A solvation-assisted model for estimating anomeric reactivity. Predicted versus observed trends in hydrolysis of n-pentenyl glycosides

Journal of Organic Chemistry

Volumn 61, Issue 16, 1996, Pages 5280-5289

  Andrews, C Webster ^a,c   Rodebaugh, Robert ^b   Fraser Reid, Bert ^b  

^a GLAXOSMITHKLINE   (United States)

^b DUKE UNIVERSITY   (United States)

^c Nat Prod Glycotechnology Res I   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000252665     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9601223     Document Type: Article

References (45)

1. We are grateful to the National Science Foundation (CHE 9311356) and Glaxo Research Institute for financial support of this work.
2. For some recent reviews on oligosaccharide syntheses, see: Khan, S. H., O'Neil, R. A., Rahman, A., Eds. Modern Methods in Carbohydrate Synthesis; Harwood Academic Publishers: Amsterdam 1996. Fraser-Reid, B.; Madsen, R.; Campbell, A. S.; Roberts, C.; Merritt, J. R. In Chemical Synthesis of Oligosaccharides; Hecht, S. M., Ed.; Oxford University Press: Oxford, 1995, in press. Khan, S. H.; Hindsgaul, O. In Frontiers in Molecular Biology; Fukuda, M., Hindsgaul, O., Eds.; IRL Press: Oxford, 1994; p 206. Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 15031. Bonoub, J.; Boullanger, P.; Lafont, D. Chem. Rev. 1992, 92, 1167.
3. For some recent reviews on oligosaccharide syntheses, see: Khan, S. H., O'Neil, R. A., Rahman, A., Eds. Modern Methods in Carbohydrate Synthesis; Harwood Academic Publishers: Amsterdam 1996. Fraser-Reid, B.; Madsen, R.; Campbell, A. S.; Roberts, C.; Merritt, J. R. In Chemical Synthesis of Oligosaccharides; Hecht, S. M., Ed.; Oxford University Press: Oxford, 1995, in press. Khan, S. H.; Hindsgaul, O. In Frontiers in Molecular Biology; Fukuda, M., Hindsgaul, O., Eds.; IRL Press: Oxford, 1994; p 206. Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 15031. Bonoub, J.; Boullanger, P.; Lafont, D. Chem. Rev. 1992, 92, 1167.
4. For some recent reviews on oligosaccharide syntheses, see: Khan, S. H., O'Neil, R. A., Rahman, A., Eds. Modern Methods in Carbohydrate Synthesis; Harwood Academic Publishers: Amsterdam 1996. Fraser-Reid, B.; Madsen, R.; Campbell, A. S.; Roberts, C.; Merritt, J. R. In Chemical Synthesis of Oligosaccharides; Hecht, S. M., Ed.; Oxford University Press: Oxford, 1995, in press. Khan, S. H.; Hindsgaul, O. In Frontiers in Molecular Biology; Fukuda, M., Hindsgaul, O., Eds.; IRL Press: Oxford, 1994; p 206. Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 15031. Bonoub, J.; Boullanger, P.; Lafont, D. Chem. Rev. 1992, 92, 1167.
5. For some recent reviews on oligosaccharide syntheses, see: Khan, S. H., O'Neil, R. A., Rahman, A., Eds. Modern Methods in Carbohydrate Synthesis; Harwood Academic Publishers: Amsterdam 1996. Fraser-Reid, B.; Madsen, R.; Campbell, A. S.; Roberts, C.; Merritt, J. R. In Chemical Synthesis of Oligosaccharides; Hecht, S. M., Ed.; Oxford University Press: Oxford, 1995, in press. Khan, S. H.; Hindsgaul, O. In Frontiers in Molecular Biology; Fukuda, M., Hindsgaul, O., Eds.; IRL Press: Oxford, 1994; p 206. Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 15031. Bonoub, J.; Boullanger, P.; Lafont, D. Chem. Rev. 1992, 92, 1167.
6. For some recent reviews on oligosaccharide syntheses, see: Khan, S. H., O'Neil, R. A., Rahman, A., Eds. Modern Methods in Carbohydrate Synthesis; Harwood Academic Publishers: Amsterdam 1996. Fraser-Reid, B.; Madsen, R.; Campbell, A. S.; Roberts, C.; Merritt, J. R. In Chemical Synthesis of Oligosaccharides; Hecht, S. M., Ed.; Oxford University Press: Oxford, 1995, in press. Khan, S. H.; Hindsgaul, O. In Frontiers in Molecular Biology; Fukuda, M., Hindsgaul, O., Eds.; IRL Press: Oxford, 1994; p 206. Toshima, K.; Tatsuta, K. Chem. Rev. 1993, 15031. Bonoub, J.; Boullanger, P.; Lafont, D. Chem. Rev. 1992, 92, 1167.
