Chromium catalyzed kinetic resolution of 2,2-disubstituted epoxides

Tetrahedron Letters

Volumn 40, Issue 41, 1999, Pages 7303-7306

  Lebel, Hélène ^a   Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CHROMIUM DERIVATIVE; EPOXIDE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL ANALYSIS; REACTION ANALYSIS; SYNTHESIS;

EID: 0033536712     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01502-6     Document Type: Article

References (24)

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3. 2. (a) Larrow, J. F.; Schaus, S. E.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 7420-7421.
4. (b) Schaus, S. E.; Jacobsen, E. N. Tetrahedron Lett. 1996, 37, 7937-7940.
5. (c) Schaus, S. E.; Larrow, J. F.; Jacobsen, E. N. J. Org. Chem. 1997, 62, 4197-4199.
6. (d) Martinez, L. E.; Leighton, J. L.; Carsten, D. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5897-5898.
7. (e) For a synthetic application, see: Wu, M. H.; Jacobsen, E. N. Tetrahedron Lett. 1997, 38, 1693-1696.
8. 3. For selected examples of kinetic resolution of 2,2-disubstituted epoxides, see: (a) Orru, R. V. A.; Mayer, S. F.; Kroutil, W.; Faber, K. Tetrahedron 1998, 54, 859-874.
9. (b) Orru, R. V. A.; Osprian, I.; Kroutil, W.; Faber, K. Synthesis 1998, 1259-1263.
10. (c) Osprian, I.; Kroutil, W.; Mischitz, M.; Faber, K. Tetrahedron: Asymmetry 1997, 8, 65-71.
11. (d) Lakner, F. J.; Hager, L. P. J. Org. Chem. 1996, 61, 3923-3925.
12. 4. For selected examples of preparation of 2,2-disubstituted epoxides, see: (a) Takayama, H.; Kurihara, M.; Kitajima, M.; Said, I. M.; Aimi, N. J. Org. Chem. 1999, 64, 1772-1773.
13. (b) Guo, J.; Duffy, K. J.; Stevens, K. L.; Dalko, P. I.; Roth, R. M; Hayward, M. M.; Kishi, Y. Angew. Chem., Int. Ed. Engl. 1998, 37, 187-192.
14. (c) Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109, 5765-5780.
15. 5. For selected examples of preparation of optically-active tertiary alcohols, see: (a) Dosa, P. I.; Fu, G. C. J. Am. Chem. Soc. 1998, 120, 445-446.
16. (b) Tietze, L. F.; Görlitzer, J. Synthesis 1998, 873-878.
17. 6. Lebel, H.; Jacobsen, E. N. J. Org. Chem. 1998, 63, 9624-9625.
18. 3 which is essential in the context of a kinetic resolution. See also: Saito, S.; Bunya, N.; Inaba, M.; Moriwake, T.; Torii, S. Tetrahedron Lett. 1985, 26, 5309-5312.
19. 8. Racemic epoxides 3, 4 and 8 have been prepared by epoxidation of the corresponding alkene. Racemic epoxides 5, 6 and 7 were obtained by methylene sulfur ylide transfer on the corresponding ketone. Epoxide 9 was produced by addition of the lithium anion of TMS-acetylene to the corresponding α-bromo ketone.
20. 9. Ager, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835-875. Blaser, H. U. Chem. Rev. 1992, 92, 935-952.
21. 9. Ager, D. J.; Prakash, I.; Schaad, D. R. Chem. Rev. 1996, 96, 835-875. Blaser, H. U. Chem. Rev. 1992, 92, 935-952.
22. 10. The regioisomeric ring-opened products were easily separable by flash chromatography.
23. rel assumes the presence of only two diastereoisomeric pathways and also that the reaction is first order in both enantiomers of the substrate.
24. 12. Full experimental details for all substrates are available upon request: jacobsen@chemistry.harvard.edu.