β-Secondary kinetic isotope effects in the clavaminate synthase- catalyzed oxidative cyclization of proclavaminic acid and in related azetidinone model reactions

Journal of the American Chemical Society

Volumn 121, Issue 49, 1999, Pages 11356-11368

  Iwata Reuyl, Dirk ^a,b   Basak, Amit ^a,c   Townsend, Craig A ^a  

^a JOHNS HOPKINS UNIVERSITY   (United States)

^b PORTLAND STATE UNIVERSITY   (United States)

^c INDIAN INSTITUTE OF TECHNOLOGY   (India)

Author keywords

[No Author keywords available]

Indexed keywords

2 OXOGLUTARIC ACID; AZETIDINONE DERIVATIVE; BETA LACTAMASE; CARBON 14; CLAVULANIC ACID; OXYGENASE; TRITIUM;

ACIDITY; ANTIBIOTIC RESISTANCE; ARTICLE; CATALYSIS; CHEMICAL REACTION KINETICS; CYCLIZATION; ENZYME INHIBITION; ISOTOPE LABELING;

EID: 0033572748     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja992649d     Document Type: Article

References (43)

1. Busby, R. W.; Chang, M. D.-T.; Busby, R. C.; Wimp, J.; Townsend, C. A. J. Biol. Chem. 1995, 270, 4262-4269.
2. Busby, R. W.; Townsend, C. A. Bioorg. Med. Chem. 1996, 4, 1059-1064.
3. Pavel, E. G.; Zhou, J.; Busby, R. W.; Gunsior, M.; Townsend, C. A.; Solomon, E. I. J. Am. Chem. Soc. 1998, 120, 743-753.
4. Zhou, J.; Gunsior, M.; Bachmann, B. O.; Townsend, C. A.; Solomon, E. I. J. Am. Chem. Soc. 1998, 120, 13539-13540.
5. Roach, P. L.; Clifton, I. J.; Hensgens, C. M. H.; Shibata, N.; Schofield, C. J.; Hajdu, J.; Baldwin, J. E. Nature 1997, 387, 827-830.
6. Salowe, S. P.; Marsh, E. N.; Townsend, C. A. Biochemistry 1990, 29, 6499-6508.
7. Salowe, S. P.; Krol, W. J.; Iwata-Reuyl, D.; Townsend, C. A. Biochemistry 1991, 30, 2281-2292.
8. Northrup, D. B. In Isotope Effects in Enzyme-Catalyzed Reactions; Cleland, W. W., O'Leary, M. H., Northrup, D. B., Eds.; University Park Press: Baltimore, MD, 1977; pp 122-152.
9. Basak, A.; Salowe, S. P.; Townsend, C. A. J. Am. Chem. Soc. 1990, 112, 1654-1656.
10. Baldwin, J. E.; Adlington, R. M.; Bryans, J. S.; Bringhen, A. O.; Coates, J. B.; Crouch, N. P.; Lloyd, M. D.; Schofield, C. J.; Elson, S. W.; Baggaley, K. H.; Cassells, R.; Nicholson, N. J. Chem. Soc., Chem. Commun. 1990, 617-619.
11. Baldwin, J. E.; Adlington, R. M.; Bryans, J. S.; Bringhen, A. O.; Coates, J. B.; Crouch, N. P.; Lloyd, M. D.; Schofield, C. J.; Elson, S. W.; Baggaley, K. H.; Cassels, R.; Nicholson, N. H. Tetrahedron 1991, 47, 4089-4100.
12. Blanchard, J. S.; Englard, S. Biochemistry 1983, 22, 5922-5929.
13. Baldwin, J. E.; Bradley, M. Chem. Rev. 1990, 90, 1079-1088.
14. Iwata-Reuyl, D.; Basak, A.; Silverman, L. S.; Engle, C. A.; Townsend, C. A. J. Nat. Prod. 1993, 56, 1373-1396.
15. Sunko, D. E.; Hehre, W. J. Prog. Phys. Org. Chem. 1983, 16, 205-246.
16. Melander, L.; Saunders, W. H. Reaction Rates of Isotopic Molecules; Wiley: New York, 1980; pp 170-201.
17. Symons, M. C. R. Tetrahedron 1962, 18, 333-341.
18. 3, will be perturbed to increase p-character to ligands in the strained, four-membered ring, and increase s-character (increase bond strength) to the C-H bonds undergoing change in the course of reaction.
19. Cleland, W. W. In Secondary and Solvent Isotope Effects; Buncel, E., Lee, C. C., Eds.; Elsevier: Amsterdam, 1987; pp 61-113.
20. Olafson, R. A.; Morrison, D. S.; Banerji, A. J. Org. Chem. 1984, 49, 2652-2653.
21. Lambert, J. B. Tetrahedron 1990, 46, 2677-2689.
