7145-99-5Relevant articles and documents
Metal-Organic Framework-Confined Single-Site Base-Metal Catalyst for Chemoselective Hydrodeoxygenation of Carbonyls and Alcohols
Antil, Neha,Kumar, Ajay,Akhtar, Naved,Newar, Rajashree,Begum, Wahida,Manna, Kuntal
supporting information, p. 9029 - 9039 (2021/06/28)
Chemoselective deoxygenation of carbonyls and alcohols using hydrogen by heterogeneous base-metal catalysts is crucial for the sustainable production of fine chemicals and biofuels. We report an aluminum metal-organic framework (DUT-5) node support cobalt(II) hydride, which is a highly chemoselective and recyclable heterogeneous catalyst for deoxygenation of a range of aromatic and aliphatic ketones, aldehydes, and primary and secondary alcohols, including biomass-derived substrates under 1 bar H2. The single-site cobalt catalyst (DUT-5-CoH) was easily prepared by postsynthetic metalation of the secondary building units (SBUs) of DUT-5 with CoCl2 followed by the reaction of NaEt3BH. X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy (XANES) indicated the presence of CoII and AlIII centers in DUT-5-CoH and DUT-5-Co after catalysis. The coordination environment of the cobalt center of DUT-5-Co before and after catalysis was established by extended X-ray fine structure spectroscopy (EXAFS) and density functional theory. The kinetic and computational data suggest reversible carbonyl coordination to cobalt preceding the turnover-limiting step, which involves 1,2-insertion of the coordinated carbonyl into the cobalt-hydride bond. The unique coordination environment of the cobalt ion ligated by oxo-nodes within the porous framework and the rate independency on the pressure of H2 allow the deoxygenation reactions chemoselectively under ambient hydrogen pressure.
Mechanistic Characterization of (Xantphos)Ni(I)-Mediated Alkyl Bromide Activation: Oxidative Addition, Electron Transfer, or Halogen-Atom Abstraction
Diccianni, Justin B.,Katigbak, Joseph,Hu, Chunhua,Diao, Tianning
supporting information, p. 1788 - 1796 (2019/01/26)
Ni(I)-mediated single-electron oxidative activation of alkyl halides has been extensively proposed as a key step in Ni-catalyzed cross-coupling reactions to generate radical intermediates. There are four mechanisms through which this step could take place: oxidative addition, outer-sphere electron transfer, inner-sphere electron transfer, and concerted halogen-atom abstraction. Despite considerable computational studies, there is no experimental study to evaluate all four pathways for Ni(I)-mediated alkyl radical formation. Herein, we report the isolation of a series of (Xantphos)Ni(I)-Ar complexes that selectively activate alkyl halides over aryl halides to eject radicals and form Ni(II) complexes. This observation allows the application of kinetic studies on the steric, electronic, and solvent effects, in combination with DFT calculations, to systematically assess the four possible pathways. Our data reveal that (Xantphos)Ni(I)-mediated alkyl halide activation proceeds via a concerted halogen-atom abstraction mechanism. This result corroborates previous DFT studies on (terpy)Ni(I)- and (py)Ni(I)-mediated alkyl radical formation, and contrasts with the outer-sphere electron transfer pathway observed for (PPh3)4Ni(0)-mediated aryl halide activation. This study of a model system provides insight into the overall mechanism of Ni-catalyzed cross-coupling reactions and offers a basis for differentiating electrophiles in cross-electrophile coupling reactions.
Endothelin antagonists benzene oxygen benzene acetic acids and its preparation method and application
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Paragraph 0072-0074, (2016/11/02)
The invention provides a phenoxy phenylacetic acid endothelin antagonist shown in a formula (I) or a pharmaceutically acceptable salt thereof, and also provides a preparation method of the benzene oxygen phenylacetic acid endothelin antagonist or the pharmaceutically acceptable salt thereof, and an application thereof in preparation of a medicament for treating cardiovascular and cerebrovascular diseases, tumors, diabetes mellitus, nephrosis, asthma or hyperthyroidism.