Catalysis and acceleration of acyl transfer by aminocyclodextrins: A biomimetic system of use in enzyme modeling and drug design

Organic Letters

Volumn 1, Issue 6, 1999, Pages 829-832

  Ferguson, Colin G ^a   Thatcher, Gregory R J ^a  

^a QUEEN S UNIVERSITY   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLODEXTRIN; ESTER; FOSCARNET;

ARTICLE; CATALYSIS; CHEMICAL MODEL; CHEMISTRY; DRUG DESIGN; KINETICS; METABOLISM; MOLECULAR MIMICRY;

CATALYSIS; CYCLODEXTRINS; DRUG DESIGN; ESTERS; FOSCARNET; KINETICS; MODELS, CHEMICAL; MOLECULAR MIMICRY;

EID: 0033598259     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol9906211     Document Type: Article

References (31)

1. Breslow, R. Acc. Chem. Res. 1995, 28, 146, and references therein. Breslow, R. H.;Dong, A. Chem. Rev. 1998, 98, 1997, and references therein. Tee, O. S. Adv. Phys. Org. Chem. 1994, 29, 1, and references therein. D'Souza, V. T.; Bender, M. L. Acc. Chem. Res. 1987, 20, 146.
2. Breslow, R. Acc. Chem. Res. 1995, 28, 146, and references therein. Breslow, R. H.;Dong, A. Chem. Rev. 1998, 98, 1997, and references therein. Tee, O. S. Adv. Phys. Org. Chem. 1994, 29, 1, and references therein. D'Souza, V. T.; Bender, M. L. Acc. Chem. Res. 1987, 20, 146.
3. Breslow, R. Acc. Chem. Res. 1995, 28, 146, and references therein. Breslow, R. H.;Dong, A. Chem. Rev. 1998, 98, 1997, and references therein. Tee, O. S. Adv. Phys. Org. Chem. 1994, 29, 1, and references therein. D'Souza, V. T.; Bender, M. L. Acc. Chem. Res. 1987, 20, 146.
4. Breslow, R. Acc. Chem. Res. 1995, 28, 146, and references therein. Breslow, R. H.;Dong, A. Chem. Rev. 1998, 98, 1997, and references therein. Tee, O. S. Adv. Phys. Org. Chem. 1994, 29, 1, and references therein. D'Souza, V. T.; Bender, M. L. Acc. Chem. Res. 1987, 20, 146.
5. Kirby, A. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 707, and references therein.
6. McCracken, P. G.; Ferguson, C. G.; Vizitiu, D.; Walkinshaw, C. S.; Wang, Y.; Thatcher, G. R. J. J. Chem. Soc., Perkin Trans. 2 1999, 911.
7. Vizitiu, D.; Thatcher, G. R. J. J. Org. Chem. In press.
8. Eliseev, A. V.; Schneider, H. J. J. Am. Chem. Soc. 1994, 116, 6088.
9. Three examples of βACD catalysis have been reported in the literature, for H/D exchange [Binder, W. H.; Menger, F. M. Tetrahedron Lett. 1996, 8963] and for imine formation [Tagaki, W.; Yano, K.; Yamanaka, K.; Yamamoto, H.; Miyasaki, T. Tetrahedron Lett. 1990, 3897. Breslow, R.; Czarniecki, M. F.; Emert, J.; Hamaguchi, H. J. Am. Chem. Soc. 1980, 102, 2, 762].
10. Three examples of βACD catalysis have been reported in the literature, for H/D exchange [Binder, W. H.; Menger, F. M. Tetrahedron Lett. 1996, 8963] and for imine formation [Tagaki, W.; Yano, K.; Yamanaka, K.; Yamamoto, H.; Miyasaki, T. Tetrahedron Lett. 1990, 3897. Breslow, R.; Czarniecki, M. F.; Emert, J.; Hamaguchi, H. J. Am. Chem. Soc. 1980, 102, 2, 762].
11. Three examples of βACD catalysis have been reported in the literature, for H/D exchange [Binder, W. H.; Menger, F. M. Tetrahedron Lett. 1996, 8963] and for imine formation [Tagaki, W.; Yano, K.; Yamanaka, K.; Yamamoto, H.; Miyasaki, T. Tetrahedron Lett. 1990, 3897. Breslow, R.; Czarniecki, M. F.; Emert, J.; Hamaguchi, H. J. Am. Chem. Soc. 1980, 102, 2, 762].
