Rational control of enzymatic enantioselectivity through solvation thermodynamics

Journal of the American Chemical Society

Volumn 118, Issue 43, 1996, Pages 10365-10370

  Wescott, Charles R ^a   Noritomi, Hidetaka ^a,b   Klibanov, Alexander M ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

^b TOKYO METROPOLITAN UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

CHYMOTRYPSIN; PROPIONIC ACID DERIVATIVE;

ARTICLE; CHIRALITY; DRUG SYNTHESIS; ENZYME ACTIVITY; REACTION ANALYSIS;

EID: 0029818293     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja961394q     Document Type: Article

References (50)

1. (a) Simon, H.; Bader, J.; Gunther, H.; Neumann, S.; Thanos, J. Angew. Chem., Int. Ed. Engl. 1985, 24, 539.
2. (b) Yamada, H.; Shimizu. S. Angew. Chem., Int. Ed. Engl. 1988, 27, 622.
3. (c) Jones, J. B. Tetrahedron 1986, 42, 3351.
4. (d) Faber, K. Biotransformations in Organic Chemistry; Springer-Verlag: Berlin, 1992.
5. (e) Poppe, L.; Novak, L. Selective Biocatalysis; VCH Publishers: New York. 1992.
6. (f) Sheldon. R. A. Chirotechnohgy: Industrial Synthesis of Optically Active Compounds; M. Dekker: New York, 1993.
7. (g) Margolin, A. L. Enzyme Microb. Technol. 1993, 15, 266.
8. (h) Wong, C.-H.; Whitesides, G. M. Enzymes in Synthetic Organic Chemistry; Pergamon: Oxford, 1994.
9. (i) Roberts, S. M.; Turner, N. J.; Willetts, A. J.; Turner, M. K. Introduction to Biocatalysis Using Enzymes and Microorganisms; Cambridge University Press: New York, 1995.
10. (j) Drauz, K.; Waldmann, H. Enzyme Catalysis in Organic Synthesis; VCH Publishers: New York, 1995.
11. (a) Klibanov, A. M. Trends Biochem. Sci. 1989. 14, 141.
12. (b) Chen, C.-S.; Sih, C. J. Angew. Chem., Int. Ed. Engl. 1989, 28, 695.
13. (c) Dordick, J. S. Enzyme Microb. Technol. 1989, 11, 194.
14. (d) Klibanov, A. M. Ace. Chem. Res. 1990, 23, 114.
15. (e) Gupta, M. N. Eur. J. Biochem. 1992, 203, 25.
16. (f) Faber, K.; Riva, S. Synthesis 1992, 895.
17. (g) Hailing, P. J. Enzyme Microb. Technol. 1994, 16, 178.
18. (h) Koskinen, A. M. P.; Klibanov, A. M., Eds. Enzymatic Reactions in Organic Media; Blackie: London. 1996.
19. For reviews, see: (a) Wescott, C. R.; Klibanov, A. M. Biochim. Biophys. Acta 1994, 1206, 1. (b) Carrea, G.; Ottolina, G.; Riva, S. Trends Biotechnol, 1995, 13, 63.
20. For reviews, see: (a) Wescott, C. R.; Klibanov, A. M. Biochim. Biophys. Acta 1994, 1206, 1. (b) Carrea, G.; Ottolina, G.; Riva, S. Trends Biotechnol, 1995, 13, 63.
21. (a) Wescott, C, R.; Klibanov, A. M. J. Am. Chem. Soc. 1993, 115, 1629.
22. (b) Wescott, C. R.; Klibanov, A. M. J. Am. Chem. Soc. 1993, 115, 10362.
23. UNIFAC is a computational method for the estimation of Rault's law activity coefficients. Being a group contribution method, it can calculate activity coefficients in systems for which there is no experimental data by assessing the individual contribution of each chemical group which makes up the system. Use of this method requires three types of parameters for each group in the system: the group's surface area, the volume of the group, and empirically determined parameters which reflect the free energy of interaction between a given group and every other group in the system, (a) Fredenslund, A.; Gmehling, J.; Rasmussen, P. Vapor-Liquid Equilibria Using UNIFAC; Elsevier: New York, 1977. (b) Steen, S.-J.; Bärbel, K.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1979, 18, 714. (c) Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Process Des. Dev. 1982. 21, 118. (d) Macedo, E. A.; Weidlich, U.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1983, 22, 678. (e) Teigs, D.: Gmehling, J.; Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Res. 1987, 26, 159. (f) Hansen, H. K.; Rasmussen, P.; Schiller, M.; Gmehling, J. Ind. Eng. Chem. Res. 1991, 30, 2355.