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13. See, for example: Roy, R.; Anderson, F. O.; Letellier, M. Tetrahedron Lett. 1992, 33, 6053. Sliedregt, L. A. J. M.; Zegelaar-Jaarsvald, K.; van der Marel, G. A.; van Boom, J. H. Synlett 1993, 335. Boons, G. J.; Isles, S. Tetrahedron Lett. 1994, 35, 3593.
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20. Deslongchamps, P. Stereoelectronic Effects in Organic Chemistry; Pergamon Press: New York, 1983; pp 30-35. Intramolecular Strategies and Stereochemical Effects: Glycosides and Orthoesters Hydrolysis Revisited. In The Anomeric Effect and Associated Stereoelectronic Effects; Thatcher, G. R. J., Ed.; ACS Symposium Series 539, American Chemical Society: Washington, D.C., 1993.
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36. 25,26 The principal error is that electron correlation is ignored at the Hartree-Fock level for both ground states and oxocarbenium ions. However, the change in relative activation energy from molecule to molecule is quite large relative to the rate changes and reflects the fact that some errors are not cancelled out, as well as the fact that real electronic and steric differences exist. In the end, the relative ordering, which is what this study requires, is satisfactory. These relative activation energies (kinetic properties) should not be compared against known ground state energy differences (thermodynamic properties).
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40. Wiberg, K. B.; Murcko, M. A. J. Am. Chem. Soc. 1989, 111, 4821. Jeffrey, G. A.; Pople, J. A.; Binkley, J. S.; Vishveshwara, S. J. Am. Chem. Soc. 1978, 100, 373. Andrews, C. W. Ph.D. Thesis, Duke University, 1989.
41. Due to the cyclic nature of these compounds, conformational differences between solution and in vacuo are expected to be small. This allowed us to do in vacuo quantum mechanics with the expectation that the same conformation would be obtained in aqueous solution. This will not always be the case. A reviewer points out that a general scheme for more flexible molecules would be to do geometry optimization (or indeed, conformational searching) using one of the continuum solvation models that are now available in semiempirical or ab initio codes. A further assumption inherent in this work is that the single minimized conformation found for each structure (formally at 0 K) represents the ensemble of structures at the temperature of the rate determination. This is also reasonable due to the cyclic nature of the compounds. An additional point relates to the use of 6-31G* charges but not energies. High-level charges are required to obtain accurate solvation energies from the GB/SA model. Since the charges are not expected to change a great deal with geometry optimization, we used 6-31G*//3-21G charges and did not pursue 6-31G* geometry optimization (and more importantly, could not afford the cpu time involved). We did not use the single-point 6-31G* energies in the rate correlations because these energies are not minimized on the 6-31G* energy surface.
42. Mohamadi, F.; Richards, N. G. J.; Guida, W. C.; Liskamp, R.; Caufield, C.; Chang, G.; Hendrickson, T.; Still, W. C. J. Comput. Chem. 1990, 11, 440.
43. GB/SA solvation model: Still, W. C.; Tempczyk, A.; Hawley, R. C.; Hendrickson, T. J. Am. Chem. Soc. 1990, 112, 6127.
44. Frisch, M. J.; Trucks, G. W.; Head-Gordon, M.; Gill, P. M. W.; Wong, M. W.; Foresman, J. B.; Johnson, B. G.; Schegel, H. B.; Robb, M. A.; Replogel, E. S.; Gomperts, R.; Andres, J. L.; Raghavachari, K.; Binkley, J. S.; Gonzalez, C.; Martin, R. L.; Fox, D. J.; Defrees, D. J.; Baker, J.; Stewart, J. J. P.; Pople, J. A. Gaussian Inc., Pittsburgh, PA, 1992.
45. a in Figure 4. Note, this is not a traditional Arrhenius analysis involving variation of temperature.