12. Oberg, B. Pharmacol. Ther. 1989, 40, 213.
13. For example, see: (a) Noren, J. O.; Helgstrand, E.; Johansson, N. G.; Misiorny, A.; Stenning, G. J. Med. Chem. 1983, 26, 264.
14. (b) Gorin, B. I.; Ferguson, C. G.; Thatcher, G. R. J. Tetrahedron Lett. 1997, 2791.
15. (c) Briggs, A. D.; Camplo, M.; Freeman, S.; Lundstromm, J.; Pring, B. Tetrahedron 1996, 52, 14937, and references therein.
16. (a) Krol, E. S.; Thatcher G. R. J. J. Chem. Soc., Perkin Trans. 2 1993, 793.
17. (b) Krol, E. S.; Davis, J. M.; Thatcher, G. R. J. J. Chem. Soc., Chem. Commun. 1991, 118.
18. (c) Mitchell, A. G.; Nichols; D. Irwin, W. J.; Freeman, S. J. Chem. Soc., Perkin Trans. 2 1992, 1145.
19. (d) Thatcher G. R. J.; Krol, E. S.; Cameron D. R. J. Chem. Soc., Perkin Trans. 2 1994, 683.
20. All ACDs homogeneous and fully characterized: (a) Gorin, B. I.; Riopelle, R. J.; Thatcher, G. R. J. Tetrahedron Lett. 1996, 4647.
21. (b) Vizitiu, D.; Walkinshaw, C. S.; Gorin, B. I.; Thatcher, G. R. J. J. Org. Chem. 1997, 62, 8760.
22. + = 1103.4 Da/e).
23. 31P NMR: the hydrolysis and aminolysis products were formed in almost equivalent amounts while the ester product was the major product, the relative yield of which increased with the proportion of ACD to substrate. The assignment of the two different ACD-PFA adducts was based upon their chemical shift proximity to known PFA amides and alkyl diesters and ES-MS results.
24. obs) were calculated by software on the spectrometer.
25. At concentrations equimolar with ACD (2 mM). partial inhibition (20%) of the aminolysis reaction between 1 and αACD was observed with traditional cavity binding inhibitors (e.g. heptanediol, see: Tee, O. S.; Donga, R. A. J. Chem. Soc. Perkin Trans. 2 1996, 2763), as expected from the weak binding of hydrophobic molecules in the ACD cavity. Greater inhibition (50%) was observed with the polyvalent binding inhibitors, α,ω-nonanedioate and α,ω-octanedioate.
26. 3 fold greater than the background aminolysis in Tris buffer (Tris, 500 mM; KCl, 500 mM, 25 °C).
27. 31P NMR δ∼-7.8 ppm): Ferguson, C. G.; Thatcher, G. R. J. Synlett 1998, 1325.
28. Kirby has reported high EM values for amine catalysis of proton transfer in the Kemp elimination by a synzyme (Hollfelder, F.; Kirby, A. J.; Tawfik, D. S. J. Am. Chem. Soc. 1997 119, 9578) and lower values for catalysis by serum albumins [ref 18a].
29. For example, serum albumins and glycosaminoglycan sulfate binding domains: (a) Hollfelder, F.; Kirby, A. J.; Tawfik, D. S. Nature 1996, 383, 60. Carter, D. C.; Ho, J. X. Adv. Prot. Chem. 1994, 45, 153.
30. For example, serum albumins and glycosaminoglycan sulfate binding domains: (a) Hollfelder, F.; Kirby, A. J.; Tawfik, D. S. Nature 1996, 383, 60. Carter, D. C.; Ho, J. X. Adv. Prot. Chem. 1994, 45, 153.
31. (b) Borrajo, A. M. P.; Gorin, B. I.; Dostaler, S. M.; Riopelle, R. J.; Thatcher, G. R. J. Bioorg. Med. Chem. Lett. 1997, 7, 1185.