Chloroperoxidase as enantioselective epoxidation catalyst: An efficient synthesis of (R)-(-)-mevalonolactone

Journal of Organic Chemistry

Volumn 61, Issue 11, 1996, Pages 3923-3925

  Lakner, Frederick J ^a   Hager, Lowell P ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

MEVALONOLACTONE;

ARTICLE; DRUG STRUCTURE; DRUG SYNTHESIS; ENANTIOMER;

EID: 0029941844     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo960074m     Document Type: Article

References (40)

1. Recent reviews concerning the discovery and role of mevalonate: Goldstein, J. L.; Brown, M. S. Nature 1990, 343, 425-30.
2. Caspi, E. Tetrahedron 1986, 42, 3-50.
3. Herbert, R. B. The Biosynthesis of Secondary Metabolites, 2nd ed.; Chapmann and Hall: London, 1989.
4. Goodwin, T. W. Natural Substances Formed Biologically from Mevalonic Acid; Academic Press: New York: 1970; pp 45-47.
5. Ray, N. C.; Raveendranath, P. C.; Spencer, T. A. Tetrahedron 1992, 48, 9427-32. Bolitt, V.; Mioskowski, C.; Bhatt, R. K.; Falck, J. R.; J. Org. Chem. 1991, 56, 4238-40. Ohta, T.; Tabei, N.; Nozoe, S. Heterocycles 1989, 28, 425-32. Schneider, J. A.; Yoshihara, K. J. Org. Chem. 1986, 51, 1077-79. Mori, K.; Okada, K. Tetrahedron 1985, 41, 557-59. Bonadies, F.; Rossi, B.; Bonini, C. Tetrahedron Lett. 1984, 25, 5431-34.
6. Ray, N. C.; Raveendranath, P. C.; Spencer, T. A. Tetrahedron 1992, 48, 9427-32. Bolitt, V.; Mioskowski, C.; Bhatt, R. K.; Falck, J. R.; J. Org. Chem. 1991, 56, 4238-40. Ohta, T.; Tabei, N.; Nozoe, S. Heterocycles 1989, 28, 425-32. Schneider, J. A.; Yoshihara, K. J. Org. Chem. 1986, 51, 1077-79. Mori, K.; Okada, K. Tetrahedron 1985, 41, 557-59. Bonadies, F.; Rossi, B.; Bonini, C. Tetrahedron Lett. 1984, 25, 5431-34.
7. Ray, N. C.; Raveendranath, P. C.; Spencer, T. A. Tetrahedron 1992, 48, 9427-32. Bolitt, V.; Mioskowski, C.; Bhatt, R. K.; Falck, J. R.; J. Org. Chem. 1991, 56, 4238-40. Ohta, T.; Tabei, N.; Nozoe, S. Heterocycles 1989, 28, 425-32. Schneider, J. A.; Yoshihara, K. J. Org. Chem. 1986, 51, 1077-79. Mori, K.; Okada, K. Tetrahedron 1985, 41, 557-59. Bonadies, F.; Rossi, B.; Bonini, C. Tetrahedron Lett. 1984, 25, 5431-34.
8. Ray, N. C.; Raveendranath, P. C.; Spencer, T. A. Tetrahedron 1992, 48, 9427-32. Bolitt, V.; Mioskowski, C.; Bhatt, R. K.; Falck, J. R.; J. Org. Chem. 1991, 56, 4238-40. Ohta, T.; Tabei, N.; Nozoe, S. Heterocycles 1989, 28, 425-32. Schneider, J. A.; Yoshihara, K. J. Org. Chem. 1986, 51, 1077-79. Mori, K.; Okada, K. Tetrahedron 1985, 41, 557-59. Bonadies, F.; Rossi, B.; Bonini, C. Tetrahedron Lett. 1984, 25, 5431-34.
9. Ray, N. C.; Raveendranath, P. C.; Spencer, T. A. Tetrahedron 1992, 48, 9427-32. Bolitt, V.; Mioskowski, C.; Bhatt, R. K.; Falck, J. R.; J. Org. Chem. 1991, 56, 4238-40. Ohta, T.; Tabei, N.; Nozoe, S. Heterocycles 1989, 28, 425-32. Schneider, J. A.; Yoshihara, K. J. Org. Chem. 1986, 51, 1077-79. Mori, K.; Okada, K. Tetrahedron 1985, 41, 557-59. Bonadies, F.; Rossi, B.; Bonini, C. Tetrahedron Lett. 1984, 25, 5431-34.
