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Synthesis 2001(6): 0947-0951
DOI: 10.1055/s-2001-13394
SPECIALTOPIC
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Natural Product Precursors by Baeyer-Villiger Oxidation with Cyclohexanone Monooxygenase from Acinetobacter

Ulrich Schwarz-Lineka, Andreas Krödela, Friedrich-Alexander Ludwiga, Alexander Schulzea, Sebastian Rissomb, Udo Kraglb, Vladimir I. Tishkovc, Marina Vogel*a
a University of Leipzig, Department of Chemistry and Mineralogy, Johannisalle 29, 04103 Leipzig, Germany
Fax: +49(341)9736599; e-Mail: vogel@organik.chemie.uni-leipzig.de;
b Institute of Biotechnology, Research Center Jülich, Germany
c Department of Chemical Enzymology, M. V. Lomonossov Moscow State University, 119899 Moscow, Russian Federation,
Fax: +7(95)9392742; e-Mail: vit@enzyme.chem.msu.ru;
Further Information

Publication History

Received 1 March 2001
Publication Date:
24 September 2004 (online)

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Abstract

The Baeyer-Villiger oxidation of the 2-substituted ketones 1 and 3 with the coupled system cyclohexanone monooxygenase from Acinetobacter NCIMB 9871 / formate dehydrogenase from Pseudomonas sp. 101 provides the lactones (R)-2 and (R)-4 with high enantiomeric excess which are precursors in the synthesis of lipoic acid. The symmetrically trisubstituted ketone 5 was oxidised to the lactones 6a and 6b in a ratio of approx. 3:1. The absolute configuration of 6a and 6b was determined by hydrolysis of the racemic lactone with PLE yielding the hydroxycarboxylic acid (-)-7 with known absolute configuration.

Key words

oxidation - enzymes - kinetic resolution - hydrolysis - natural products

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The reaction was published without any experimental details.

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The lactone (R)-2 was described only in ref. 27 but without any physical data.