ISBN: 978-83-60043-10-3 - eurobic9

Eurobic9, 2-6 September, 2008, Wrocław, Poland
O10. Biocatalytic Alkene Cleavage Using Molecular Oxygen
F.G. Mutti a , M. Lara b , S.M. Glueck b , W. Kroutil b
a
Dipartimento di chimica inorganica, metallorganica, University of Milan, via Venezian 21, I-20133, Milano,
Italy
e-mail: francesco.mutti@unimi.it
b
Department of organic and bioorganic chemistry, University of Graz, Heinrichstrasse 28, A-8010, Graz,
Austria
The oxidative cleavage of alkenes is a widely employed method in synthetic chemistry, particularly to
introduce oxygen functionalities into molecules and remove protecting groups. Ozonolysis[1] is the most
common way to perform this reaction although it shows some disadvantages as the need of low temperature (-
78°C) and reducing reagents in molar amount. Alternative protocols envisage the use of heavy metals as Cr,
Os or Ru. Some peroxidases[2] and dioxygenases[3] display this activity as a minor side reaction.
An enviromentally friendly, biocatalytic approach is presented here. An enzyme preparation from the fungus
Trametes hirsuta G FCC 047 was employed for the C=C cleavage of different compounds in aqueous buffer
and using dioxygen (2 bar) as sole oxidative reagent[4] (Fig. 1).
A double bond conjugated with a phenyl ring is required for the biocatalytic activity. Quantitative conversion
was reached with t-anethole on analytical scale, whereas upscaling to 500 mg furnished 81% conversion (57%
isolated yield).
Experiments with labelled O2 and H2O using indene as substrate showed that only oxygen atoms from O2 were
incorporated, although derived from different molecules. Thus, alkene cleavage undergoes neither a
dioxygenase mechanism nor a monoxygenase one. Reactions in presence of superoxide dismutase did not
influence the reaction, so free radical superoxide anion is not the active species. Additionally, this study
indicated that the reaction is catalysed by a single enzyme.
References:
[1] Berglund, R.A., in Encyclopedia of Reagents for Organic Synthesis, Vol. 6 (ed.: L. A. Paquette), Wiley,
New York (1995) 3837-3843.
[2] a) Ozaki, S. and Ortiz de Montellano, P.R., J. Am. Chem. Soc. 117 (1995) 7056-7064. b) Tuynman, J.L.,
Ingeborg, M.K., Shoemaker, H.E. and Wever, R., J. Biol. Chem. 275 (2000) 3025-3030.
[3] Bugg, T.D.H., Tetrahedron 59 (2003) 7075-7101.
[4] a) Mang, H., Gross, J., Lara, M., Goessler, H.E., Shoemaker, G.M., Guebitz, W. and Kroutil W., Angew.
Chem. Int. Ed. 45 (2006) 5201-5203. b) Mang, H., Gross, J., Lara, M., Goessler, H.E., Shoemaker, G.M.,
Guebitz, W. and Kroutil W., Tetrahedron 63 (2007) 3350-3354. c) Lara, M., Mutti, F.G., Glueck, S.M. and
Kroutil W., Eur. J. Org. Chem. (2008) in press.
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