Rearrangement of epoxides in non-aldol aldol process: Allylic vs. tertiary and secondary carbocationic centers

Tetrahedron Letters

Volumn 40, Issue 16, 1999, Pages 3129-3132

  Jung, Michael E ^a   Marquez, Rodolfo ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATION; EPOXIDE;

ARTICLE; DIASTEREOISOMER; EPOXIDATION; MOLECULAR INTERACTION; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; STEREOSPECIFICITY; STRUCTURE ACTIVITY RELATION; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0033574551     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)00458-X     Document Type: Article

References (35)

1. UCLA President's Fellow, 1994-1998. Awardee of Excellence for First Year Graduate Study Award, 1995.
2. Jung, M. E.; D'Amico, D. C. J. Am. Chem. Soc. 1993, 115, 12208. For an extension of this method tobis(propionates), see: Jung, M. E.; Lee, W. S., submitted for publication.
3. Jung, M. E.; D'Amico, D. C. J. Am. Chem. Soc. 1993, 115, 12208. For an extension of this method to bis(propionates), see: Jung, M. E.; Lee, W. S., submitted for publication.
4. For reviews of the aldol reaction, see: a) Mukaiyama, T.; Kobayashi, S. Org. React. 1995, 46, 1.
5. b) Franklin, A. S.; Paterson, I. Contemporary Org. Syn. 1994, 1, 317.
6. c) Heathcock, C. H. "The aldol addition reaction," in Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1984; Vol. 3, Ch. 2, pp 111-212.
7. d) Braun, M. "Recent developments in stereoselective aldol reactions," in Advances in Carbanion Chemistry, Snieckus, V., Ed.; Jai Press: Greenwich, CT, 1992; Vol. 1, Ch. 4.
8. e) Togni, A.; Pastor, S. D. Chirality 1991, 3, 331.
9. f) Evans, D. A.; Nelson, J. V.; Taber, T. R. Top. Stereochem. 1982, 13, 1.
10. g) Masamune, S.; Choy, W. Aldrichim. Acta 1982, 15, 47.
11. For some recent examples, see: a) Paterson, I.; Cowden, C. J.; Woodrow, M. D. Tetrahedron Lett. 1998, 39, 6037.
12. b) Paterson, I.; Woodrow, M. D.; Cowden, C. J. Tetrahedron Lett. 1998, 39, 6041.
13. c) Evans, D. A.; Kim, A. S.; Metternich, R.; Novack, V. J. J. Am. Chem. Soc. 1998, 120, 5921.
14. d) Corey, E. J.; Lee, D.-H.; Choi, S. Tetrahedron Lett. 1992, 33, 6735.
15. e) Corey, E. J.; Lee, D.-H. Tetrahedron Lett. 1993, 34, 1737.
16. f) Corey, E. J.; Kim, S. S. J. Am. Chem. Soc. 1990, 112, 4976.
17. g) Duthaler, R. O.; Herold, P.; Wyler-Helfer, S.; Riediker, M. Helv. Chim. Acta 1990, 73, 659.
18. h) Singer, R. A.; Carreira, E. M. Tetrahedron Lett. 1997, 38, 927.
19. i) Carreira, E. M.; Singer, R. A.; Lee, W. S. J. Am. Chem. Soc. 1994, 116, 8837.
20. a) Finn, M. G.; Sharpless, K. B. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1985; Vol. 5, Ch. 8, pp 247-308.
21. b) Martin, V. S.; Woodard, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237.
22. c) Rossiter, B. E.; Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 464.
23. d) Katsuki, T.; Sharpless, K. B. J. Am. Chem. Soc. 1980, 102, 5974.
24. a) Schmitz, F. J.; Gunasekera, S. P.; Yalamanchili, G.; Hossain, M. B.; van der Helm, D. J. Am. Chem. Soc. 1984, 106, 7251.
25. b) Fusetani, N.; Sugawara, T.; Matsunaga, S.; Hirota, H. J. Org. Chem. 1991, 56, 4971.
26. a) Jung, M. E.; Andersen, K. L. Tetrahedron Lett. 1997, 38, 2605.
27. b) Maruoka, K.; Sato, J.; Yamamoto, H. Tetrahedron 1992, 48, 3749.
28. c) Maruoka, K.; Ooi, T.; Yamamoto, H. J. Am. Chem. Soc. 1989, 111, 6431.
29. d) Maruoka, K.; Ooi, T.; Nagahara, S.; Yamamoto, H. Tetrahedron 1991, 47, 6983.
30. Note that the alternative mechanism of migration of the alkenyl group to the tertiary homoallylic cation in A would not lead to but rather to the quaternary aldehyde (for examples, see: Jung, M. E.; D'Amico, D. C. J. Am. Chem. Soc. 1995, 117, 7379). Thus while one cannot rule out this mechanism in the other rearrangements reported, e.g., 18 to 20, we believe that if it did not occur when a tertiary homoallylic cation was possible, it would certainly not occur when a less stable secondary homoallylic cation was involved and thus favor the mechanism described, namely rearrangement via the allylic cation, as shown in A.
31. a) We have assigned the stereochemistry based on the 'inside oxygen' model, e.g., via the transition state with the bromide approaching from the less-hindered face in the conformation in which the epoxide oxygen is nearly coplanar with the vinyl hydrogen. For an explanation, see: Haller, J.; Niwayama, S.; Duh., H. Y.; Houk, K. N. J. Org. Chem. 1997, 62, 5728; Raimondi, L.; Wu, Y. D.; Brown, F. K.; Houk, K. N. Tetrahedron Lett.1992, 33, 4409.
32. a) We have assigned the stereochemistry based on the 'inside oxygen' model, e.g., via the transition state withthe bromide approaching from the less-hindered face in the conformation in which the epoxide oxygen is nearlycoplanar with the vinyl hydrogen. For an explanation, see: Haller, J.; Niwayama, S.; Duh., H. Y.; Houk, K.N. J. Org. Chem. 1997, 62, 5728; Raimondi, L.; Wu, Y. D.; Brown, F. K.; Houk, K. N. Tetrahedron Lett. 1992, 33, 4409.
33. b) For other highly diastereoselective cyclizations of this type, see: Jung, M. E.; Karama, U.; Marquez, R. J. Org. Chem. 1999, 64, 663.
34. For the use of protic acids in this rearrangement, see: D'Amico, D. C. Ph. D. thesis, UCLA, 1994.
35. 1H NMR spectra of the acetonides i and ii formed from the diols formed by hydride reduction of 10 and 11, respectively, followed by acetonide formation. (formula presented)