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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Catalysis letters 41 (1996), S. 199-202 
    ISSN: 1572-879X
    Keywords: enantioselective ; hydrogenation ; cinchonidine ; Pd/alumina ; methylpentenoic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract A chiral alkanoic acid was prepared with up to 52% excess of the (S) enantiomer by hydrogenating anα,β-unsaturated carboxylic acid with a cinchonidine-Pd/Al2O3 catalyst system. Favourable conditions are: high surface hydrogen concentration (⩾ 60 bar hydrogen pressure, low catalyst concentration and apolar solvents), near ambient temperature and a cinchonidine/reactantmolar ratio of at least 0.4 mol%. It is proposed that high hydrogen solubility and the presence of 2-methyl-2-pentenoic acid reactant as dimers are advantageous for enantiodifferentiation.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Catalysis letters 69 (2000), S. 129-132 
    ISSN: 1572-879X
    Keywords: enantioselective ; hydrogenation ; cinchonidine ; cinchonine ; palladium ; pyrone
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Various 2‐pyrone derivatives are important intermediates in the synthesis of biologically active compounds. Pd chirally modified by cinchona alkaloids has a potential in the enantioselective hydrogenation of 4‐hydroxy‐6‐methyl‐2‐pyrone to the corresponding 5,6‐dihydropyrone. A study of various parameters (solvent, temperature, pressure, concentration) and catalyst systems (Pd/alumina and Pd/titania, modified by cinchonidine or cinchonine) revealed striking variations of the reaction rate and enantioselectivity with conversion. This transient behavior is interpreted by the effect of competitive adsorption and hydrogenation of the substrate and modifier.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1572-879X
    Keywords: enantioselective ; hydrogenation ; ketopantolactone ; cinchonidine ; catalyst pretreatment ; adsorbate‐induced restructuring
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The influence of reductive and oxidative heat treatment on the enantioselectivity of chirally modified Pt/alumina has been reinvestigated, using the hydrogenation of ketopantolactone as a test reaction. Enhancement in ee by 39–49% has been observed after treatment in hydrogen at 250–600°C, as compared to untreated or preoxidized catalysts. The changes in ee after reductive and oxidative treatments are reversible, and always the final treatment is decisive. A HRTEM study indicates that adsorbate‐induced restructuring of Pt crystallites during hydrogen treatment at elevated temperature can play a role in the selectivity improvement, but the changes are superimposed by the strong structure‐directing effect of the alumina support. The possible contribution of other effects (complete reduction of Pt n+ surface species, removal of impurities, or change of Pt particle size) could be excluded.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    Springer
    Catalysis letters 59 (1999), S. 95-97 
    ISSN: 1572-879X
    Keywords: enantioselective ; hydrogenation ; isomerization ; cinchonidine ; Pd/alumina ; alkenoic acid
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The enantioselective hydrogenation of 2-ethyl-propenoic acid over Pd/alumina modified with cinchonidine has been studied. The reaction, carried out in a batch reactor at 1 bar hydrogen pressure and room temperature, revealed that the isomerization of the C=C double bond is a competing side reaction. Double-bond migration and the subsequent hydrogenation of the two isomer alkenoic acids lowered the enantioselectivity drastically due to the formation of opposite enantiomers.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    Springer
    Topics in catalysis 8 (1999), S. 115-124 
    ISSN: 1572-9028
    Keywords: catalyst potential ; hydrogenation ; alcohol oxidation ; supported metal catalysts ; oxidation state
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The experimental technique and possible applications of the steady state catalyst potential measurement during Pt metal catalyzed hydrogenation and oxidation reactions in slurry reactors has been reviewed. The value of this in situ method is illustrated by many examples, including the separation of consecutive reaction steps, determination of the oxidation state of platinum metal catalyst and promoter during reaction, elucidation of the role of surface impurities, and controlling the rate of alcohol oxidation by optimizing the surface concentration of the oxidizing species.
    Type of Medium: Electronic Resource
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