- Mechanistic Studies on the Hexadecafluorophthalocyanine–Iron-Catalyzed Wacker-Type Oxidation of Olefins to Ketones**
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The hexadecafluorophthalocyanine–iron complex FePcF16 was recently shown to convert olefins into ketones in the presence of stoichiometric amounts of triethylsilane in ethanol at room temperature under an oxygen atmosphere. Herein, we describe an extensive mechanistic investigation for the conversion of 2-vinylnaphthalene into 2-acetylnaphthalene as model reaction. A variety of studies including deuterium- and 18O2-labeling experiments, ESI-MS, and 57Fe M?ssbauer spectroscopy were performed to identify the intermediates involved in the catalytic cycle of the oxidation process. Finally, a detailed and well-supported reaction mechanism for the FePcF16-catalyzed Wacker-type oxidation is proposed.
- Grinenko, Vadim,Klau?, Hans-Henning,Kn?lker, Hans-Joachim,Puls, Florian,Seewald, Felix
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p. 16776 - 16787
(2021/11/04)
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- Silica-supported ultra small gold nanoparticles as nanoreactors for the etherification of silanes
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Ultra small gold nanoparticles supported by porous silica (Au-SiO2) were successfully synthesized. Due to enrichment of reactants by silica, the Au-SiO2 particles functioned as nanoreactors for catalytic etherification of silanes wit
- Wang, Cui,Lin, Xijie,Ge, Yuzhen,Shah, Zameer Hussain,Lu, Rongwen,Zhang, Shufen
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p. 102102 - 102108
(2016/11/09)
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- Meerwein's reagent mediated, significantly enhanced nucleophilic fluorination on alkoxysilanes
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We developed a new facile method to fluorosilanes from alkoxysilanes using Meerwein's reagent. Our protocol afforded fluorosilanes in excellent yields in various organic solvents including acetonitrile under mild reaction conditions at room temperature. We also proposed a reaction mechanism with the probable silyloxonium intermediates. Georg Thieme Verlag Stuttgart · New York.
- Jorapur, Yogesh R.,Shimada, Toyoshi
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supporting information; experimental part
p. 1064 - 1068
(2012/06/17)
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- An efficient method for the synthesis of symmetrical disiloxanes from alkoxysilanes using Meerwein's reagent
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We report here a new and efficient route to symmetrical disiloxanes from their corresponding alkoxysilanes using Meerwein's reagent as mediator and potassium carbonate as additive under mild reaction conditions in acetonitrile. Our methodology is very simple, economic, and high yielding. We have also proposed a reaction mechanism with the plausible silyloxonium intermediates. Georg Thieme Verlag Stuttgart · New York.
- Jorapur, Yogesh R.,Shimada, Toyoshi
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supporting information; experimental part
p. 1633 - 1638
(2012/08/07)
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- An Efficient Catalyst for the Conversion of Hydrosilanes to Alkoxysilanes
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The copper(I) hydride 6 is an efficient catalyst for the alcoholysis of primary and secondary silanes.The reactions proceed at room temperature within a few hours and give the alkoxysilanes in high yields.Only with bulky alcohols or silanes are longer reaction times and/or increased temperatures required.The presence of air accelarates the reactions and gives rise to higher yields of alkoxysilanes, particularly with bulky alcohols.Diols react with PhRSiH2 (R = Me, Ph) to afford 1,3-dioxo-2-silacycloalkanes and with tertiary silanes to furnish the bissilylated diols.When unsaturated alcohols (2-propen-1-ol or 2-propyn-1-ol) are employed, the double or triple bond is retained. - Keywords: Catalytic silane alcoholysis; Alkoxysilanes
- Lorenz, Catrin,Schubert, Ulrich
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p. 1267 - 1270
(2007/10/03)
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- Mechanism of Thermal Eliminations. Part 29. The Effect of Different Silyl groups upon Thermal Elimination of Ketene from Ethyl Silylacetates
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A series of ethyl silylacetates, R3SiCH2CO2Et where R3 = Me3, Me2Ph, MePh2, Ph3, have been prepared and their rates of gas-phase thermal elimination to ketene and the corresponding ethyl silyl ether measured, each over 50 deg C temperature range.Activation energies are in the range of 136-144 kJ mol-1, and log(A/s-1) values 10.1-10.8.Increase in the electrophilicity of silicon through replacement of one methyl group by phenyl produces a minor increase in reactivity, but further similar replacements eventually produce a rate decrease, which is attributed to steric hinderance.Overall the kinetic data indicate that the strength of the silicon-oxygen bond formed is sufficiently important that alteration in the ester structure is incapable of producing substantial variation in the rate of ketene formation.
- Chapman, Sara E.,Taylor, Roger
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p. 1119 - 1120
(2007/10/02)
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