22. All substrates were planned to be equally labeled with deuterium at both C-3 methylene positions to amplify the β-isotope effect. While the CS-catalyzed oxidative cyclization is a stereospecific process and the β-secondary kinetic isotope effect may differ depending on which hydrogen (deuterium) at C-3′ is syn clinal or gauche to the breaking C-H bond, this stereochemical distinction will escape analysts. However, if a fully developed p-orbital exists at the transition state, the effects of both C-3 deuteria will be the same.
23. Krol, W. J.; Mao, S.-s.; Steele, D. L.; Townsend, C. A. J. Org. Chem. 1991, 56, 728-731.
24. Ojima, I.; Komata, T.; Qiu, X. J. Am. Chem. Soc. 1990, 112, 770-774.
25. Shibasaki, M.; Nishida, A.; Ikegami, S. J. Chem. Soc., Chem. Commun. 1982, 1324-1325.
26. Clauss, K.; Grimm, D.; Possel, G. Liebigs Ann. Chem. 1974, 539-560.
27. Kobayashi, T.; Iwano, Y.; Hirai, K. Chem. Pharm. Bull. 1978, 26, 1761-1767.
28. Chatgilialoglu, C.; Griller, D.; Lesage, M. J. Org. Chem. 1988, 53, 3641-3642.
29. Bentley, P. H.; Brooks, G.; Gilpin, M. L.; Hunt, E. Tetrahedron Lett. 1979, 1889-1890.
30. Neumann, W. P. Synthesis 1987, 665-683.
31. Koppel, G. A.; McShane, L.; Jose, F.; Cooper, R. D. G. J. Am. Chem. Soc. 1978, 100, 3933-3935.
32. Vogel, P. C.; Stern, M. J. J. Chem. Phys. 1971, 54, 779-796.
33. Ojima, I.; Kogure, T. Tetrahedron Lett. 1973, 2475-2478.
34. Kursanov, D. N.; Loim, N. M.; Baranova, V. A.; Moiseeva, L. V.; Zalukaev, L. P.; Parnes, Z. N. Synthesis 1973, 420-422.
35. Radom, L.; Paviot, J.; Pople, J. A. J. Chem. Soc., Chem. Commun. 1974, 58-60.
36. This is likely to be quite variable and not accurately represented by a macroscopic value (Warshel, A. J. Biol. Chem. 1998, 273, 27035-27038). Nonetheless, macroscopic dielectrics for active sites have been variously estimated to range from 4 to 40 with 10 taken as an average value (Warshel, A. Annu. Rev. Biophys. Biophys. Chem. 1991, 20, 267-298). Jordan has experimentally determined an ∈ = 13-15 in a very recent example (Jordan, F.; Li, H.; Brown, A. Biochemists 1999, 38, 6369-6373).
37. This is likely to be quite variable and not accurately represented by a macroscopic value (Warshel, A. J. Biol. Chem. 1998, 273, 27035-27038). Nonetheless, macroscopic dielectrics for active sites have been variously estimated to range from 4 to 40 with 10 taken as an average value (Warshel, A. Annu. Rev. Biophys. Biophys. Chem. 1991, 20, 267-298). Jordan has experimentally determined an ∈ = 13-15 in a very recent example (Jordan, F.; Li, H.; Brown, A. Biochemists 1999, 38, 6369-6373).
38. This is likely to be quite variable and not accurately represented by a macroscopic value (Warshel, A. J. Biol. Chem. 1998, 273, 27035-27038). Nonetheless, macroscopic dielectrics for active sites have been variously estimated to range from 4 to 40 with 10 taken as an average value (Warshel, A. Annu. Rev. Biophys. Biophys. Chem. 1991, 20, 267-298). Jordan has experimentally determined an ∈ = 13-15 in a very recent example (Jordan, F.; Li, H.; Brown, A. Biochemists 1999, 38, 6369-6373).
39. Townsend, C. A. Biochem. Soc. Trans. 1993, 21, 208-213.
40. Brookhart, M.; Green, M. L. H. J. Organomet. Chem. 1983, 250, 395-408.
41. The microscopic reverse of this process would be protodemetalation. For the case of protodemercurations, β-secondary kinetic isotope effects have been observed to be very low or nonexistent, in contrast to the CS-catalyzed reaction (Bencivengo, D. J.; Brownawell, M. L.; Li, M.-Y.; San Filippo, Jr., J. J. Am. Chem. Soc. 1984, 106, 3703-3704).
42. Baldwin, J. E.; Adlington, R. M.; Marquess, D. G.; Pitt, A. R.; Porter, M. J.; Russell, A. T. Tetrahedron 1996, 52, 2537-2556.
43. Baldwin, J. E.; Adlington, R. M.; Marquess, D. G.; Pitt. A. R.; Russell, A. T. J. Chem. Soc., Chem. Commun. 1991, 856-858.