24. UNIFAC is a computational method for the estimation of Rault's law activity coefficients. Being a group contribution method, it can calculate activity coefficients in systems for which there is no experimental data by assessing the individual contribution of each chemical group which makes up the system. Use of this method requires three types of parameters for each group in the system: the group's surface area, the volume of the group, and empirically determined parameters which reflect the free energy of interaction between a given group and every other group in the system, (a) Fredenslund, A.; Gmehling, J.; Rasmussen, P. Vapor-Liquid Equilibria Using UNIFAC; Elsevier: New York, 1977. (b) Steen, S.-J.; Bärbel, K.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1979, 18, 714. (c) Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Process Des. Dev. 1982. 21, 118. (d) Macedo, E. A.; Weidlich, U.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1983, 22, 678. (e) Teigs, D.: Gmehling, J.; Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Res. 1987, 26, 159. (f) Hansen, H. K.; Rasmussen, P.; Schiller, M.; Gmehling, J. Ind. Eng. Chem. Res. 1991, 30, 2355.
25. UNIFAC is a computational method for the estimation of Rault's law activity coefficients. Being a group contribution method, it can calculate activity coefficients in systems for which there is no experimental data by assessing the individual contribution of each chemical group which makes up the system. Use of this method requires three types of parameters for each group in the system: the group's surface area, the volume of the group, and empirically determined parameters which reflect the free energy of interaction between a given group and every other group in the system, (a) Fredenslund, A.; Gmehling, J.; Rasmussen, P. Vapor-Liquid Equilibria Using UNIFAC; Elsevier: New York, 1977. (b) Steen, S.-J.; Bärbel, K.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1979, 18, 714. (c) Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Process Des. Dev. 1982. 21, 118. (d) Macedo, E. A.; Weidlich, U.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1983, 22, 678. (e) Teigs, D.: Gmehling, J.; Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Res. 1987, 26, 159. (f) Hansen, H. K.; Rasmussen, P.; Schiller, M.; Gmehling, J. Ind. Eng. Chem. Res. 1991, 30, 2355.
26. UNIFAC is a computational method for the estimation of Rault's law activity coefficients. Being a group contribution method, it can calculate activity coefficients in systems for which there is no experimental data by assessing the individual contribution of each chemical group which makes up the system. Use of this method requires three types of parameters for each group in the system: the group's surface area, the volume of the group, and empirically determined parameters which reflect the free energy of interaction between a given group and every other group in the system, (a) Fredenslund, A.; Gmehling, J.; Rasmussen, P. Vapor-Liquid Equilibria Using UNIFAC; Elsevier: New York, 1977. (b) Steen, S.-J.; Bärbel, K.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1979, 18, 714. (c) Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Process Des. Dev. 1982. 21, 118. (d) Macedo, E. A.; Weidlich, U.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1983, 22, 678. (e) Teigs, D.: Gmehling, J.; Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Res. 1987, 26, 159. (f) Hansen, H. K.; Rasmussen, P.; Schiller, M.; Gmehling, J. Ind. Eng. Chem. Res. 1991, 30, 2355.
