Collect. Czech. Chem. Commun. 2005, 70, 1709-1726

Toluene Dioxygenase-Mediated Oxidation of Bromo(methylsulfanyl)benzenes. Absolute Configuration of Metabolites and Evaluation of Chemo- and Regioselectivity Trends

Kevin J. Finn, Oksana Pavlyuk and Tomáš Hudlický*

Department of Chemistry, Brock University, St. Catharines, Ontario, Canada L2S 3A1


1. Gibson D. T., Koch J. R., Schuld C. L., Kallio R. E.: Biochemistry 1968, 7, 3795. <>
2a. Johnson R. A.: Org. React. 2004, 63, 117.
2b. Hudlický T., Gonzalez D., Gibson D. T.: Aldrichim. Acta 1999, 32, 35.
2c. Boyd D. R., Sheldrake G. N.: Nat. Prod. Rep. 1998, 15, 309. <>
3a. Hudlický T., Reed J. W. in: Advances in Asymmetric Synthesis (A. Hassner, Ed.), p. 271. JAI Press, Greenwich, CT 1995.
3b. Carless H. A. J.: Tetrahedron: Asymmetry 1992, 3, 795. <>
3c. Widdowson D. A., Ribbons D. W., Thomas S. D.: Janssen Chim. Acta 1990, 8, 3.
3d. Sheldrake G. N. in: Chirality and Industry (A. N. Collins, G. N. Sheldrake and J. Crosby, Eds), p. 127. John Wiley and Sons, Ltd., Chichester, U.K. 1992.
3e. Brown S. M., Hudlický T. in: Organic Synthesis: Theory and Applications (T. Hudlicky, Ed.), Vol. 2, p. 113. JAI Press, Greewich, CT 1993.
3f. Grund A. D.: SIMS News 1995, 45, 59.
3g. Hudlický T.: Chem. Rev. 1996, 96, 3. <>
3h. Hudlický T., Entwistle D. A., Pitzer K. K., Thorpe A. J.: Chem. Rev. 1996, 96, 1195. <>
3i. Hudlický T. in: Green Chemistry: Designing Chemistry for the Environment (P. T. Anastas and T. C. Williamson, Eds), Vol. 626, p. 180. ACS Symp. Ser., 1996.
3j. Hudlický T. in: Green Chemistry: Frontiers in Benign Chemical Syntheses and Processes (P. T. Anastas and T. C. Williamson, Eds), Chap. 10, p. 166. Oxford University Press, Oxford, U.K. 1998.
4. Zylstra G., Gibson D. T.: J. Biol. Chem. 1989, 264, 14940.
5. For indication of yields of more commonly used diols as well as a full description of medium-scale fermentation, see: Endoma M. A., Bui V. P., Hansen J., Hudlický T.: Org. Process Res. Dev. 2002, 6, 525. <>
6. Boyd D. R., Sharma N. D., Byrne B. E., Haughey S. A., Kennedy M. A., Allen C. C. R.: Org. Biomol. Chem. 2004, 2, 2530. <>
7a. Boyd D. R., Sharma N. D., Brannigan I. F., Haughey S. A., Malone J. F., Clarke D. A., Dalton H.: Chem. Commun. 1996, 2361. <>
7b. Boyd D. R., Sharma N. D., Boyle R., McMurray B. T., Evans T. A., Malone J. F., Dalton H., Chima J., Sheldrake G. N.: J. Chem. Soc., Chem. Commun. 1993, 49. <>
7c. Boyd D. R., Sharma N. D., Boyle R., Evans T. A., Malone J. F., McCombe K. M., Dalton H., Chima J.: J. Chem. Soc., Perkin Trans. 1 1996, 1757. <>
7d. Boyd D. R., Sharma N. D., Hempenstall F., Kennedy M. A., Malone J. F., Allen C. C. R.: J. Org. Chem. 1999, 64, 4005. <>
7e. Alien C. C. R., Boyd D. R., Dalton H., Sharma N. D., Haughey S. A., McMordie R. A. S., McMurray B. T., Sheldrake G. N., Sproule K.: J. Chem. Soc., Chem. Commun. 1995, 119. <>
8. Finn K. J., Cankař P., Jones R. T. B., Hudlický T.: Tetrahedron: Asymmetry 2004, 15, 2833. <>
9. The optical purity was found to be greater than 90% based on comparison of optical rotation values for methyl phenyl sulfoxide found in the literature: Holland H. L., Brown F. H., Larsen B. G.: Biorg. Med. Chem. Lett. 1994, 647. <>
10. Lee K., Brand J. M., Gibson D. T.: Biochem. Biophys. Res. Commun. 1995, 212, 9. <>
11. Hudlický T., Claeboe C. D., Brammer L. E., Koroniak L., Butora G., Ghiviriga I.: J. Org. Chem. 1999, 64, 4909. <>
12. Boyd D. R., Hand M. V., Sharma N. D., Chima J., Dalton H., Sheldrake G. N.: J. Chem. Soc., Chem. Commun. 1991, 1630. <>
13. Eliel E. L., Wilen S. H., Doyle M. P.: Basic Organic Stereochemistry, p. 443. John Wiley & Sons, Inc., New York 2001.
14. Capozzi M., Cardellicchio C., Naso F., Tortorella P.: J. Org. Chem. 2000, 65, 2843. <>
15. Optical puritiy of 2-bromophenyl methyl sulfoxide: 93%, [α__MATH__ +32.5 (c 1.8, CHCl3) (lit.6 [α]D +35 (c 1.8, CHCl3)); optical purity of 3-bromophenyl methyl sulfoxide: 34%, [α__MATH__ +39.8 (c 1.2, acetone) (lit.14 [α]D +116.3 (c 1.2, acetone)).
16. Cortese N. A., Heck R. F.: J. Org. Chem. 1977, 42, 3491. <>
17. The basic washing step was necessary since trace amounts of acid have been known to catalyze rapid and extremely exothermic dehydration and aromatization of cis- cyclohexadienediols.
18. Boyd D. R., Sharma N. D., Byrne B., Hand M. V., Malone J. F., Sheldrake G. N., Blacker J., Dalton H.: J. Chem. Soc., Perkin Trans. 1 1998, 1935. <>
19. Bui V. P., Nguyen M., Hansen J., Baker J., Hudlicky T.: Can. J. Chem. 2002, 80, 708. <>
20. Hudlický T., Oppong K., Duan C., Stanton C., Laufensweiler M. J., Natchus M. G.: Biorg. Med. Chem. Lett. 2001, 11, 627. <>