On the mechanism of lithium amide-induced rearrangements of Q-substituted cyclopentene oxides to cyclopentenols

Tetrahedron Letters

Volumn 38, Issue 51, 1997, Pages 8907-8910

  Hodgson, David M ^a   Gibbs, Andrew R ^a  

^a UNIVERSITY OF OXFORD   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOALKANOL DERIVATIVE; CYCLOPENTENE DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; IN VITRO STUDY; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0030817395     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(97)10358-6     Document Type: Article

References (25)

1. Crandall, J. K.; Apparu, M. Org. React. (N. Y.) 1983, 29, 345-443; Satoh, T. Chem. Rev. 1996, 96, 3303-3325.
2. Crandall, J. K.; Apparu, M. Org. React. (N. Y.) 1983, 29, 345-443; Satoh, T. Chem. Rev. 1996, 96, 3303-3325.
3. Hodgson, D. M.; Gibbs, A. R.; Lee, G. P. Tetrahedron 1996, 52, 14361-14384.
4. Hodgson, D. M.; Gibbs, A. R. Synlett 1997, 657-658.
5. Thummel, R. P.; Rickborn, B. J. Am. Chem. Soc. 1970, 92, 2064-2067.
6. Morgan, K. M.; Gajewski, J. J. J. Org. Chem. 1996, 67, 820-821.
7. Chickos, J. S; Bausch, M.; Alul, R. J. Org. Chem. 1981, 46, 3559-3562; see also: Chickos, J. S; Uang, J. Y.-J.; Keiderling, T. A. J. Org. Chem. 1991, 56, 2594-2596.
8. Chickos, J. S; Bausch, M.; Alul, R. J. Org. Chem. 1981, 46, 3559-3562; see also: Chickos, J. S; Uang, J. Y.-J.; Keiderling, T. A. J. Org. Chem. 1991, 56, 2594-2596.
9. Bobbitt, J. M.; Amundsen, L. H.; Steiner, R. I. J. Org. Chem. 1960, 25, 2230-2231;
10. Deprés, J.-P.; Greene, A. E. ibid. 1984, 49, 928-931.
11. Isolated total yields of chromatographically homogeneous, spectroscopically pure products are reported.
12. Hodgson, D. M.; Witherington, J.; Moloney, B. A. J. Chem. Soc., Perkin Trans. 1 1994, 3373-3378.
13. Hodgson, D. M.; Gibbs, A. R. Tetrahedron: Asymmetry 1996, 7, 407-408.
14. Identical deuterium levels at the vinylic and allylic positions in alcohol 6 suggest no detectable enantioselectivity in this reversible α-deprotonation process (8% ee was observed in the rearrangement of exo-norbornene oxide to nortricyclanol using base 5: Hodgson, D. M.; Wisedale, R. Tetrahedron: Asymmetry 1996, 7, 1275-1276).
15. In ether, the isolated yield of alcohol 6e does not strictly rule out mainly (or exclusively) β-deprotonation operating in combination with a secondary deuterium isotope effect; the result in THF is more convincing that some of alcohol 6t arises via α-deprotonation.
16. Krow, G. R. Org. React. (N. Y.) 1993, 43, 251-798; Cooper, M. S.; Heaney, H.; Newbold, A. J.; Sanderson, W. R. Synlett 1990, 533-535; Kang, H.-J.; Jeong, H.-S. Bull. Korean Chem. Soc. 1996, 17, 5-6.
17. Krow, G. R. Org. React. (N. Y.) 1993, 43, 251-798; Cooper, M. S.; Heaney, H.; Newbold, A. J.; Sanderson, W. R. Synlett 1990, 533-535; Kang, H.-J.; Jeong, H.-S. Bull. Korean Chem. Soc. 1996, 17, 5-6.
18. Krow, G. R. Org. React. (N. Y.) 1993, 43, 251-798; Cooper, M. S.; Heaney, H.; Newbold, A. J.; Sanderson, W. R. Synlett 1990, 533-535; Kang, H.-J.; Jeong, H.-S. Bull. Korean Chem. Soc. 1996, 17, 5-6.
19. Saito, I.; Nagata, R.; Yuba, K.; Matsuura, T. Tetrahedron Lett. 1983, 24, 1737-1740.
20. 3)}. Our results therefore indicate that the predominant sense of asymmetric induction indicated in Milne and Murphy's work should be reversed.
21. 3)}. Our results therefore indicate that the predominant sense of asymmetric induction indicated in Milne and Murphy's work should be reversed.
22. 3)}. Our results therefore indicate that the predominant sense of asymmetric induction indicated in Milne and Murphy's work should be reversed.
23. Asami, M. Bull. Chem. Soc. Jpn. 1990, 63, 1402-1408.
24. 0.90 at both vinylic and carbinol carbons).
25. The slight difference in deuterium levels in epoxides 4 and 10, reflect different runs in the formation of cis-2,3-dideuterio-2-butene-1,4-diol.