The reductive Nazarov cyclization

Tetrahedron Letters

Volumn 39, Issue 46, 1998, Pages 8393-8396

  Giese, Sören ^a   West, F G ^a  

^a UNIVERSITY OF UTAH   (United States)

Author keywords

Annulation; Cyclization; Dienones; Electrocyclic reactions; Nazarov reactions

Indexed keywords

CYCLOPENTANONE DERIVATIVE;

CHEMICAL REACTION; CYCLIZATION; REACTION ANALYSIS; REVIEW;

EID: 0032511931     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(98)01934-0     Document Type: Article

References (25)

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13. 6. Bender, J. A.; Blize, A. E.; Browder, C. C.; Giese, S.; West, F. G. J. Org. Chem. 1998, 63, 2430.
14. 7. Preservation of the β and β' stereocenters has also been accomplished using the Si-directed Nazarov cyclization: Denmark, S. E.; Klix, R. C. Tetrahedron 1988, 44, 4043.
15. 8. (a) Substrates 1a and 1c have been previously described. 1a: Yates, P.; Yoda, N.; Brown, W.; Mann, B. J. Am. Chem. Soc. 1958, 50, 202. 1c: Eaton, P. E.; Giordano, C.; Schloemer, G.; Vogel, U. J. Org. Chem. 1976, 41, 2238.
16. 8. (a) Substrates 1a and 1c have been previously described. 1a: Yates, P.; Yoda, N.; Brown, W.; Mann, B. J. Am. Chem. Soc. 1958, 50, 202. 1c: Eaton, P. E.; Giordano, C.; Schloemer, G.; Vogel, U. J. Org. Chem. 1976, 41, 2238.
17. 4.
18. 3) δ 7.29-7.12 (m, 10H), 3.89 (dd, J = 11.9, 8.5 Hz, 1H), 3.28 (dd, J = 11.9, 11.9 Hz, 1H), 2.85 (dqd, J = 8.4, 8.1, 1.3 Hz, 1H), 2.45 (dqd, J = 11.9, 6.9, 1.6 Hz, 1H), 1.12 (d, J = 7.0 Hz, 3H), 0.78 (d, J = 7.9 Hz, 3H). (b) These reactions have been carried out on up to a 2 mmol scale with little diminution in yield (e.g., 1a → 5a, 87% comb. yield).
19. 10. The formation of 5a under reductive conditions (HI and red phosphorus) has been previously described: Shoppee, C. W.; Cooke, B. J. A. J. Chem. Soc., Perkin Trans. 1 1973, 1026.
20. 3Si-X species generated in situ may contribute to this process.
21. 4 mediated Z-E isomerization of a dienone: White, T. W. Torquoselectivity and Chloride Trapping in the Nazarov Cyclization of Facially Biased Dienones, University of Utah, 1998.
22. (b) For a somewhat related example of Lewis acid-mediated alkene isomerization, see: Faita, G.; Mella, M.; Righetti, P. P.; Tacconi, G. Tetrahedron 1994, 50, 10955.
23. 13. We assume delivery of hydride to the more substituted terminus of the intermediate oxyallyl cation due to greater charge localization at that carbon.
24. 14. (a) Kursanov, D. N.; Parnes, Z. N.; Loim, N. M. Synthesis 1974, 633.
25. (b) Weber, W. P. Silicon Reagents for Organic Synthesis; Springer-Verlag: New York, 1983; pp 273-287.