Biocatalytic and chemical preparation of all four diastereomers of methionine sulfoxide

Tetrahedron Asymmetry

Volumn 9, Issue 4, 1998, Pages 535-538

  Holland, Herbert L ^a   Brown, Frances M ^a  

^a BROCK UNIVERSITY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

HYDROGEN PEROXIDE; METHIONINE; METHIONINE SULFOXIDE;

ARTICLE; BIOTRANSFORMATION; CATALYSIS; DIASTEREOISOMER; DRUG OXIDATION; DRUG SYNTHESIS; FUNGUS; PRIORITY JOURNAL;

EID: 0032570485     PISSN: 09574166     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0957-4166(98)00042-1     Document Type: Article

References (17)

1. Ciorba, M. A.; Heinemann, S. H.; Weissbach, H.; Brot, N.; Hoshi, T. Proc. Natl. Acad. Sci. 1997, 94, 9932.
2. Moskovitz, J.; Berlett, B. S.; Poston, J. M.; Stadtman, E. R. Proc. Natl. Acad. Sci. 1997, 94, 9598.
3. Kyung, K. H.; Han, D. C.; Fleming, H. P. J. Food Sci. 1997, 62, 406.
4. Chin, H.-W.; Lindsay, R. C. J. Agric. Food Chem. 1994, 42, 1529.
5. Lucas, F.; Levenbook, L. Biochem. J. 1966, 100, 473.
6. Christensen, B. W.; Kjær, A. J. Chem. Soc., Chem. Commun. 1965, 225.
7. Greenstein, J. P.; Winitz, M. Chemistry of the Amino Acids, vol. 3; Wiley, New York, 1961, p. 2145.
8. Holland, H. L.; Brown, F. M.; Lakshmaiah, G.; Larsen, B. G.; Patel, M. Tetrahedron: Asymmetry, 1997, 8, 683.
9. Holland, H. L.; Bornmann, M. J.; Lakshmaiah, G. J. Mol. Cat. (B), 1996, 1, 97.
10. Bose, A. K. Org. Synth. 1960, 40, 82.
11. The application of this microorganism for chiral sulfoxidation has not hitherto been reported, but its use was suggested to us by preliminary studies using B. bassiana for the oxidation of benzyl methyl sulfides: Holland, H. L.; Reese, P. B.; Brown, F. M. Unpublished data.
12. Beauveria bassiana ATCC 7159 was grown in 1 L Erlenmeyer flasks at 27°C, 180 rpm, in a medium consisting of glucose (10 g), and cornsteep liquor (20 g) per L of tap water, adjusted to pH 4.85. After 72 hours growth, the fungus was harvested by filtration and resuspended in a volume of distilled water equal to that of the original medium. A solution of substrate (750 mg) in ethanol (30 mL) was then added to achieve a final concentration of 0.75 g substrate per L of water. Biotransformation was allowed to proceed for a further 48 hours, at which time conversion to sulfoxide was complete. No sulfone products were detected. The fungus was then removed by filtration, the medium pH adjusted to 3.0, and the medium then extracted with dichloromethane (continuous extraction for 96 h). The residue obtained by evaporation of the extract was treated with decolourising carbon in chloroform solution, and then either crystallised or chromatographed as described in the text.
13. Christensen, B. W.; Kjær, A. J. Chem. Soc., Chem. Commun. 1969, 934.
14. The crude biotransformation product after decolourisation (3.5 g from 4 g substrate) was dissolved in hot methanol (30 mL). The volume of the solution was reduced to ca 15 mL by boiling, and the solution then allowed to cool to room temperature, yielding 2.56 g of product.
15. 13C NMR, MS and rotation data.
16. C) product, d.e. ca 80-85%. One recrystallisation from methanol (10 mL) then afforded 0.85-0.9 g of diastereomerically pure material.
17. Trial experiments indicate that biotransformation of N-phthaloyl L- and D-ethionines by B. bassiana proceeds in high yield to give sulfoxides with d.e.s of 86% and 76%, respectively