Asymmetric synthesis of trifluoromethylated allylic amines using α,β-unsaturated N-tert-butanesulfinimines

Organic Letters

Volumn 3, Issue 18, 2001, Pages 2847-2850

  Prakash, G K Surya ^a   Mandal, Mihirbaran ^a   Olah, George A ^a  

^a UNIVERSITY OF SOUTHERN CALIFORNIA   (United States)

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EID: 0001046257     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol010134x     Document Type: Article

References (29)

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7. Carbohydrate derivatives: Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993, 115, 444.
8. For a recent review, see: Johannsen, M.; Jørgensen, K. A. Chem. Rev. 1998, 98, 1689. For a recent example of an enantioselective approach to allylic amines, see: Evans, P. A.; Robinson, J. E.; Nelson, J. D. J. Am. Chem. Soc. 1999, 121, 6761.
9. For a recent review, see: Johannsen, M.; Jørgensen, K. A. Chem. Rev. 1998, 98, 1689. For a recent example of an enantioselective approach to allylic amines, see: Evans, P. A.; Robinson, J. E.; Nelson, J. D. J. Am. Chem. Soc. 1999, 121, 6761.
10. Importance of fluorine in medicinal chemistry: (a) McCarthy, J. Utility of Fluorine In Biologically Active Molecules; Division of Fluorine Chemistry Tutorial, 219th National Meeting of the American Chemical Society, San Francisco, March 26, 2000.
11. (b) Filler, R.; Kobayashi, Y.; Yagulpolskii, Y. L. Organofluorine Compounds in Medicinal Chemistry and Biomedical Applications; Elsevier: Amsterdam, 1993.
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13. (d) Hudlicky, M.; Pavlath, A. E. Chemistry of Organic Fluorine Compounds II. A Critical Review; ACS Monograph 187; American Chemical Society: Washington, DC, 1995.
14. (e) Welch, J. T., Ed. Selective Fluorination in Organic and Bioorganic Chemistry, ACS Symposium Series 456; American Chemical Society: Washington, DC, 1991.
15. There is no report on the addition of vinylmetallic derivatives to the trifluoromethylated imines. For the addition of allylmetal to trifluoromethylated ketimines: see, Felix, C.; Laurent, A.; Lesniak, S.; Mison, P. J. Chem. Res., Synop. 1991, 32.
16. (a) Xu, Y.; Dolbier, W. R., Jr. J. Org. Chem. 2000, 65, 2134.
17. (b) Kumadaki, I.; Jonoshita, S.; Harada, A.; Omote, M.; Ando, A. J. Fluorine Chem. 1999, 97, 61.
18. (a) Prakash, G. K. S.; Mandal, M.; Olah, G. A. Synlett 2001, 77.
19. (b) Prakash, G. K. S.; Mandal, M.; Olah, G. A. Angew. Chem., Int. Ed. 2001, 40, 589.
20. For our other nucleophilic trifluoromethylation reactions, see: (c) Prakash, G. K. S.; Krishnamurti, R.; Olah, G. A. J. Am. Chem. Soc. 1989, 111, 393.
21. (d) Krishnamurti, R.; Bellew, A. D. R.; Prakash, G. K. S. J. Org. Chem. 1991, 56, 984.
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23. (f) Prakash, G. K. S.; Ramaiah, R. Synlett 1991, 643.
24. (g) Wiedemann, J.; Heiner, T.; Mloston, G.; Prakash, G. K. S.; Olah, G. A. Angew. Chem., Int. Ed. 1998, 37, 820.
25. Addition of organometallic reagents to tert-butanesulfinimines is known in the literature. (a) Liu, G.; Cogan, D. A.; Ellman, J. A. J. Am. Chem. Soc. 1997, 119, 9913.
26. 4 was added slowly via a syringe. After 0.5 h of stirring at 0°C, the reaction mixture was warmed to room temperature and stirred until TLC indicated the reaction was complete (4-6 h). At this time, the reaction mixture was added to an ice-cooled solution of brine (5 mL). The resulting suspension was filtered through a plug of Celite. The Celite was washed three times with ethyl acetate. The resulting biphasic mixture was transferred to a separating funnel, the aqueous layer was separated, and the organic layer was washed with water (10 mL), dried, and concentrated to afford pure sulfinimines (as analyzed by NMR).
27. 4, and concentrated to give the crude 4a in 90:10 diastereomeric ratio. Reaction with TMAF (tetramethylammonium fluoride) was also carried out under similar conditions.
28. Davis, F. A.; McCoull, W. J. Org. Chem. 1999, 64, 3396.
29. We thank Prof. Robert Bau and Mr. Kavin Jin for their help in obtaining the crystal structure of 4a.