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Studies on Substituted Aromatic Diselenides as Catalysts for Selective Alcohol Oxidation Using tert-Butyl Hydroperoxide

  1. John C. van der Toorn1,
  2. Gerjan Kemperman2,
  3. Roger A. Sheldon1,
  4. Isabel W. C. E. Arends1

Article first published online: 10 JUN 2011

DOI: 10.1002/ejoc.201100487

Issue

European Journal of Organic Chemistry

European Journal of Organic Chemistry

Volume 2011, Issue 23, pages 4345–4352, August 2011

Additional Information

How to Cite

van der Toorn, J. C., Kemperman, G., Sheldon, R. A. and Arends, I. W. C. E. (2011), Studies on Substituted Aromatic Diselenides as Catalysts for Selective Alcohol Oxidation Using tert-Butyl Hydroperoxide. Eur. J. Org. Chem., 2011: 4345–4352. doi: 10.1002/ejoc.201100487

Author Information

  1. 1

    Department of Biotechnology, Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands, Fax: +31-15-2781415

  2. 2

    Department of Process Chemistry, Merck Sharp and Dohme, Molenstraat 110, 5342 CC Oss, The Netherlands

Publication History

  1. Issue published online: 2 AUG 2011
  2. Article first published online: 10 JUN 2011
  3. Manuscript Received: 6 APR 2011

Funded by

  • Netherlands Organisation for Scientific Research (NWO)

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Keywords:

  • Selenium;
  • Oxidation;
  • Calorimetry;
  • Peroxides;
  • Alcohols

Abstract

We have investigated the Ph2Se2-catalysed oxidation of alcohols with tert-butyl hydroperoxide (TBHP) by using a variety of spectroscopic techniques and reaction calorimetry. We showed that the active oxidant is benzeneseleninic anhydride (BSA), formed by reaction of Ph2Se2 with TBHP. The influence of aromatic substituents on the activity of a selection of nine aromatic diselenides involved in alcohol oxidations was studied. Calorimetric experiments showed that compounds that are activated more rapidly have higher initial activity in the catalytic oxidation of benzyl alcohol. An exception to this rule was observed when the diselenide contained a dimethylamino group in the ortho position, which can apparently compensate for its slow pre-activation by a special ortho effect. An aliphatic alcohol, 1-decanol was also used as a substrate. Besides diphenyl diselenide only three of the substituted diaryl diselenides studied showed reasonable activity after pre-activation with TBHP. Dimesityl diselenide displayed the highest activity and selectivity for the oxidation of 1-decanol. Specificity for a given aldehyde could be achieved by using an oxidant and substrate feed protocol.

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