Silyl triflate-catalyzed oxonium-ene reaction of lactol allylic ethers: A new and stereocontrolled route to substituted oxygen heterocycles

Tetrahedron Letters

Volumn 37, Issue 21, 1996, Pages 3705-3708

  Mikami, Koichi ^a   Kishino, Hiroyuki ^a  

^a TOKYO INSTITUTE OF TECHNOLOGY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

FURAN DERIVATIVE; PYRAN DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029934884     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00646-6     Document Type: Article

References (23)

1. Reviews: (a) Semple, J. E.; Joullie, M. M. Heterocycles 1980, 14, 1825-1870.
2. (b) Bartlett, P. A. In Asymmetric Synthesis; Morrison, J. D. Ed.; Academic Press: New York, 1984; Vol. 3; pp 411-454.
3. (c) Boivin, T. L. B. Tetrahedron 1987, 43, 3309-3362.
4. (d) Harding, K. E.; Tiner, T. H. In Comprehensive Organic Synthesis; Trost B. M.; Fleming, I. Ed.; Pergamon: Oxford, 1991; Vol. 4; pp 363-421.
5. (e) Harmange, J.-C.; Figadère, B. Tetrahedron: Asymmetry 1993, 4, 1711-1754.
6. (f) Koert, U. Synthesis 1995, 115-132.
7. Reviews on ene reactions: (a) Hoffmann, H. M. R. Angew. Chem. Int. Ed. Engl. 1969, 8, 556-577.
8. (b) Fujita, Y.; Suzuki, S.; Kanehira, K. J. Synth. Org. Chem., Jpn. 1983, 41, 1152-1167.
9. (c) Snider, B. B. In Comprehensive Organic Synthesis; Trost B. M.; Fleming, I. Ed.; Pergamon: Oxford, 1991; Vol. 2 and 5.
10. Our reviews on carbonyl-ene reactions: (a) Mikami, K.; Shimizu, M. Chem. Rev. 1992, 92, 1021-1050.
11. (b) Mikami, K. In Advances in Asymmetric Synthesis; Hassner, A., Ed.; JAI Press: Greenwich, Connecticut, 1995; Vol. 1, pp 1-44.
12. 2, see: Mikami, K.; Kishino, H. J. Chem. Soc., Chem. Commun. 1993, 1843-1844.
13. The ene reactions involving oxonium ion intermediates have been reported in the case of medium ring cyclization: Overman, L. E.; Thompson, A. S. J. Am. Chem. Soc. 1988, 110, 2248-2256; Blumenkopf, T. A.; Bratz, M.; Castenada, A.; Look, G.G.; Overman, L. E.; Rodriguez, D.; Thompson, A. S.; ibid. 1990, 112, 4386-4399.
14. The ene reactions involving oxonium ion intermediates have been reported in the case of medium ring cyclization: Overman, L. E.; Thompson, A. S. J. Am. Chem. Soc. 1988, 110, 2248-2256; Blumenkopf, T. A.; Bratz, M.; Castenada, A.; Look, G.G.; Overman, L. E.; Rodriguez, D.; Thompson, A. S.; ibid. 1990, 112, 4386-4399.
15. 2AlCl provides lower yield of the product 2.
16. At 0 °C, only low level of diastereoselectivity (1:1) was observed.
17. Typical experimental procedure is as follows. To a dichloromethane solution of lactol-derived allylic ether 1a (n=1, R=Me) was added trimethylsilyl triflate (TMSOTf) in a catalytic amount (20 mol%) at -78 °C. After 1 hour, the usual work-up followed by silica gel chromatography gave the furanyl aldehyde 2a in 58% yield with 80% diastereoselectivity.
18. Mikami, K.; Shimizu, M. Tetrahedron Lett. 1992, 33, 6315-6318; Tetrahedron in press. Also see: Bloch, R.; Bortolussi, M.; Girard, C.; Seek, M. Tetrahedron 1992, 48, 453-462.
19. Mikami, K.; Shimizu, M. Tetrahedron Lett. 1992, 33, 6315-6318; Tetrahedron in press. Also see: Bloch, R.; Bortolussi, M.; Girard, C.; Seek, M. Tetrahedron 1992, 48, 453-462.
20. Mikami, K.; Shimizu, M. Tetrahedron Lett. 1992, 33, 6315-6318; Tetrahedron in press. Also see: Bloch, R.; Bortolussi, M.; Girard, C.; Seek, M. Tetrahedron 1992, 48, 453-462.
21. Petit, Y.; Sanner, C.; Larcheveque, M. Tetrahedron Lett. 1990, 31, 2149-2152.
22. (a) Mikami, K.; Loh, T.-P.; Nakai, T. Tetrahedron Lett. 1988, 29, 6305-6308.
23. (b) Mikami, K.; Loh, T.-P.; Nakai, T. Tetrahedron; Asymmetry. 1990, 1, 13-16.