On the synergism between H 2O and a tetrahydropyran template in the regioselective cyclization of an epoxy alcohol

Journal of the American Chemical Society

Volumn 131, Issue 18, 2009, Pages 6383-6385

  Byers, Jeffery A ^a   Jamison, Timothy F ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CONFORMATIONAL DIFFERENCES; CYCLIZATIONS; EPOXY ALCOHOLS; FASTER REACTIONS; HYDROPHOBIC EFFECT; KINETIC CONTROL; KINETIC MEASUREMENT; NEUTRAL WATER; REGIO-SELECTIVE; TETRAHYDROPYRAN; WATER MOLECULE;

HYDROPHOBICITY; MOLECULES; OXYGEN; REACTION RATES;

CYCLIZATION;

ALCOHOL; CARBON; DIMETHYL SULFOXIDE; EPOXIDE; LITHIUM CHLORIDE; TETRAHYDROPYRAN DERIVATIVE; WATER; ALCOHOL DERIVATIVE; PYRAN DERIVATIVE;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; HYDROGEN BOND; HYDROPHOBICITY; KINETICS; SOLVATE; CHEMICAL STRUCTURE; CHEMISTRY;

ALCOHOLS; CYCLIZATION; EPOXY COMPOUNDS; KINETICS; MOLECULAR STRUCTURE; PYRANS; WATER;

EID: 66149116790     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9004909     Document Type: Article

References (37)

1. Vilotijevic, I.; Jamison, T. F. Science 2007, 317, 1189.
2. In this context, a template is defined as a functional group or collection of functional groups that favors otherwise atypical reactivity and/or selectivity.
3. Nakanishi, K. Toxicon 1985, 23, 473.
4. Alternative methods for regioselective epoxy alcohol cyclizations: (a) Nicolaou, K. C.; Prasad, C. V. C.; Somers, P. K.; Hwang, C.-K. J. Am. Chem. Soc. 1989, 111, 5330.
5. Janda, K. D.; Shevlin, C. G.; Lerner, R. A. Science 1993, 259, 490.
6. Fujiwara, K.; Tokiwano, T.; Murai, A. Tetrahedron Lett. 1995, 36, 8063.
7. Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1996, 118, 8158.
8. Wu, M. H.; Hansen, K. B.; Jacobsen, E. N. Angew. Chem., Int. Ed. 1999, 38, 2012.
9. Heffron, T. P.; Jamison, T. F. Org. Lett. 2003, 5, 2339.
10. Valentine, J. C.; McDonald, F. E.; Neiwert, W. A.; Hardcastle, K. I. J. Am. Chem. Soc. 2005, 127, 4586.
11. Simpson, G. L.; Heffron, T. P.; Merino, E.; Jamison, T. F. J. Am. Chem. Soc. 2006, 128, 1056.
12. Narayan, S.; Muldoon, J.; Finn, M. G.; Fokin, V. V.; Kolb, H. C.; Sharpless, B. K. Angew. Chem., Int. Ed. 2005, 44, 3275.
13. Jung, Y.; Marcus, R. A. J. Am. Chem. Soc. 2007, 129, 5492.
14. Tascioglu, S. Tetrahedron 1996, 52, 11113.
15. Dwars, T.; Paetzold, E.; Oehme, G. Angew. Chem., Int. Ed. 2005, 44, 7174.
16. Breslow, R.; Maitra, U.; Rideout, D. Tetrahedron Lett. 1983, 24, 1901.
17. Grieco, P. A.; Garner, P.; He, Z.-M. Tetrahedron Lett. 1983, 24, 1897.
18. Breslow, R. Acc. Chem. Res. 1991, 24, 159. (d) Breslow, R. Acc. Chem. Res. 2004, 37, 471.
19. Spectra were assigned in analogy to C-glycosides, which show similar conformational preferences: (a) Babirad, S. A.; Wang, Y.; Goekjian, P. G.; Kishi, Y. J. Org. Chem. 1987, 52, 4825.
20. Houk, K. N.; Eksterowicz, J. E.; Wu, Y. D.; Fuglesang, C. D.; Mitchell, D. B. J. Am. Chem. Soc. 1993, 115, 4170.
21. Leading and most relevant examples: (a) Hammond, G. S.; Reeder, C. E.; Fang, F. T.; Kochi, J. K. J. Am. Chem. Soc. 1958, 80, 568.
22. Olavi, P.; Virtanen, I. Suom. Chem. B 1965, B38, 135.
23. Olavi, P.; Virtanen, I. Suom. Chem. B 1966, B39, 115.
24. Hand, E. S.; Jencks, W. P. J. Am. Chem. Soc. 1975, 97, 6221.
25. Henderson, J. W.; Haake, P. J. Org. Chem. 1977, 42, 3989.
26. Gopalakrishnan, G.; Hogg, J. L. J. Org. Chem. 1984, 49, 3161.
27. For example: (a) El Seoud, O. A.; El Seoud, M. I.; Farah, J. P. S. J. Org. Chem. 1997, 62, 5928.
28. Humeres, E.; Nunes, R. J.; Machado, V. G.; Gasques, M. D. G.; Machado, C. J. Org. Chem. 2001, 66, 1163.
29. Relative permittivity varies slightly in this concentration range: (a) Kaatze, U.; Pottel, R.; Schafer, M. J. Phys. Chem. 1989, 93, 5623.
30. Puranik, S. M.; Kumbharkhane, A. C.; Mehrotra, S. C. J. Chem. Soc., Faraday Trans. 1992, 88, 433. See Supporting Information for other linear free energy relationships.
31. Pocker, Y.; Ronald, B. P.; Anderson, K. W. J. Am. Chem. Soc. 1988, 110, 6492.
32. x) vs log[water] for determining the kinetic order in water because a misleading order would be obtained.
33. Hydrogen bond stabilization of twist conformations: (a) Booth, H.; Gidley, G. C. Tetrahedron Lett. 1964, 23, 1449.
34. Stolow, R. D.; McDonagh, P. M.; Bonaventura, M. M. J. Am. Chem. Soc. 1964, 86, 2165.
35. Lambert, J. B.; Featherman, S. I. Chem. Rev. 1975, 75, 611.
36. Na, J.; Houk, K. N.; Shevlin, C. G.; Janda, K. D.; Lerner, R. A. J. Am. Chem. Soc. 1993, 115, 8453.
37. Coxon, J. M.; Thorpe, A. J. J. Org. Chem. 1999, 64, 5530.