Intramolecular 2-propylidene-13-bis(silane) imine cyclizations. An efficient new procedure for the stereocontrolled synthesis of pyrrolidines, isotropanes, and bridged pyrrolizidines

Journal of the American Chemical Society

Volumn 118, Issue 17, 1996, Pages 4200-4201

  Kercher, Timothy ^a   Livinghouse, Tom ^a  

^a MONTANA STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

PYRROLIDINE DERIVATIVE; PYRROLIZIDINE DERIVATIVE;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029886698     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja954136m     Document Type: Article

References (24)

1. The Electrophilic Substitution of Allylsilanes and Vinylsilanes. Fleming, I.; Dunosuès, J., Smithers, R. In Organic Reactions, Kende, A. S., Ed.: John Wiley and Sons: New York, 1989, Vol. 37, Chapter 2, p 57.
2. (a) Heerding, D. A.; Hona, C. Y.; Kado, N.; Look, G. C.; Overman, L. E. J. Org. Chem. 1993, 58, 6947.
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4. (c) Hiemstra, H.; Forgens, H. P.; Speckamp, W. N Tetrahedron Lett. 1985, 26, 3155.
5. (d) Hiemstra, H.; Sno, M. H. A. M., Vijn, R. J.; Speckamp, W. N. J. Org. Chem. 1985, 50, 4014.
6. (e) An account addressing stereoselective cyclizadons of allylsilanes with iminium ions generated by a Beckmann rearrangement has appeared, see: Schinzer, D.; Bo, Y. Angew. Chem., Int. Ed. Engl. 1991, 30, 687.
7. (a) Jin, J.; Smith, D. T.; Weinreb, S. M J. Org. Chem. 1995, 60, 5366.
8. (b) Borzilleri, R. M.; Weinreb, S. M. J. Am. Chem. Soc. 1994, 116, 9789.
9. (a) In contrast to allylsilanes, 2-propylidene-1.3-bis(silane)s have seen relatively little use in synthesis. For pertinent references concerning the use of these compounds as well as related methodology, see: Rubiralt, M.; Diez, A.; Miguel, D. Syn. Commun. 1992, 22, 359.
10. (b) Guyot, B.; Pornet, J.; Miginiac, L. J. Organomet. Chem. 1990, 386, 19.
11. (c) Guyot, B.; Pornet, J ; Miginiac, L. Tetrahedron 1991, 47, 3981.
12. (a) Rie, H.; Masaki, N.; Ohno, K.; Osaki, K.; Taga, T.; Uyeo, S. J. Chem. Soc., Chem. Commun. 1973, 125.
13. (b) Sakata, K.; Aoki, K.; Chang, C.; Sakurai, A.; Tamura, S.; Murakoshi, S. Azric. Biol. Chem. 1978, 42, 457.
14. Danishefsky, C.; McKee, R.; Singh, R. K. J. Am. Chem. Soc. 1977, 99, 7711.
15. 13C NMR and IR and possess satisfactory combustion analyses or exact mass.
16. 1H NMR.
17. 4, filtered, and concentrated. The residual oil was dissolved in pentane (10 mL), filtered through a celite pad, and concentrated in vacuo to furnish the title pyrrolidine 8a (272 mg. 98%) as a colorless oil.
18. -] in these instances.
19. Significantly, the majority of cases involving cyclization onto imines derived from ketones which have been examined thus far proceed with comparatively poor efficiency.
20. Isotropanes of this substructure type have been shown to possess activity in combatting dementia resulting from Alzheimer's disease: Jenkins, S. M.; Wadsworth, H. J.; Bromidge, S., Orlek, B. S.; Wyman, P. A.; Riley, G. J.; Hawkins, J. J. Med. Chem. 1992, 35, 2392.
21. (a) Larsen, S. D ; Grieco, P. A.; Fobare, W. F. J. Am. Chem. Soc. 1986, 108, 3512.
22. (b) Grieco, P. A.; Fobare, W. F. Tetrahedron Lett. 1986, 27, 5067.
23. The volatile isotropane was isolated by extraction of the basified reaction mixture followed by neutralization with 1 equiv of TFA.
24. NMR analysis of the crude cyclizadon product provided no evidence for the formation of the diastereomeric cyclization product.