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Catalytic Activation (catalytic + activation)
Selected AbstractsCatalytic Activation of Silylated Nucleophiles Using tBu-P4 as a Base.CHEMINFORM, Issue 39 2005Masahiro Ueno Abstract For Abstract see ChemInform Abstract in Full Text. [source] Catalytic activation through metal enolization of nucleophile precursors and synthetic applications to enantioselective Michael additionsTHE CHEMICAL RECORD, Issue 3 2007Shuji Kanemasa Abstract Catalytic activation methods of nucleophile precursors recently developed in our research group were reviewed in this paper. These include (i) the catalytic double activation method of nucleophile precursors through enol formation and of electrophiles through coordination in alcohols; (ii) the double catalytic activation method by use of both catalytic amounts of chiral Lewis acid and external achiral amine; (iii) the catalytic activation method of nucleophile precursors with a chiral cationic Lewis acid in the presence of molecular sieves; and (iv) the single catalytic activation of nucleophile precursors through metal enolization in alcohol media. © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 137,149; 2007: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20105 [source] Synthesis and Electrochemical Study of an Original Copper(II)-Capped Salen,Cyclodextrin ComplexEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 29 2010Elise Deunf Abstract A new metallocapped cyclodextrin (CD) was synthesized by the regioselective debenzylation, induced by diisobutylaluminium hydride (DIBAL-H), of perbenzylated cyclodextrins. This reaction allowed for the efficient preparation of an unprecedented CD,salen type copper(II) complex. The electrochemical behavior of both the bound and unbound CD,salen compounds was investigated by cyclic voltammetry. Notably, it was shown that the presence of tert -butyl groups at the ortho - and para -positions of the salen aromatic rings stabilized the copper(II) phenoxyl radical species that was generated upon the one-electron oxidation of the starting compound. Importantly, this stabilization remained effective when the salen-type ligand was covalently attached to the CD. This allowed for investigations of the reactivity of the copper(II) phenoxyl radical complex towards a primary alcohol to be performed by cyclic voltammetry. This reaction can be considered as mimicking the behavior of galactose oxidase. However, under these conditions, no reactivity was observed in the presence of benzyl alcohol. This may be due to distortion, either of the initially square planar salen ligand after its grafting to the CD primary face, and/or of the CD itself. On the other hand, the electrochemical reduction of the un-grafted copper(II) salen-type ligand led to a transient anionic species that exhibited significant stability on the time-scale of the slow cyclic voltammetry measurement in the absence of the CD, but was unstable in the presence of the CD. In the latter case, it was demonstrated that the anionic species was protonated by the CD. Importantly, this protonation was not fast enough to prevent catalytic activation of iodomethane by the electro-generated copper(I)-capped salen CD complex. [source] The Extraordinary Cocatalytic Action of Polymethylaluminoxane (MAO) in the Polymerization of Terminal Olefins by Metallocenes: Chemical Change in the Group 4 Metallocene Dimethyl Derivatives Induced by MAO,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 20 2005John J. Eisch Abstract In the polymerization of olefins with Group 4 metallocene dichlorides or dimethyl derivatives as procatalysts the use of polymethylaluminoxane (MAO) as the cocatalyst, especially in extreme excess (102,103 times the metallocene equivalent), has been shown to have an extraordinary accelerating effect on the rate of olefin polymerization, when compared with the cocatalytic action of alkylaluminum halides. In attempts at explaining the greatly superior catalytic activity of MAO in olefin polymerization (the MAO conundrum), hypotheses have generally paralleled the steps involved in the cocatalytic action of RnAlCl3,n, namely the alkylation of Cp2MtCl2, ionization of Cp2Mt(R)Cl into the metallocenium cation, [Cp2Mt,R]+, and anion, [Rn,1AlCl4,n], and subsequent ion-pair separation. In order to understand any differences in catalytic action between such cocatalysts, we have studied the individual action of MAO (100 equiv.) and of MeAlCl2 (1,2 equiv.) on each of the Group 4 metallocene derivatives, Cp2TiCl2, Cp2ZrCl2, Cp2Ti(CH3)2 and Cp2Zr(CH3)2. With MeAlCl2 each of the metallocene derivatives appeared to form the cation, [Cp2Mt,CH3]+, with greater (Ti) or lesser (Zr) ease, because an alkyne such as diphenylacetylene was then found to insert into the Mt,CH3 bond stereoselectively. In striking contrast, treatment of each metallocene with MAO gave two reactions very different from MeAlCl2, namely a steady evolution of methane gas upon mixing and a finding upon hydrolytic workup that the diphenylacetylene present had undergone no insertion into the Mt,CH3 bond but instead had been reductively dimerized completely to (E,E)-1,2,3,4-tetraphenyl-1,3-butadiene. To account for this astonishing difference in chemical behavior between MAO and MeAlCl2 in their cocatalytic activation of Group 4 metallocenes to olefin polymerization, it is necessary to postulate a novel, unique sequence of reaction steps occurring between MAO and the metallocene. If one starts with the metallocene dichloride, then the free TMA present in the MAO would generate the Cp2Mt(CH3)2. This metallocene dimethyl derivative, complexed with an oligomeric MAO unit, would undergo a transfer-epimetallation with added olefin or acetylene to form a metallacyclopropane or metallacyclopropene, respectively. With added diphenylacetylene the resulting 2,3-diphenylmetallacyclopropene would be expected rapidly to insert a second alkyne to form the 2,3,4,5-tetraphenyl-1-metallacyclopentadiene. Simple hydrolysis of the latter intermediate would generate (E,E)-1,2,3,4-tetraphenyl-1,3-butadiene while alternative workup with D2O would give the 1,4-dideuterio derivative of this butadiene. Both such expectations were confirmed by experiment. In the case of added olefin, similar metallacyclopropane and metallacyclopentane intermediates should be produced until ring opening of the latter five-membered ring leads to an open-chain zwitterion, a process having ample precedent in the research of Gerhard Erker. The solution to the MAO conundrum then, namely the extraordinary cocatalytic activity of MAO in olefin polymerization by metallocenes, lies in the unique catalytic activation of the Group 4 metallocene dimethyl derivative, which occurs by transfer-epimetallation of the olefin monomer by the Cp2Mt(CH3)2,MAO complex. The most advantageous Lewis acidic sites in the MAO,oligomeric mixture for such metallocene,MAO complexation are suggested to be terminal Me2Al,O,AlMe, segments of an open-chain oligomer. