.. (by machine translation)
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Paragraph 0060-0063
(2017/01/02)
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- Multiple fluorescent behaviors of phenothiazine-based organic molecules
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We have designed a conventional one-step Suzuki coupling synthetic method to prepare 3,7-di-aryl substituted 10H-phenothiazine derivatives and investigated their optical behaviors. The compound 3,7-Bis (4-aminophenyl) phenothiazine (compound 1), substituting with electron-donating aniline, can exhibit photodamage behavior toward cancer cells. Furthermore, the compound 1 can form fluorescent organic nanoparticle (FON) in acidic aqueous whereas can emit red fluorescence in alkaline organic solvent. More importantly, compound 1 can be oxidized to manufactured a stable near-IR dye (>950 nm). Alternatively, the control compound 3,7-Bis (4-nitrophenyl) phenothiazine (compound 2) enabled us to determine that an electron-withdrawing group, when attaching on the phenothiazine, is unfavorable for molecular design to manufacture a cation form of NIR dye but is favorable to stabilize the phenothiazinate core and manufacture an anion form of NIR dye.
- Hsieh, Tung-Sheng,Wu, Jhen-Yi,Chang, Cheng-Chung
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- Discovery of biphenyl-aryl ureas as novel VEGFR-2 inhibitors. Part 4: Exploration of diverse hinge-binding fragments
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Abstract VEGFR-2 plays an essential role in angiogenesis and is an important target for cancer therapy. A series of biphenyl-aryl ureas were synthesized and evaluated as novel VEGFR-2 inhibitors. The pyridine, methylamine carbonyl pyridine and pivaloyl amide pyridine were introduced as novel hinge binding fragment. The majority of title compounds displayed potent VEGFR-2 inhibition. In particular, L1, L9, W14 and W15 exhibited significant enzymatic inhibitory activity with IC50 values of 0.36 nM, 0.22 nM, 0.15 nM and 0.14 nM. Compounds L1, L9 and W15 displayed potent antiproliferative activity against A549 and SMMC-7721 cells. SAR study suggested that incorporation of 3-trifluoromethyl and methylamine carbonyl on terminal pyridine could improve VEGFR-2 inhibitory activity. Molecular docking illustrated that urea moiety formed two critical hydrogen bonds with the DFG residues of VEGFR-2. The results indicated that these biphenyl-aryl ureas could serve as promising lead compounds for further optimization.
- Su, Ping,Wang, Jinfeng,Shi, Yaling,Pan, Xiaoyan,Shao, Ruili,Zhang, Jie
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p. 3228 - 3236
(2015/08/03)
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- Discovery of novel VEGFR-2 inhibitors. Part 5: Exploration of diverse hinge-binding fragments via core-refining approach
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Pathological angiogenesis plays a critical role in numerous diseases including malignancy. VEGFR-2 is the central regulators in angiogenesis and has become a promising target for anticancer drug design. We have identified a novel biphenyl-aryl urea incorporated with salicyladoxime (BPS-7) as potent VEGFR-2 inhibitor. As a continuation to our previous research, various aromatic-heterocyclic were introduced as hinge-binding fragment via a core-refining approach. Interestingly, many compounds exhibited comparable VEGFR-2 inhibition to Sorafenib. In particular, 12e and 12o displayed excellent VEGFR-2 inhibitory activity with IC50 values of 0.50 nM and 0.79 nM, respectively. Several title compounds showed considerable antiproliferative activity against A549 and SMMC-7721 cells. In addition, molecular docking was performed to rationalize the efficiency of the better compounds. These results will be instructive for further inhibitor design and optimization.
- Shan, Yuanyuan,Gao, Hongping,Shao, Xiaowei,Wang, Jinfeng,Pan, Xiaoyan,Zhang, Jie
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