Efficient, Aerobic, Ruthenium-Catalyzed Oxidation of Alcohols into Aldehydes and Ketones

Markó, István E.; Giles, Paul R.; Tsukazaki, Masao; Chellé-Regnaut, Isabelle; Urch, Christopher J.; Brown, Stephen M.

doi:10.1021/ja973227b

Cited by 294 publications

(99 citation statements)

References 23 publications

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“…The method is effective for the conversion of a broad range of primary, secondary, and allylic alcohols to the corresponding aldehydes or ketones. Many other examples of selective catalytic aerobic oxidation of alcohols have been recently reported [32].…”

Section: Catalytic Oxidationmentioning

confidence: 99%

Atom efficiency and catalysis in organic synthesis

Sheldon

2000

Pure and Applied Chemistry

731

322

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Abstract:The key to waste minimization in fine chemicals manufacture is the widespread substitution of classical organic syntheses employing stoichiometric amounts of inorganic reagents with cleaner, catalytic alternatives. The E factors (by waste per kg product) of chemical processes increase dramatically on going downstream from bulk to fine chemicals and pharmaceuticals, mainly owing to the use of "stoichiometric" methods. The concept of atom efficiency is a useful tool for rapid evaluation of the amount of waste generated by alternative processes. The general theme of atom-efficient, catalytic processes is illustrated with industrially relevant examples. These include catalysis by solid acids and bases, catalytic reductions and oxidations, catalytic C-C bond formation, asymmetric catalysis, biocatalysis, and catalysis in novel media (aqueous and fluorous biphasic systems, supercritical fluids, and ionic liquids).

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Section: Catalytic Oxidationmentioning

confidence: 99%

Atom efficiency and catalysis in organic synthesis

Sheldon

2000

Pure and Applied Chemistry

731

322

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“…Particularly efficient homogeneous catalyst systems that also enable the oxidation of non-activated alcohols with dioxygen are those based on palladium, [9±15] ruthenium, [16,17] copper [18] and those based on TEMPO in the presence of a co-catalyst. [19±25] With respect to alcohol oxidation with aqueous hydrogen peroxide, notably homogeneous catalysts based on tungsten are efficient.…”

Section: Introductionmentioning

confidence: 99%

Selective Oxidation of Alcohols to Carbonyl Compounds and Carboxylic Acids with Platinum Group Metal Catalysts

et al. 2003

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The use of platinum group metal (PGM) catalysts for the selective oxidation of various primary and secondary alcohols under mild conditions is described. High throughput screening (HTS) techniques have been used to identify trends in catalyst activity and product selectivity. Using air as oxidant and water as solvent 5% Pt, 1% Bi/C has been identified as an efficient catalyst for the transformation of 2-octanol to 2-octanone and 1-octanol to octanoic acid. To improve aldehyde selectivity the promotion of Pt/Al 2 O 3 and Ru/C catalysts has been investigated. The use of H 2 O 2 as oxidant has been demonstrated as a suitable alternative to air.

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“…alcohols to ketones and amines to nitriles. [6][7][8] Many approaches have been used to heterogenize ruthenium onto porous supports, thereby combining the selectivity control of a nanoporous material (commonly oxidic or carbon-based) with the catalytic potential of the metallic species. [9][10][11] A variety of metal precursors and post-synthesis thermal treatments have been used, which have proved effective in enhancing the catalytic activity of Ru.…”

Section: Introductionmentioning

confidence: 99%

Understanding the molecular basis for the controlled design of ruthenium nanoparticles in microporous aluminophosphates

Potter

Purkis

Perdjon

et al. 2016

Mol. Syst. Des. Eng.

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Controling the structural properties of nanoparticle catalysts within a microporous framework is a major challenge. Using in situ X-ray Absorption Fine Structure (XAFS) Spectroscopy we detail the influence of activation parameters on the nature of ruthenium particles that are located within the confines of a nanoporous aluminophosphate (RuAlPO-5) architecture. These in situ studies confirm that controlled annealing conditions can tailor the formation of specific ruthenium species, which alter the catalytic performance towards the oxidation of cyclohexane to KA oil (a 1:1 mixture of cyclohexanone and cyclohexanol), the precursor for Nylon-6 and Nylon-6,6. IntroductionGiven the chemical industry's dependence on crude oil, the activation of inert hydrocarbons is of fundamental interest. [1][2][3][4] Once oxidized these molecules gain significant value as precursors in the fine-chemical and polymer industries. Heterogenized ruthenium species have been used for a variety of sustainable oxidation processes, [5] as the wide-range of available oxidation states makes ruthenium highly versatile for performing transformations of activated functional groups, e.g. alcohols to ketones and amines to nitriles. [6][7][8] Many approaches have been used to heterogenize ruthenium onto porous supports, thereby combining the selectivity control of a nanoporous material (commonly oxidic or carbon-based) with the catalytic potential of the metallic species. [9][10][11] A variety of metal precursors and post-synthesis thermal treatments have been used, which have proved effective in enhancing the catalytic activity of Ru. [12][13][14][15][16][17] In order to optimize catalytic performance many synthesis procedures have been developed with a view to creating uniform ruthenium sites. Ionic liquids are increasingly employed to generate nanoparticles (NPs) with a narrow size distribution, as the ionic liquid hinders particle agglomeration. [18][19][20] Similarly polymers such as poly(vinylpyrrolidone) are used as capping agents to restrict the size of the NPs formed via a micellar method, [21] before they are bound to a surface. The size and ensuing stability of ruthenium NPs has also been modified by inorganic additives, whereby a secondary metal can coat ruthenium NPs, maintaining metallic state and hindering subsequent formation of oxidic species. [22] A range of ruthenium-containing complexes have also been developed, aiming to preserve the integrity and isolated (< 10 atoms) nature of the precursor. Arguably, the most common of these are multimetallic nanoclusters, which form defined nanoparticles with distinct stoichiometry, concordant with the original cluster. [23,24] However, these strategies are commonly hindered by complex and sensitive precursors, such as multimetallic metal clusters, or precisely tailored organometallic species. [23,24] The use of isomorphously substituted metal atoms into a microporous framework (as outlined in Scheme S1, where small quantities of dopant transition metals can be used to replace Al(III) and P(V...

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Efficient, Aerobic, Ruthenium-Catalyzed Oxidation of Alcohols into Aldehydes and Ketones

Cited by 294 publications

References 23 publications

Atom efficiency and catalysis in organic synthesis

Atom efficiency and catalysis in organic synthesis

Selective Oxidation of Alcohols to Carbonyl Compounds and Carboxylic Acids with Platinum Group Metal Catalysts

Understanding the molecular basis for the controlled design of ruthenium nanoparticles in microporous aluminophosphates

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