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Lam WW Yiu SM Lee JM Yau SK Kwong HK Lau TC Liu D Lin Z 《Journal of the American Chemical Society》2006,128(9):2851-2858
The oxidation of alkanes and arylalkanes by KMnO(4) in CH(3)CN is greatly accelerated by the presence of just a few equivalents of BF(3), the reaction occurring readily at room temperature. Carbonyl compounds are the predominant products in the oxidation of secondary C-H bonds. Spectrophotometric and kinetics studies show that BF(3) forms an adduct with KMnO(4) in CH(3)CN, [BF(3).MnO(4)](-), which is the active species responsible for the oxidation of C-H bonds. The rate constant for the oxidation of toluene by [BF(3).MnO(4)](-) is over 7 orders of magnitude faster than by MnO(4)(-) alone. The kinetic isotope effects for the oxidation of cyclohexane, toluene, and ethylbenzene at 25.0 degrees C are as follows: k(C6H12)/k(C6D12) = 5.3 +/- 0.6, k(C7H8)/k(C7D8) = 6.8 +/- 0.5, k(C8H10)/k(C8D10) = 7.1 +/- 0.5. The rate-limiting step for all of these reactions is most likely hydrogen-atom transfer from the substrate to an oxo group of the adduct. A good linear correlation between log(rate constant) and C-H bond energies of the hydrocarbons is found. The accelerating effect of BF(3) on the oxidation of methane by MnO(4)(-) has been studied computationally by the Density Functional Theory (DFT) method. A significant decrease in the reaction barrier results from BF(3) coordination to MnO(4)(-). The BF(3) coordination increases the ability of the Mn metal center to achieve a d(1) Mn(VI) electron configuration in the transition state. Calculations also indicate that the species [2BF(3).MnO(4)](-) is more reactive than [BF(3).MnO(4)](-). 相似文献
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Proietti Silvestri I Andemarian F Khairallah GN Yap SW Quach T Tsegay S Williams CM O'Hair RA Donnelly PS Williams SJ 《Organic & biomolecular chemistry》2011,9(17):6082-6088
Silver acetylides and organic azides react under copper(I) catalysis to afford 1,4-disubstituted 1,2,3-triazoles. Mechanistic studies implicate a process involving transmetallation to copper acetylides prior to cycloaddition. This work demonstrates that silver acetylides serve as suitable precursors for entry into copper-mediated coupling reactions. This methodology allows the incorporation of volatile and difficult-to-handle acetylenes into the triazole core. 相似文献
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Dr. Chi‐Ming Ho Chi‐Kit Wong Dr. Sammi King‐Woon Yau Dr. Chun‐Nam Lok Prof. Chi‐Ming Che 《化学:亚洲杂志》2011,6(9):2506-2511
We have recently reported a kinetic and mechanistic study on oxidative dissolution of silver nanoparticles (AgNPs) by H2O2. In the present study, the parameters that govern the dissolution of AgNPs by O2 were revealed by using UV/Vis spectrophotometry. Under the same reaction conditions (Tris‐HOAc, pH 8.5, I=0.1 M at 25 °C) the apparent dissolution rate (kapp) of AgNPs (10±2.8 nm) by O2 is about 100‐fold slower than that of H2O2. The reaction rate is first‐order with respect to [Ag0], [O2], and [Tris]T, and inverse first‐order with respect to [Ag+] (where [Ag0]=total concentration of Ag metal and [Tris]T=total concentration of Tris). The rate constant is dependent on the size of AgNPs. No free superoxide (O2−) and hydroxyl radical (⋅OH) were detected by trapping experiments. On the basis of kinetic and trapping experiments, an amine‐activated pathway for the oxidation of AgNPs by O2 is proposed. 相似文献
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Chi‐Ming Ho Dr. Sammi King‐Woon Yau Dr. Chun‐Nam Lok Dr. Man‐Ho So Chi‐Ming Che Prof. 《化学:亚洲杂志》2010,5(2):285-293
The oxidative dissolution of silver nanoparticles (AgNPs) plays an important role in the synthesis of well‐defined nanostructured materials, and may be responsible for their activities in biological systems. In this study, we use stopped‐flow spectrophotometry to investigate the kinetics and mechanism of the oxidative dissolution of AgNPs by H2O2 in quasi‐physiological conditions. Our results show that the reaction is first order with respect to both [Ag0] and [H2O2], and parallel pathways that involve the oxidation of H2O2 and HO2? are proposed. The order of the reaction is independent of the size of the AgNPs (≈5–20 nm). The rate of dissolution increases with increasing pH from 6.0 to 8.5. At 298 K and I=0.1 M , the value of kb is five orders of magnitude higher than that of ka (where ka and kb are the rate constants for the oxidative dissolution of AgNPs by H2O2 and HO2?, respectively). In addition, the effects of surface coating and the presence of halide ions on the dissolution rates are investigated. A possible mechanism for the oxidative dissolution of AgNPs by H2O2 is proposed. We further demonstrate that the toxicities of AgNPs in both bacteria and mammalian cells are enhanced in the presence of H2O2, thereby highlighting the biological relevance of investigating the oxidative dissolution of AgNPs. 相似文献
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Tim Quach Sammi Tsegay Andrew J. Thompson Nikolay V. Kukushkin Dominic S. Alonzi Terry D. Butters Gideon J. Davies Spencer J. Williams 《Tetrahedron: Asymmetry》2012,23(13):992-997
3-O-α-d-Glucopyranosyl-swainsonine was originally proposed17 as a potential inhibitor of the mammalian enzyme endo-α-mannosidase, but its synthesis has not been reported. Herein we report the total synthesis of this enigmatic compound, utilizing a halide-ion catalysed glycosylation of a swainsonine lactam with a glucosyl iodide donor as the key step. The resulting inhibitor was evaluated as an inhibitor of human endo-α-mannosidase, and as a ligand for bacterial orthologs from Bacteroides thetaiotaomicron and Bacteroides xylanisolvens, including active-centre variants, although no evidence for binding or inhibition was observed. The surprising lack of binding was rationalized by using structural alignment with an endo-α-mannosidase inhibitor complex, which identified deleterious interactions with the swainsonine piperidine ring and an essential active site residue. 相似文献
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