Highly efficient catalysts in directed oxygen-transfer processes: Synthesis, structures of novel manganese-containing heteropolyanions, and applications in regioselective epoxidation of dienes with hydrogen peroxide

Journal of the American Chemical Society

Volumn 120, Issue 29, 1998, Pages 7252-7259

  Bösing, Michael ^a   Nöh, Andreas ^a   Loose, Ina ^a   Krebs, Bernt ^a  

^a UNIVERSITY OF MÜNSTER   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

ALKADIENE; ANTIMONIOTUNGSTATE; HYDROGEN PEROXIDE; LIMONENE; MANGANESE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; CYCLIC POTENTIOMETRY; EPOXIDATION; GAS CHROMATOGRAPHY; INFRARED SPECTROSCOPY; MASS SPECTROMETRY; SYNTHESIS; X RAY ANALYSIS;

EID: 0032578148     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja974281v     Document Type: Article

References (34)

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22. Reaction conditions: substrate/oxidant (PhIO)/catalyst = 500/10/ 1, 20°C 2 h fi 7.5 turnovers to 1,2-limonene oxide (mixture of cis and trans isomers) based upon starting PhIO, ratio 1,2-limonene oxide:8,9-limonene oxide = 2.4:1.
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26. (R)-(+)-Limonene was taken as a model substrate due to its role as a very useful starting material for many organic syntheses, cf.: Szabo, W. A.; Lee, H. T. Aldrichim. Acta 1980, 13, 13. In qualitative experiments, the epoxidation of another important organic precursor compound, norbornene, under analogous condition with 1 as a catalyst was also successful.
27. Since no buffer was used during epoxidation of (R)-(+)-limonene a fairly acidic pH was maintained in the reaction mixture. Accordingly, the resulting epoxides can be converted to diols which will most likely move preferentially into the aqueous phase containing the hydrogen peroxide reactant. However, this effect is found not to be strong: The internal standard p-cymene does not increase appreciably during reaction, and analysis of the organic products gives no hint to this conversion either.
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