27. UNIFAC is a computational method for the estimation of Rault's law activity coefficients. Being a group contribution method, it can calculate activity coefficients in systems for which there is no experimental data by assessing the individual contribution of each chemical group which makes up the system. Use of this method requires three types of parameters for each group in the system: the group's surface area, the volume of the group, and empirically determined parameters which reflect the free energy of interaction between a given group and every other group in the system, (a) Fredenslund, A.; Gmehling, J.; Rasmussen, P. Vapor-Liquid Equilibria Using UNIFAC; Elsevier: New York, 1977. (b) Steen, S.-J.; Bärbel, K.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1979, 18, 714. (c) Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Process Des. Dev. 1982. 21, 118. (d) Macedo, E. A.; Weidlich, U.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1983, 22, 678. (e) Teigs, D.: Gmehling, J.; Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Res. 1987, 26, 159. (f) Hansen, H. K.; Rasmussen, P.; Schiller, M.; Gmehling, J. Ind. Eng. Chem. Res. 1991, 30, 2355.
28. UNIFAC is a computational method for the estimation of Rault's law activity coefficients. Being a group contribution method, it can calculate activity coefficients in systems for which there is no experimental data by assessing the individual contribution of each chemical group which makes up the system. Use of this method requires three types of parameters for each group in the system: the group's surface area, the volume of the group, and empirically determined parameters which reflect the free energy of interaction between a given group and every other group in the system, (a) Fredenslund, A.; Gmehling, J.; Rasmussen, P. Vapor-Liquid Equilibria Using UNIFAC; Elsevier: New York, 1977. (b) Steen, S.-J.; Bärbel, K.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1979, 18, 714. (c) Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Process Des. Dev. 1982. 21, 118. (d) Macedo, E. A.; Weidlich, U.; Gmehling, J.; Rasmussen, P. Ind. Eng. Chem. Process Des. Dev. 1983, 22, 678. (e) Teigs, D.: Gmehling, J.; Rasmussen, P.; Fredenslund, A. Ind. Eng. Chem. Res. 1987, 26, 159. (f) Hansen, H. K.; Rasmussen, P.; Schiller, M.; Gmehling, J. Ind. Eng. Chem. Res. 1991, 30, 2355.
29. Ke, T.; Wescott, C. R.; Klibanov, A. M. J. Am. Chem. Soc. 1996, 118, 3366.
30. Such cross-linked crystals of various enzymes have been employed as robust catalysts in synthetic transformations: (a) St. Clair, N. L.; Navia, M. A. J. Am. Chem. Soc. 1992, 114, 7314. (b) Sobolov, S. B.; Bartoszko-Malik, A.; Oeschger, T. R.; Monlelbano, M. M. Tetrahedron Lett. 1994, 35, 7751. (c) Persichetti, R. A.; St. Clair, N. L.; Griffith, J. P.; Navia, M. A.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 2732. (d) Lalonde, J. J.; Govardhan, C.; Khalaf, N.; Martinez, A. G.; Visuri, K.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 6845. (e) Sobolov, S. B.; Leonida, M. D.; Bartoszko-Malik, A.; Veivodov, K. I.; McKinney, F.; Kim, J.; Fry, A. J. J. Org. Chem. 1996, 61, 2125. (f) Schmitke, J. L.; Wescott, C. R.: Klibanov, A. M. J. Am. Chem. Soc. 1996, 118, 3360.
