214360-73-3Relevant articles and documents
Synthesis of a photostable near-infrared-absorbing photosensitizer for selective photodamage to cancer cells
Hsieh, Tung-Sheng,Wu, Jhen-Yi,Chang, Cheng-Chung
, p. 9709 - 9715 (2014)
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.
A practical and scalable process for the preparation of 4-aminophenylboronic acid pinacol ester
Xue, Feng,Li, Chang-Gong,Zhu, Yong,Lou, Tian-Jun,He, Guang-Jie
, p. 2739 - 2744 (2014)
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.
Terphenyl based 'Turn On' fluorescent sensor for mercury
Bhalla, Vandana,Tejpal, Ruchi,Kumar, Manoj,Puri, Rajiv Kumar,Mahajan, Rakesh K.
, p. 2649 - 2652 (2009)
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
Palladium-catalyzed borylation of aryl bromides and chlorides using phosphatrioxa-adamantane ligands
Christopher Maumela, Munaka,Holzapfel, Cedric W.,Lamola, Jairus L.,Moshapo, Paseka T.
supporting information, (2021/12/13)
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%).
Photo-induced thiolate catalytic activation of inert Caryl-hetero bonds for radical borylation
K?nig, Burkhard,Wang, Hua,Wang, Shun
supporting information, p. 1653 - 1665 (2021/06/17)
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.
Catalytic Boration of Alkyl Halides with Borane without Hydrodehalogenation Enabled by Titanium Catalyst
Wang, Xianjin,Cui, Penglei,Xia, Chungu,Wu, Lipeng
supporting information, p. 12298 - 12303 (2021/05/07)
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.
Recyclable Pd2dba3/XPhos/PEG-2000 System for Efficient Borylation of Aryl Chlorides: Practical Access to Aryl Boronates
Cai, Mingzhong,Huang, Bin,Luo, Chengkai,Xu, Caifeng
, (2021/12/02)
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.
Cyclic (Alkyl)(amino)carbene Ligand-Promoted Nitro Deoxygenative Hydroboration with Chromium Catalysis: Scope, Mechanism, and Applications
Zhao, Lixing,Hu, Chenyang,Cong, Xuefeng,Deng, Gongda,Liu, Liu Leo,Luo, Meiming,Zeng, Xiaoming
supporting information, p. 1618 - 1629 (2021/01/25)
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.
Aluminum Metal-Organic Framework-Ligated Single-Site Nickel(II)-Hydride for Heterogeneous Chemoselective Catalysis
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Dwivedi, Ashutosh,Manna, Kuntal
, p. 3943 - 3957 (2021/04/12)
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.
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
Zhou, Zhixu,Liu, Ye,Ren, Qian,Yu, Dehou,Lu, Hongguang
, (2021/03/22)
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.
