Synthesis and evaluation of new 1,7-dioxaspiro[5.5]undecane ligands: Implications for the use of diols in the desymmetrization of meso epoxides

Tetrahedron

Volumn 56, Issue 4, 2000, Pages 507-513

  Patra, Debasis ^a   Yang, Lihua ^a   Totah, Nancy I ^a  

^a E11 SSH   (United States)

Author keywords

Asymmetric induction; Asymmetric synthesis; Catalysis; Spiro compounds

Indexed keywords

EPOXIDE; LIGAND; ORGANIC COMPOUND; SPIRO COMPOUND; TITANIUM DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL ANALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; ENANTIOMER; PRIORITY JOURNAL; REACTION ANALYSIS; SYNTHESIS;

EID: 0034695465     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(99)01044-3     Document Type: Article

References (24)

1. Eppley A.W., Totah N.I. Tetrahedron. 53:1997;16545-16552.
2. (a) Nugent, W. A. J. Am. Chem. Soc. 1992, 114, 2768-2769.
3. (b) Martinez, L. E.; Leighton, J. L.; Carsten, D. H.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5897-5898.
4. (c) Hayashi, M.; Kohmura, K.; Oguni, N. Synlett 1991, 774-776.
5. For mechanistic discussions on the desymmetrization of meso epoxides, see: (a) Hansen, K. B.; Leighton, J. L.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 10924-10925.
6. (b) Palucki, M.; Finney, N. S.; Pospisil, P. J.; Güler, M. L.; Ishida, T.; Jacobsen, E. N. J. Am. Chem. Soc. 1998, 120, 948-954.
7. (c) McCleland, B. W.; Nugent, W. A.; Finn, M. G. J. Org. Chem., 1998, 63, 6656-6666.
8. (a) Schreiber, S. L.; Wang, Z. J. Am. Chem. Soc. 1985, 107, 5303-5305.
9. (b) Enders, D.; Dahmen, W.; Dederichs, E.; Gatzweiler, W.; Weuster, P. Synthesis 1990, 1013-1019.
10. 2EtN).
11. Kolb H.C., Van Nieuwenhze M.S., Sharpless K.B. Chem. Rev. 94:1994;2483-2547.
12. Mixed fractions from the initial column chromatography of 2 and 8 are most conveniently separated into their component alcohols by monosilylation and subsequent chromatographic separation on silica gel. The enantiomeric purity of the monosilylated axial isomer can then be evaluated directly by gas chromatography.
13. 2).
14. The anticipated mode of complexation is as indicated in Scheme 3, though the specifics of this structure remain to be elucidated.
15. (a) Choukroun, R.; Gervais, D. J. Chem. Soc., Dalton Trans. 1980, 1800-1802.
16. (b) Blandy, C.; Choukroun, R.; Gervais, D. Tetrahedron Lett. 1983, 24, 4189-4192.
17. See also: (c) Caron, M.; Sharpless, K. B. J. Org. Chem. 1985, 50, 1557-5189.
18. Absolute configurations are assigned by comparison of the relative retention times of individual enantiomers with those reported by Jacobsen. See Ref. 2b.
19. Emziane K.I., Sutowardoyo K.I., Sinou D.J. Organomet. Chem. 346:1988;C7.
20. None of the corresponding bis-silylated ligand is obtained, presumably due to the increased steric hindrance about the axial alcohol at C4.
21. Shibasaki has recently reported the use of a binaphthol based system for the desymmetrization of meso epoxides using nonsilylated nucleophiles. See: Iida, T.; Yamamoto, N.; Sasai, H.; Shibasaki, M. J. Am. Chem. Soc. 1997, 119, 4783-4784.
22. Sarmah B.K., Barua N.C. Tetrahedron. 49:1993;2253-2260.
23. Daqiang X., Crispino G.A., Sharpless K.B. J. Am. Chem. Soc. 114:1992;7570-7571.
24. When ligand 15 is used in this application, reaction times increase substantially. Thus, the reaction requires approximately six days after addition of the epoxide to reach 50% conversion.