591-87-7Relevant articles and documents
OXIDATIVE ACETOXYLATION OF PROPYLENE IN THE PRESENCE OF PALLADIUM CATALYSTS. I. CATALYTIC COMPOSITION
Politanskii, S. F.,Shkitov, A. M.,Kharlamov, V. V.,Minachev, Kh. M.,Moiseev, I. I.,Nefedov, O. M.
, p. 1180 - 1185 (1981)
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Huyser,Rose
, p. 649 (1972)
Effect of palladium and copper content of zeolite catalysts on the kinetic parameters of the oxidative acetylation of propylene
Kharlamov,Pogorelov,Panov,Yanchevskaya,Minachev
, p. 2424 - 2429 (1989)
1. Using the methods of mathematical planning of an experiment, a kinetic model has been obtained for the oxidative acetylation of propylene to allyl acetate and the effect of the composition of the Pd, Cu/mordenite catalyst on its parameters has been determined. 2. The kinetic parameters (1g k0)0, Q, 1g a0 and E0 correlate strongly and form a gully on the surface of the minimized functional. Regularization of the values of the kinetic parameters was carried out by isolating a subregion of the gully satisfying the Boudart thermodynamic relationships. 3. On varying the Pd and Cu content of the catalyst within the limits 0.1 to 3.0%, the activation energy and the logarithm of the preexponential factor of the rate constant vary over the range 2-11 kcal/mole and 0.255-3.453, respectively.
How to Design Selective Ligands for Highly Conserved Binding Sites: A Case Study Using N-Myristoyltransferases as a Model System
Kersten, Christian,Fleischer, Edmond,Kehrein, Josef,Borek, Christoph,Jaenicke, Elmar,Sotriffer, Christoph,Brenk, Ruth
, p. 2095 - 2113 (2019/09/10)
A model system of two related enzymes with conserved binding sites, namely N-myristoyltransferase from two different organisms, was studied to decipher the driving forces that lead to selective inhibition in such cases. Using a combination of computational and experimental tools, two different selectivity-determining features were identified. For some ligands, a change in side-chain flexibility appears to be responsible for selective inhibition. Remarkably, this was observed for residues orienting their side chains away from the ligands. For other ligands, selectivity is caused by interfering with a water molecule that binds more strongly to the off-target than to the target. On the basis of this finding, a virtual screen for selective compounds was conducted, resulting in three hit compounds with the desired selectivity profile. This study delivers a guideline on how to assess selectivity-determining features in proteins with conserved binding sites and to translate this knowledge into the design of selective inhibitors.
Catalytic application of zinc complex of oxygen depleted 1,3-bis(pyrazole)-p-tert-butylcalix[4]arene
Sinha, Anshu Kumar,Vigalok, Arkadi,Rawat, Varun
supporting information, p. 796 - 799 (2019/02/14)
In this paper we have described the synthesis and coordination properties of monometallic Zinc complex of oxygen depleted bis(pyrazole)-p-tert-butylcalix[4]arene ligand. We also present the catalytic activity of the Zinc–bis(pyrazole) complex, in acetylation of alcohols and lactide polymerization.
Palladium-Catalyzed Aerobic Homocoupling of Alkynes: Full Mechanistic Characterization of a More Complex Oxidase-Type Behavior
Toledo, Alberto,Funes-Ardoiz, Ignacio,Maseras, Feliu,Albéniz, Ana C.
, p. 7495 - 7506 (2018/07/21)
A combined experimental and computational approach has been used to shed light on the mechanism of the Pd-catalyzed oxidative homocoupling of alkynes using oxygen as the oxidant. Mechanistic understanding is important because of the synthetically relevant direct involvement of oxygen in the oxidative coupling and because of the presence of related processes as undesired side reactions in cross-coupling reactions involving terminal alkynes. A low-ligated [Pd(PPh3)(alkyne)] complex is key in the process, and it can be conveniently generated from allylic palladium(II) complexes in the presence of a base or from Pd(I) allylic dimers as precatalysts. The catalytic coupling occurs by alkyne metalation to give an anionic [Pd(PPh3)(alkynyl)]- complex that is then oxidized by oxygen. The interaction with oxygen occurs only on this electron-rich Pd(0) anionic species and leads to a (κO,κO-peroxo)palladium(II) singlet intermediate that undergoes subsequent protonolysis to give a (κO-hydroperoxo)palladium(II) complex and then hydrogen peroxide. The second alkyne metalation occurs on a Pd(II) derivative to give a bis(alkynyl)palladium(II) complex that evolves to the product by reductive elimination as the product-forming step. This reaction is an oxidase-type process that, in contrast to most Pd-catalyzed oxidative processes, occurs without separation of the substrate transformation and the catalyst oxidation, with these two processes being intertwined and dependent on one another.