31. Such cross-linked crystals of various enzymes have been employed as robust catalysts in synthetic transformations: (a) St. Clair, N. L.; Navia, M. A. J. Am. Chem. Soc. 1992, 114, 7314. (b) Sobolov, S. B.; Bartoszko-Malik, A.; Oeschger, T. R.; Monlelbano, M. M. Tetrahedron Lett. 1994, 35, 7751. (c) Persichetti, R. A.; St. Clair, N. L.; Griffith, J. P.; Navia, M. A.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 2732. (d) Lalonde, J. J.; Govardhan, C.; Khalaf, N.; Martinez, A. G.; Visuri, K.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 6845. (e) Sobolov, S. B.; Leonida, M. D.; Bartoszko-Malik, A.; Veivodov, K. I.; McKinney, F.; Kim, J.; Fry, A. J. J. Org. Chem. 1996, 61, 2125. (f) Schmitke, J. L.; Wescott, C. R.: Klibanov, A. M. J. Am. Chem. Soc. 1996, 118, 3360.
32. Such cross-linked crystals of various enzymes have been employed as robust catalysts in synthetic transformations: (a) St. Clair, N. L.; Navia, M. A. J. Am. Chem. Soc. 1992, 114, 7314. (b) Sobolov, S. B.; Bartoszko-Malik, A.; Oeschger, T. R.; Monlelbano, M. M. Tetrahedron Lett. 1994, 35, 7751. (c) Persichetti, R. A.; St. Clair, N. L.; Griffith, J. P.; Navia, M. A.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 2732. (d) Lalonde, J. J.; Govardhan, C.; Khalaf, N.; Martinez, A. G.; Visuri, K.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 6845. (e) Sobolov, S. B.; Leonida, M. D.; Bartoszko-Malik, A.; Veivodov, K. I.; McKinney, F.; Kim, J.; Fry, A. J. J. Org. Chem. 1996, 61, 2125. (f) Schmitke, J. L.; Wescott, C. R.: Klibanov, A. M. J. Am. Chem. Soc. 1996, 118, 3360.
33. Such cross-linked crystals of various enzymes have been employed as robust catalysts in synthetic transformations: (a) St. Clair, N. L.; Navia, M. A. J. Am. Chem. Soc. 1992, 114, 7314. (b) Sobolov, S. B.; Bartoszko-Malik, A.; Oeschger, T. R.; Monlelbano, M. M. Tetrahedron Lett. 1994, 35, 7751. (c) Persichetti, R. A.; St. Clair, N. L.; Griffith, J. P.; Navia, M. A.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 2732. (d) Lalonde, J. J.; Govardhan, C.; Khalaf, N.; Martinez, A. G.; Visuri, K.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 6845. (e) Sobolov, S. B.; Leonida, M. D.; Bartoszko-Malik, A.; Veivodov, K. I.; McKinney, F.; Kim, J.; Fry, A. J. J. Org. Chem. 1996, 61, 2125. (f) Schmitke, J. L.; Wescott, C. R.: Klibanov, A. M. J. Am. Chem. Soc. 1996, 118, 3360.
34. Such cross-linked crystals of various enzymes have been employed as robust catalysts in synthetic transformations: (a) St. Clair, N. L.; Navia, M. A. J. Am. Chem. Soc. 1992, 114, 7314. (b) Sobolov, S. B.; Bartoszko-Malik, A.; Oeschger, T. R.; Monlelbano, M. M. Tetrahedron Lett. 1994, 35, 7751. (c) Persichetti, R. A.; St. Clair, N. L.; Griffith, J. P.; Navia, M. A.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 2732. (d) Lalonde, J. J.; Govardhan, C.; Khalaf, N.; Martinez, A. G.; Visuri, K.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 6845. (e) Sobolov, S. B.; Leonida, M. D.; Bartoszko-Malik, A.; Veivodov, K. I.; McKinney, F.; Kim, J.; Fry, A. J. J. Org. Chem. 1996, 61, 2125. (f) Schmitke, J. L.; Wescott, C. R.: Klibanov, A. M. J. Am. Chem. Soc. 1996, 118, 3360.
