Zirconium-catalyzed kinetic resolution of cyclic allylic ethers. An enantioselective route to unsaturated medium ring systems

Journal of the American Chemical Society

Volumn 118, Issue 15, 1996, Pages 3779-3780

  Visser, Michael S ^a   Harrity, Joseph P A ^a   Hoveyda, Amir H ^a  

^a BOSTON COLLEGE   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOHEXENE DERIVATIVE; ETHER DERIVATIVE;

ARTICLE; DRUG PURIFICATION; ENANTIOMER; TECHNIQUE;

EID: 0029954622     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja960263m     Document Type: Article

References (22)

1. (a) Martin, V. S.; Woodard, S. S.; Katsuki, T.; Yamada, Y.; Ikeda, M.; Sharpless, K. B. J. Am. Chem. Soc. 1981, 103, 6237-6240.
2. (b) Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109, 5765-5780.
3. For recent reviews of kinetic resolution, see: (a) Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249-330. (b) Finn, M. G.; Sharpless, K. B. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1985; 247-308.
4. For recent reviews of kinetic resolution, see: (a) Kagan, H. B.; Fiaud, J. C. Top. Stereochem. 1988, 18, 249-330. (b) Finn, M. G.; Sharpless, K. B. In Asymmetric Synthesis; Morrison, J. D., Ed.; Academic Press: New York, 1985; 247-308.
5. Kitamura, M.; Kasahara, I.; Manabe, K.; Noyori, R.; Takaya, H. J. Org. Chem. 1988, 53, 708-710. For Pd-catalyzed enantioselective synthesis of cyclic allylic esters, see: Trost, B. M.; Organ, M. G. J. Am. Chem. Soc. 1994, 116, 10320-10321.
6. Kitamura, M.; Kasahara, I.; Manabe, K.; Noyori, R.; Takaya, H. J. Org. Chem. 1988, 53, 708-710. For Pd-catalyzed enantioselective synthesis of cyclic allylic esters, see: Trost, B. M.; Organ, M. G. J. Am. Chem. Soc. 1994, 116, 10320-10321.
7. For previous reports on kinetic resolution processes through Zr-catalyzed carbomagnesation, see: (a) Morken, J. P.; Didiuk, M. T.; Visser, M. S.; Hoveyda, A. H J. Am. Chem. Soc. 1994, 116, 3123-3124. (b) Visser, M. S.; Hoveyda, A. H. Tetrahedron 1995, 51, 4383-4394. (c) Visser, M. S.; Heron, N. M.; Didiuk, M. T.; Sagal, J. F.; Hoveyda, A. H. J. Am. Chem. Soc. in press.
8. For previous reports on kinetic resolution processes through Zr-catalyzed carbomagnesation, see: (a) Morken, J. P.; Didiuk, M. T.; Visser, M. S.; Hoveyda, A. H J. Am. Chem. Soc. 1994, 116, 3123-3124. (b) Visser, M. S.; Hoveyda, A. H. Tetrahedron 1995, 51, 4383-4394. (c) Visser, M. S.; Heron, N. M.; Didiuk, M. T.; Sagal, J. F.; Hoveyda, A. H. J. Am. Chem. Soc. in press.
9. For previous reports on kinetic resolution processes through Zr-catalyzed carbomagnesation, see: (a) Morken, J. P.; Didiuk, M. T.; Visser, M. S.; Hoveyda, A. H J. Am. Chem. Soc. 1994, 116, 3123-3124. (b) Visser, M. S.; Hoveyda, A. H. Tetrahedron 1995, 51, 4383-4394. (c) Visser, M. S.; Heron, N. M.; Didiuk, M. T.; Sagal, J. F.; Hoveyda, A. H. J. Am. Chem. Soc. in press.
10. (a) Morken, J. P.; Didiuk, M. T.; Hoveyda, A. H. J. Am. Chem. Soc. 1993, 115, 6997-6998.
11. (b) Didiuk, M. T.; Johannes, C W.; Morken, J. P.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 7097-7104. For application of asymmetric Zr-catalyzed carbomagnesation to natural product synthesis, see: Houri, A. F.; Xu, Z-M.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943-2944.
12. (b) Didiuk, M. T.; Johannes, C W.; Morken, J. P.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 7097-7104. For application of asymmetric Zr-catalyzed carbomagnesation to natural product synthesis, see: Houri, A. F.; Xu, Z-M.; Cogan, D. A.; Hoveyda, A. H. J. Am. Chem. Soc. 1995, 117, 2943-2944.
13. (a) Wild, F. R. W. P.; Waiucionek, M.; Huttner, G.; Brintzinger, H. H. J. Organomet. Chem. 1985, 288, 63-67.
14. (b) Diamond, G. M.; Rodewald, S., Jordan, R. F. Organometallics 1995, 14, 5-7 and references cited therein.
15. 1H NMR spectrum of the unpurified mixture. In instances where volatility is not a hindrance, the product was fully characterized (e.g., with 9 and 10, i and ii were obtained, respectively). Details (including product stereocontrol) will be provided in the full account of this study. (Equation Presented)
16. All the catalytic resolutions described herein must be earned out with freshly prepared catalyst batches of high purity Sluggish reactions and/or inferior enantioselectivities will be otherwise observed.
17. The phenyl ether derived from cyclopentenol reacts with the alkylmagnesium halide in the absence of the catalyst, preempting the possibility of catalytic kinetic resolution (both at 22 and 70°C) Nonetheless, the starting material is recovered in ∼40% ee after 60% conversion.
18. Relame rates were calculated by an equation reported previously. See ref 2.
19. For deprotection of p-anisyl ethers, see: Fukuyama, T.; Laird, A. A.; Hotchkiss, L. M. Tetrahedron Lett. 1985, 26, 6291-6292. A benzyl ether of an allylic carbinol can be efficiently removed: Hwu, J. R.; Chua, V.; Schroeder, J. E.; Barrans, R. E.; Khoudary, K. P.; Wang, N.; Wetzel, J. M. J. Org. Chem. 1986, 51, 4733-4734
20. For deprotection of p-anisyl ethers, see: Fukuyama, T.; Laird, A. A.; Hotchkiss, L. M. Tetrahedron Lett. 1985, 26, 6291-6292. A benzyl ether of an allylic carbinol can be efficiently removed: Hwu, J. R.; Chua, V.; Schroeder, J. E.; Barrans, R. E.; Khoudary, K. P.; Wang, N.; Wetzel, J. M. J. Org. Chem. 1986, 51, 4733-4734
21. Hoveyda, A. H.; Morken, J. P. J. Org. Chem. 1993, 58, 4237-4244.
22. 2O. Evaporation of the organic solvents in vacuo and purification by silica gel chromatography afforded 122 mg (0.65 mmol, 98% yield based on percent conversion) of 12 which was shown to be >99% ee by chiral GLC analysis (minor enantiomer not detected).