10. Ray, N. C.; Raveendranath, P. C.; Spencer, T. A. Tetrahedron 1992, 48, 9427-32. Bolitt, V.; Mioskowski, C.; Bhatt, R. K.; Falck, J. R.; J. Org. Chem. 1991, 56, 4238-40. Ohta, T.; Tabei, N.; Nozoe, S. Heterocycles 1989, 28, 425-32. Schneider, J. A.; Yoshihara, K. J. Org. Chem. 1986, 51, 1077-79. Mori, K.; Okada, K. Tetrahedron 1985, 41, 557-59. Bonadies, F.; Rossi, B.; Bonini, C. Tetrahedron Lett. 1984, 25, 5431-34.
11. Mash, E. A.; Arterburn, J. B. J. Org. Chem. 1991, 56, 885-88.
12. Frye, S. V.; Eliel, E. L. J. Org. Chem. 1985, 50, 3402-04.
13. Takano, S.; Shimazaki, Y.; Iwabuchi, Y.; Ogasawara, K. Tetrahedron Lett. 1990, 31, 3619-22. Takano, S.; Morimoto, M.; Ogasawara, K. J. Chem. Soc., Chem. Commun. 1984, 82-83. Wilson, W. K.; Scallen, T. J.; Morrow, C. J. J. Lipid Res. 1982, 23, 645-52. Cornforth, R. H.; Cornforth, J. W.; Popjak, G. Tetrahedron 1962, 1351-54. Eberle, M.; Arigoni, D. Helv. Chim. Acta 1960, 43, 1508.
14. Takano, S.; Shimazaki, Y.; Iwabuchi, Y.; Ogasawara, K. Tetrahedron Lett. 1990, 31, 3619-22. Takano, S.; Morimoto, M.; Ogasawara, K. J. Chem. Soc., Chem. Commun. 1984, 82-83. Wilson, W. K.; Scallen, T. J.; Morrow, C. J. J. Lipid Res. 1982, 23, 645-52. Cornforth, R. H.; Cornforth, J. W.; Popjak, G. Tetrahedron 1962, 1351-54. Eberle, M.; Arigoni, D. Helv. Chim. Acta 1960, 43, 1508.
15. Takano, S.; Shimazaki, Y.; Iwabuchi, Y.; Ogasawara, K. Tetrahedron Lett. 1990, 31, 3619-22. Takano, S.; Morimoto, M.; Ogasawara, K. J. Chem. Soc., Chem. Commun. 1984, 82-83. Wilson, W. K.; Scallen, T. J.; Morrow, C. J. J. Lipid Res. 1982, 23, 645-52. Cornforth, R. H.; Cornforth, J. W.; Popjak, G. Tetrahedron 1962, 1351-54. Eberle, M.; Arigoni, D. Helv. Chim. Acta 1960, 43, 1508.
16. Takano, S.; Shimazaki, Y.; Iwabuchi, Y.; Ogasawara, K. Tetrahedron Lett. 1990, 31, 3619-22. Takano, S.; Morimoto, M.; Ogasawara, K. J. Chem. Soc., Chem. Commun. 1984, 82-83. Wilson, W. K.; Scallen, T. J.; Morrow, C. J. J. Lipid Res. 1982, 23, 645-52. Cornforth, R. H.; Cornforth, J. W.; Popjak, G. Tetrahedron 1962, 1351-54. Eberle, M.; Arigoni, D. Helv. Chim. Acta 1960, 43, 1508.
17. Takano, S.; Shimazaki, Y.; Iwabuchi, Y.; Ogasawara, K. Tetrahedron Lett. 1990, 31, 3619-22. Takano, S.; Morimoto, M.; Ogasawara, K. J. Chem. Soc., Chem. Commun. 1984, 82-83. Wilson, W. K.; Scallen, T. J.; Morrow, C. J. J. Lipid Res. 1982, 23, 645-52. Cornforth, R. H.; Cornforth, J. W.; Popjak, G. Tetrahedron 1962, 1351-54. Eberle, M.; Arigoni, D. Helv. Chim. Acta 1960, 43, 1508.
18. Krohn, K.; Meyer, A. Liebigs Ann. Chem. 1994, 167-74.
19. Abushanab, E.; Reed, D.; Suzuki, P.; Sih, C. J. Tetrahedron Lett. 1978, 3415-18.
20. Kawakami, U.; Hiratake, J.; Yamamoto, Y.; Oda, J. J. Chem. Soc., Chem. Commun. 1984, 779-81.
21. Ferraboschosi, P.; Grisenti, P.; Casati, S.; Santaniello, E. Synlett 1994, 754-56. Sugai, T.; Kakeya, H.; Ohta, H. Tetrahedron 1990, 46, 3463-68.
22. Ferraboschosi, P.; Grisenti, P.; Casati, S.; Santaniello, E. Synlett 1994, 754-56. Sugai, T.; Kakeya, H.; Ohta, H. Tetrahedron 1990, 46, 3463-68.