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Essential role of PSM/SH2-B variants in insulin receptor catalytic activation and the resulting cellular responsesJOURNAL OF CELLULAR BIOCHEMISTRY, Issue 1 2008Manchao Zhang Abstract The positive regulatory role of PSM/SH2-B downstream of various mitogenic receptor tyrosine kinases or gene disruption experiments in mice support a role of PSM in the regulation of insulin action. Here, four alternative PSM splice variants and individual functional domains were compared for their role in the regulation of specific metabolic insulin responses. We found that individual PSM variants in 3T3-L1 adipocytes potentiated insulin-mediated glucose and amino acid transport, glycogenesis, lipogenesis, and key components in the metabolic insulin response including p70 S6 kinase, glycogen synthase, glycogen synthase kinase 3 (GSK3), Akt, Cbl, and IRS-1. Highest activity was consistently observed for PSM alpha, followed by beta, delta, and gamma with decreasing activity. In contrast, dominant-negative peptide mimetics of the PSM Pro-rich, pleckstrin homology (PH), or src homology 2 (SH2) domains inhibited any tested insulin response. Potentiation of the insulin response originated at the insulin receptor (IR) kinase level by PSM variant-specific regulation of the Km (ATP) whereas the Vmax remained unaffected. IR catalytic activation was inhibited by peptide mimetics of the PSM SH2 or dimerization domain (DD). Either peptide should disrupt the complex of a PSM dimer linked to IR via SH2 domains as proposed for PSM activation of tyrosine kinase JAK2. Either peptide abolished downstream insulin responses indistinguishable from PSM siRNA knockdown. Our results implicate an essential role of the PSM variants in the activation of the IR kinase and the resulting metabolic insulin response. PSM variants act as internal IR ligands that in addition to potentiating the insulin response stimulate IR catalytic activation even in the absence of insulin. J. Cell. Biochem. 103: 162,181, 2008. © 2007 Wiley-Liss, Inc. [source] The water extract of Omija protects H9c2 cardiomyoblast cells from hydrogen peroxide through prevention of mitochondrial dysfunction and activation of caspases pathwayPHYTOTHERAPY RESEARCH, Issue 1 2007Channy Park Abstract The water extract of Omija (Omija) has been used traditionally in the treatment of ischemic damage of the heart and brain tissues. However, little is known about the mechanism by which it rescues myocardial cells from oxidative stress. This study was designed to investigate the protective mechanisms of Omija on H2O2 -induced cytotoxicity in H9c2 cardiomyoblast cells. Treatment with H2O2 resulted in the death of H9c2 cells, characterized by apparent apoptotic features, including fragmentation of the nucleus and an increase in the sub-G0/G1 fraction of the cell cycle. However, Omija markedly suppressed the apoptotic characteristics of H9c2 cells induced by H2O2. In addition, Omija suppressed the features of mitochondrial dysfunction, including changes in the mitochondrial membrane potential and cytosolic release of cytochrome c in H2O2 -treated cells. Treatment with Omija further inhibited the catalytic activation of caspase-9 and caspase-3 and induction of Fas by H2O2. Taken together, these data indicate that the water extract of Omija protects H9c2 cardiomyoblast cells from oxidative stress of H2O2 through inhibition of mitochondrial dysfunction and activation of intrinsic caspase cascades, including caspase-3 and caspase-9. Copyright © 2006 John Wiley & Sons, Ltd. [source] Caspase activation, inhibition, and reactivation: A mechanistic viewPROTEIN SCIENCE, Issue 8 2004Yigong Shi Abstract Caspases, a unique family of cysteine proteases, execute programmed cell death (apoptosis). Caspases exist as inactive zymogens in cells and undergo a cascade of catalytic activation at the onset of apoptosis. The activated caspases are subject to inhibition by the inhibitor-of-apoptosis (IAP) family of proteins. This inhibition can be effectively removed by diverse proteins that share an IAP-binding tetrapeptide motif. Recent structural and biochemical studies have revealed the underlying molecular mechanisms for these processes in mammals and in Drosophila. This paper reviews these latest advances. [source] Catalytic activation through metal enolization of nucleophile precursors and synthetic applications to enantioselective Michael additionsTHE CHEMICAL RECORD, Issue 3 2007Shuji Kanemasa Abstract Catalytic activation methods of nucleophile precursors recently developed in our research group were reviewed in this paper. These include (i) the catalytic double activation method of nucleophile precursors through enol formation and of electrophiles through coordination in alcohols; (ii) the double catalytic activation method by use of both catalytic amounts of chiral Lewis acid and external achiral amine; (iii) the catalytic activation method of nucleophile precursors with a chiral cationic Lewis acid in the presence of molecular sieves; and (iv) the single catalytic activation of nucleophile precursors through metal enolization in alcohol media. © 2007 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 7: 137,149; 2007: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.20105 [source] | ||||||||||