Dynamic Catalysis in Aerobic Oxidation by Sol-Gel Living Materials

Ciriminna, Rosaria; Campestrini, Sandro; Carraro, Massimo; Pagliaro, Mario

doi:10.1002/adfm.200400409

Cited by 9 publications

(9 citation statements)

References 39 publications

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“…The corresponding rate constants ( k cat ) were obtained from integrated pseudo‐first‐order plots, that is, ln(1−[aldehyde] t = t /[aldehyde] t =∞ ) versus time, which are linear up to 80–90 % completion of the reaction as reported in Figure 1; the graphic also shows the kinetics of the aerobic benzyl alcohol oxidation mediated by 2 % mol perruthenate entrapped in Silc1 and Silc2 compared with that of the most active ORMOSIL‐entrapped perruthenate oxidation catalyst recently reported by some of us 22…”

Section: Resultsmentioning

confidence: 72%

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Aerobic Oxidation of Alcohols in Carbon Dioxide with Silica‐Supported Ionic Liquids Doped with Perruthenate

Ciriminna

Hesemann

Moreau

et al. 2006

Chemistry A European J

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The replacement of toxic Cr(VI) for O2 and of chlorinated solvents for supercritical carbon dioxide (or ionic liquids) in the oxidation of alcohols remains hindered by the low selectivity and activity of the current heterogeneous catalysts. Using an integrated approach that combines sol-gel entrapped perruthenate as aerobic catalyst, an encapsulated ionic liquid as solubility promoter, and scCO2 as the reaction solvent, we have developed a system capable of rapidly converting different alcohols into carbonyl compounds with complete selectivity, including substrates which are otherwise difficult to oxidise. The methodology is generally applicable and may easily be extended to other waste-free, catalytic syntheses of fine chemicals.

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Section: Resultsmentioning

confidence: 72%

“…For comparison (Table 3), this value is almost four times higher than that of our most active Ru‐based oxidation catalyst,22 that is, a 75 % methyl‐modified ORMOSIL which has a kinetic constant of 0.798×10 −2 upon eighteen months of catalyst aging under the same reaction conditions.…”

Section: Resultsmentioning

confidence: 83%

Aerobic Oxidation of Alcohols in Carbon Dioxide with Silica‐Supported Ionic Liquids Doped with Perruthenate

Ciriminna

Hesemann

Moreau

et al. 2006

Chemistry A European J

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“…Consequently, the dry gel (xerogel) obtained by removal of the residual solvent is also unstable, since the remaining hydroxyl (OH) groups can further condense. The net result is a “living” material that undergoes structural modifications, even months after preparation so that, for instance, an entrapped transition metal catalyst migrates to the surface of newly formed porosity, affording a solid catalyst several times more active compared to the freshly prepared material (Figure ) 1 1.…”

Section: Tailored Structures Through Control Of the Sol−gel Processmentioning

confidence: 99%

Better Chemistry through Ceramics: The Physical Bases of the Outstanding Chemistry of ORMOSIL

et al. 2006

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Twenty years after their invention, sol-gel organically modified silicates (ORMOSIL) are finding a number of impressive applications that range from efficient deliver of genes into mouse brains to self-ordered helices of interest to fields as diverse as optics, catalysis, molecular recognition, and chromatography. The physical bases of this mulifaceted chemistry, therefore, are of immense importance to scientists working toward new applications such as photovoltaics and catalysis that are crucially important in making sustainable global development. The purpose of this article is to provide a general picture of ORMOSIL's physical chemistry that will be useful in the creative development of new materials capable to solve a number of relevant open problems.

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“…Examples of lactolto-lactone oxidations effected by TPAP/NMO/PMS/CH 2 Cl 2 include a step for thapsigargin syntheses [152,153], and TPAP/NMO/PMS/CH 3 CN [64] for a tetrol to lactone oxidation [152]. The supported reagent Si-TPAP/O 2 /toluene or supercritical CO 2 /75°C oxidised secondary alcohols to ketones [154]; for oxidations using supported TPAP for secondary and primary alcohols cf. [66].…”

Section: Specific Examplesmentioning

confidence: 99%

Oxidation of Alcohols, Carbohydrates and Diols

Griffith

2009

Catalysis by Metal Complexes

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This is one of the most important classes of oxidation effected by Ru complexes, particularly by RuO 4 , [RuO 4 ] − , [RuO 4 ] 2− and RuCl 2 (PPh 3 ) 3 , though in fact most Ru oxidants effect these transformations. The chapter covers oxidation of primary alcohols to aldehydes (section 2.1), and to carboxylic acids (2.2), and of secondary alcohols to ketones (2.3). Oxidation of primary and secondary alcohol functionalities in carbohydrates (sugars) is dealt with in section 2.4, then oxidation of diols and polyols to lactones and acids (2.5). Finally there is a short section on miscellaneous alcohol oxidations in section 2.6.In this chapter the first of the two most important categories of oxidations catalysed by Ru complexes (the other being alkene and alkyne oxidations in Chapter 3) are considered. The approach in this and subsequent chapters differs from that of Chapter 1, concentrating here on the substrate rather than on the oxidant. The text is divided into the categories of alcohols and their oxidations. There are summaries in section 2.3.6 of systems of limited applicability which are mentioned only in Chapter 1, and in section 2.3.7 of large-scale (>1 g) oxidations.The first oxidations of alcohols by stoicheiometric RuO 4 /H 2 O were reported in 1958, of primary alcohols to aldehydes or carboxylic acids and secondary alcohols to ketones [1]. The first Ru-catalysed oxidation of an alcohol was reported in 1965 when Parikh and Jones used RuO 2 /aq. Na(IO 4 )/CCl 4 1 ( Table 2.3) [2] to oxidise secondary alcohol groups in carbohydrates.Oxidation of alcohols is the most frequently reviewed topic for Ru-catalysed oxidations [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Mechanisms of alcohol oxidation by Ru complexes have been reviewed [21].

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Dynamic Catalysis in Aerobic Oxidation by Sol-Gel Living Materials

Cited by 9 publications

References 39 publications

Aerobic Oxidation of Alcohols in Carbon Dioxide with Silica‐Supported Ionic Liquids Doped with Perruthenate

Aerobic Oxidation of Alcohols in Carbon Dioxide with Silica‐Supported Ionic Liquids Doped with Perruthenate

Better Chemistry through Ceramics: The Physical Bases of the Outstanding Chemistry of ORMOSIL

Oxidation of Alcohols, Carbohydrates and Diols

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