23. Francis, C. J.; Jones, J. B. J. Chem. Soc., Chem. Commun. 1984, 579-80. Huang, F.-C.; Lee, L. F. H.; Mittal, R. S. D.; Ravikumar, P. R.; Chan, J. A.; Sih, C. J.; Caspi, E.; Eck, C. R. J. Am. Chem. Soc. 1975, 97, 4144-45.
24. Francis, C. J.; Jones, J. B. J. Chem. Soc., Chem. Commun. 1984, 579-80. Huang, F.-C.; Lee, L. F. H.; Mittal, R. S. D.; Ravikumar, P. R.; Chan, J. A.; Sih, C. J.; Caspi, E.; Eck, C. R. J. Am. Chem. Soc. 1975, 97, 4144-45.
25. Ohta, H.; Tetsukawa, H.; Noto, N. J. Org. Chem. 1982, 47, 2400-404.
26. Irwin A. J.; Jones, J. B. J. Am. Chem. Soc. 1977, 99, 556-61.
27. Dexter, A. F.; Lakner, F. J.; Campbell, R. A.; Hager, L. P. J. Am. Chem. Soc. 1995, 117, 6412-13.
28. Chloroperoxidase (EC 1.11.1.10) is commercially available from Sigma Chemical Co. or Chirazyme Laboratories. From the latter source, the 0.44 mmol required for the preparation described herein would currently cost approximately $90.
29. If the alcohol is left to incubate with chloroperoxidase and t-BuOOH for 0.5 h, and a known substrate is then added, epoxidation proceeds smoothly with the known substrate. Therefore, we believe 3-methyl-3-butenol does not inactivate the enzyme, but merely fails to act as a substrate. This is consistent with other polar alkenes that we have tested (unpublished results). Preliminary observations of the active site as revealed by an X-ray crystal structure of chloroperoxidase (Sundaramoorthy, M.; Terner, J; Poulos, T. L. Structure 1995, 3, 1367-77) suggest that two phenylalanine residues flanking the active site may inhibit proper binding orientation through hydrophobic-hydrophilic repulsion. Molecular modeling studies currently underway are directed at testing this hypothesis.
30. GLC yield using decane as internal standard indicated complete conversion and 95% yield. The reaction currently stands at approximately 6800 turnovers and has not been optimized.
31. 4/ethanol: Mauger, J.; Robert, A. Tetrahedron 1988, 44, 2493-502.
32. The specific rotation for "high purity" (R)-(-)-mevalonolactone varies considerably in the literature. See ref 4, Wilson et al. for a discussion. Chiral GLC of our sample indicated 93% ee, demonstrating no measurable racemization during the synthetic sequence.
33. Cory, R. M.; Ritchie, B. M.; Shrier, A. M. Tetrahedron Lett. 1990, 31, 6789-92.
34. Murahashi, S.-I.; Imada, Y.; Tanguchi, Y.; Higashiura, S. Tetrahedron Lett. 1988, 29, 4945-48. Milstein, D. Organometallics 1982, 1, 888-90.
35. Murahashi, S.-I.; Imada, Y.; Tanguchi, Y.; Higashiura, S. Tetrahedron Lett. 1988, 29, 4945-48. Milstein, D. Organometallics 1982, 1, 888-90.
36. Mohr, P.; Rosslein, L.; Tamm, C. Tetrahedron Lett. 1989, 30, 2513-16.
37. Eggerer, von H.; Lynen, F. Justus Liebigs Ann. Chem. 1960, 630, 58-70.
38. Our method of choice: Herold, P.; Mohr, P.; Tamm, C. Helv. Chim. Acta 1983, 66, 744-54.
39. Racemic material has been reported, but only boiling point was provided as characterization. Courregelongue, J.; Lalo, J.; Maffrand, J. P. Fr. Demande PR 2,556,341, 1985. Chem. Abstr. 104: P 50556x.
40. Omichi, H.; Machida, H.; Miyakoshi, T.; Saito, S. Nippon Kagaku Kaishi 1977, 1021.