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

Ulrich Schwarz-Linek; Andreas Krödel; Friedrich-Alexander Ludwig; Alexander Schulze; Sebastian Rissom; Udo Kragl; Vladimir I. Tishkov; Marina Vogel

doi:10.1055/s-2001-13394

SPECIALTOPIC

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

Ulrich Schwarz-Linek^a, Andreas Krödel^a, Friedrich-Alexander Ludwig^a, Alexander Schulze^a, Sebastian Rissom^b, Udo Kragl^b, Vladimir I. Tishkov^c, 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;

Abstract

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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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Referenzen

References

1a

Present address: Department of Biochemistry, University of Oxford, South Parks Road, Oxford OX1 3QU, U.K.; E-mail: mailto:uli@bioch.ox.ac.uk

1b

New address: U. Kragl, University of Rostock, Department of Chemistry, Buchbinderstrasse 9, 18051 Rostock, Germany, Fax +49(0)3814981763, E-mail: udo.kragl@chemie.uni-rostock.de

2 Hoberg JO. Tetrahedron 1998, 54: 12631

3 Krow GR. Org. React. 1993, 43: 251

4 Renz M. Meunier B. Eur. J. Org. Chem. 1999, 737

5 Strukul G. Angew. Chem., Int. Ed. Engl. 1998, 37: 1198

6 Sugimura T. Fujiwara Y. Tai A. Tetrahedron Lett. 1997, 38: 6019

7 Lopp M. Paju A. Kanger T. Pehk T. Tetrahedron Lett. 1996, 37: 7583

8 Alphand V. Furstoss R. In Enzyme Catalysis in Organic Synthesis Drauz K. Waldmann H. VCH; Weinheim: 1995. p.745-773

9 Roberts SM. Wan PWH. J. Mol. Catal. B: Enzymatic 1998, 4: 111

10 Kelly DR. Wan PWH. Tang J. In Biotechnology: Biotransformations I Vol. 8a: Rehm H.-J. Wiley-VCH; Weinheim: 1998. p.535-587

11 Donoghue NA. Norris DB. Trudgill PW. Eur. J. Biochem. 1976, 63: 175

12 Latham JA. Walsh C. J. Am. Chem. Soc. 1987, 109: 3421

13 Stewart JD. Curr. Org. Chem. 1998, 2: 195

14 Gagnon R. Grogan G. Roberts SM. Villa R. Willetts AJ. J. Chem. Soc., Perkin Trans.1 1995, 1505

15 Taschner MJ. Black DJ. J. Am. Chem. Soc. 1988, 110: 6892

16 Stewart JD. Reed KW. Martinez CA. Zhu J. Chen G. Kayser MM. J. Am. Chem. Soc. 1998, 120: 3541

17 Chen G. Kayser MM. Mihovilovic MD. Mrstik ME. Martinez CA. Stewart JD. New J. Chem. 1999, 827

18 Mihovilovic MD. Chen G. Wang S. Kyte B. Rochon F. Kayser MM. Stewart JD. J. Org. Chem. 2001, 66: 733

19 Abril O. Ryerson CC. Walsh C. Whitesides GM. Bioorg. Chem. 1989, 17: 41

20 Chenault HK. Simon ES. Whitesides GM. Biotechnol. Genet. Eng. Rev. 1988, 6: 221

21 Tishkov VI. Galkin AG. Marchenko GN. Tsygankov YD. Egorov HM. Biotechnol. Appl. Biochem. 1993, 18: 201

22 Tishkov VI. Galkin AG. Fedorchuk VV. Savitsky PA. Rojkova AM. Gieren H. Kula M.-R. Biotechnol. Bioeng. 1999, 64: 187

23 Seelbach K. Riebel B. Hummel W. Kula M.-R. Tishkov VI. Egorov AM. Wandrey C. Kragl U. Tetrahedron Lett. 1996, 37: 1377

24 Rissom S. Schwarz-Linek U. Vogel M. Tishkov VI. Kragl U. Tetrahedron: Asymmetry 1997, 8: 2523

25 Vogel M. Schwarz-Linek U. In Bioorganic Chemistry. Highlights and New Aspects Diederichsen U. Lindhorst TK. Westermann B. Wessjohann LA. Wiley-VCH; Weinheim: 1999. p.102-110

26 Hambach B. Biselli M. Runstadler PW. Wandrey C. In Animal Cell Technology, Developments, Processes and Products Spier RE. Griffiths JB. MacDonald C. Butterworth-Heinemann; Oxford: 1992. p.381-385

27 Schneider M. Reymond F. Marison IW. vonStockar U. Enzyme Microb. Technol. 1995, 17: 839

28 Adger B. Bes MT. Grogan G. McCague R. Pedragosa-Moreau S. Roberts SM. Villa R. Wan PWH. Willetts AJ. J. Chem. Soc., Chem. Commun. 1995, 1563

29 Bringmann G. Herzberg D. Adam G. Balkenhohl F. Paust J. Z. Naturforsch., B: Chem. Sci. 1999, 54: 655

30

The reaction was published without any experimental details.

31 Adger B. Bes MT. Grogan G. McCague R. Pedragosa-Moreau S. Roberts S. Villa R. Wan PWH. Willetts AJ. Bioorg. Med. Chem. 1997, 5: 253

32

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

33 Bes TM. Villa R. Roberts SM. Wan PWH. Willetts A. J. Mol. Catal. B: Enzymatic 1996, 1: 127

34 Kuwahara Y. Yen LTM. Tominaga Y. Matsumoto K. Wada Y. Agric. Biol. Chem. 1982, 46: 2283

35 Mori K. Kuwahara S. Tetrahedron 1986, 42: 5539

36 Fouque E. Rousseau G. Synthesis 1989, 661

37 Fellous R. Lizzani-Cuvellier L. Loiseau MA. Sassy E. Tetrahedron: Asymmetry 1994, 5: 343

38a Schwarz-Linek U. PhD Thesis University of Leipzig; Germany: 1998.

38b

Details of the enzyme preparation will be reported in due course.