35. Such cross-linked crystals of various enzymes have been employed as robust catalysts in synthetic transformations: (a) St. Clair, N. L.; Navia, M. A. J. Am. Chem. Soc. 1992, 114, 7314. (b) Sobolov, S. B.; Bartoszko-Malik, A.; Oeschger, T. R.; Monlelbano, M. M. Tetrahedron Lett. 1994, 35, 7751. (c) Persichetti, R. A.; St. Clair, N. L.; Griffith, J. P.; Navia, M. A.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 2732. (d) Lalonde, J. J.; Govardhan, C.; Khalaf, N.; Martinez, A. G.; Visuri, K.; Margolin, A. L. J. Am. Chem. Soc. 1995, 117, 6845. (e) Sobolov, S. B.; Leonida, M. D.; Bartoszko-Malik, A.; Veivodov, K. I.; McKinney, F.; Kim, J.; Fry, A. J. J. Org. Chem. 1996, 61, 2125. (f) Schmitke, J. L.; Wescott, C. R.: Klibanov, A. M. J. Am. Chem. Soc. 1996, 118, 3360.
36. Reynolds, J. E. F., Ed. Martindale, the Extra Pharmacopoeia, 28th ed.; Pharmaceutical Press: London, 1982; p 304.
37. 10 then it also should be the same in other organic solvents because the differences in physicochemical properties among them are less than those between water and hexane. Furthermore, cross-linking followed by placement in acetonitrile does not affect the structure of two other serine proteases, subtilisin Carlsberg (Fitzpatrick, P. A.; Steinmetz, A. C. U.; Ringe, D.; Klibanov, A. M. Proc. Natl. Acad. Sci. U.S.A. 1993, 90, 8653. Fitzpatrick, P. A.; Ringe, D.; Klibanov, A. M. Biochem. Biophys. Res. Commun. 1994, 198, 675) and porcine pancreatic elastase (Allen, K. N.; Bellamacina, C. R.; Ding, X.; Jeffery, C. J.; Mattos, C.; Petsko, G. A.; Ringe, D. J. Phys. Chem. 1996, 100, 2605).
38. 10 then it also should be the same in other organic solvents because the differences in physicochemical properties among them are less than those between water and hexane. Furthermore, cross-linking followed by placement in acetonitrile does not affect the structure of two other serine proteases, subtilisin Carlsberg (Fitzpatrick, P. A.; Steinmetz, A. C. U.; Ringe, D.; Klibanov, A. M. Proc. Natl. Acad. Sci. U.S.A. 1993, 90, 8653. Fitzpatrick, P. A.; Ringe, D.; Klibanov, A. M. Biochem. Biophys. Res. Commun. 1994, 198, 675) and porcine pancreatic elastase (Allen, K. N.; Bellamacina, C. R.; Ding, X.; Jeffery, C. J.; Mattos, C.; Petsko, G. A.; Ringe, D. J. Phys. Chem. 1996, 100, 2605).
39. 10 then it also should be the same in other organic solvents because the differences in physicochemical properties among them are less than those between water and hexane. Furthermore, cross-linking followed by placement in acetonitrile does not affect the structure of two other serine proteases, subtilisin Carlsberg (Fitzpatrick, P. A.; Steinmetz, A. C. U.; Ringe, D.; Klibanov, A. M. Proc. Natl. Acad. Sci. U.S.A. 1993, 90, 8653. Fitzpatrick, P. A.; Ringe, D.; Klibanov, A. M. Biochem. Biophys. Res. Commun. 1994, 198, 675) and porcine pancreatic elastase (Allen, K. N.; Bellamacina, C. R.; Ding, X.; Jeffery, C. J.; Mattos, C.; Petsko, G. A.; Ringe, D. J. Phys. Chem. 1996, 100, 2605).
40. (a) Yennawar, N. H.; Yennawar, H. P.; Farber, G. K. Biochemistry 1994, 33, 7326.
41. (b) Yennawar, H. P.; Yennawar, N. H.; Farber, G. K. J. Am. Chem. Soc. 1995, 117, 577.
42. Boudart, M.; Burwell, R. L. In Techniques in Chemistry, 3rd ed.; Lewis, E. S., Ed.; Wiley: New York, 1973; Vol. 6, Chapter 12.
43. Chen, C-S.; Fujimoto, Y.; Girdaukas, G.; Sih, C. J. J. Am. Chem. Soc. 1982, 104, 7294.
44. 4,6,7f
45. Connolly, M. L. Science 1983, 221, 709.
46. 5
47. Stoddard, B. L.; Bruhnke, J.; Porter, N.; Ringe, D.; Petsko, G. A. Biochemistry 1990, 29, 4871.
48. Laitinen, H. A.; Harris, W. E. Chemical Analysis, 2nd ed.; McGraw-Hill: New York, 1975; pp 361-363.
49. Warshel, A.; Naray-Szabo, G.; Sussman, F.; Hwang, J.-K. Biochemistry 1989, 28, 3629.
50. This work was financially supported by NIH grant GM39794. H.N. gratefully acknowledges a fellowship from the Tokyo Metropolitan Government.