Highly enantioselective catalytic Pauson-Khand type formation of bicyclic cyclopentenones

Journal of the American Chemical Society

Volumn 118, Issue 46, 1996, Pages 11688-11689

  Hicks, Frederick A ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPENTENONE DERIVATIVE;

ARTICLE; CYCLIZATION; DRUG SYNTHESIS; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0029909515     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9630452     Document Type: Article

References (22)

1. Schore, N. E. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Kidlington, 1995; Vol. 12, p 703.
2. For Ti, see: (a) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1993, 115, 4912. (b) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 8593. (c) Hicks, F. A.; Berk, S. C.; Buchwald, S. L. J. Org. Chem. 1996, 61, 2713. (d) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 9450.
3. For Ti, see: (a) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1993, 115, 4912. (b) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 8593. (c) Hicks, F. A.; Berk, S. C.; Buchwald, S. L. J. Org. Chem. 1996, 61, 2713. (d) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 9450.
4. For Ti, see: (a) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1993, 115, 4912. (b) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 8593. (c) Hicks, F. A.; Berk, S. C.; Buchwald, S. L. J. Org. Chem. 1996, 61, 2713. (d) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 9450.
5. For Ti, see: (a) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1993, 115, 4912. (b) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 8593. (c) Hicks, F. A.; Berk, S. C.; Buchwald, S. L. J. Org. Chem. 1996, 61, 2713. (d) Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 9450.
6. For Co, see: (e) Jeong, N.; Hwang, S. H.; Lee, Y.; Chung, Y. K. J. Am. Chem. Soc. 1994, 116, 3159. (f) Lee, B. Y.; Chung, Y. K.; Jeong, N.; Lee, Y.; Hwang, S. H. J. Am. Chem. Soc. 1994, 116, 8793. (g) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285. (h) Lee, N. Y.; Chung, Y. K. Tetrahedron Lett. 1996, 37, 3145.
7. For Co, see: (e) Jeong, N.; Hwang, S. H.; Lee, Y.; Chung, Y. K. J. Am. Chem. Soc. 1994, 116, 3159. (f) Lee, B. Y.; Chung, Y. K.; Jeong, N.; Lee, Y.; Hwang, S. H. J. Am. Chem. Soc. 1994, 116, 8793. (g) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285. (h) Lee, N. Y.; Chung, Y. K. Tetrahedron Lett. 1996, 37, 3145.
8. For Co, see: (e) Jeong, N.; Hwang, S. H.; Lee, Y.; Chung, Y. K. J. Am. Chem. Soc. 1994, 116, 3159. (f) Lee, B. Y.; Chung, Y. K.; Jeong, N.; Lee, Y.; Hwang, S. H. J. Am. Chem. Soc. 1994, 116, 8793. (g) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285. (h) Lee, N. Y.; Chung, Y. K. Tetrahedron Lett. 1996, 37, 3145.
9. For Co, see: (e) Jeong, N.; Hwang, S. H.; Lee, Y.; Chung, Y. K. J. Am. Chem. Soc. 1994, 116, 3159. (f) Lee, B. Y.; Chung, Y. K.; Jeong, N.; Lee, Y.; Hwang, S. H. J. Am. Chem. Soc. 1994, 116, 8793. (g) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285. (h) Lee, N. Y.; Chung, Y. K. Tetrahedron Lett. 1996, 37, 3145.
10. For examples of stoichiometric asymmetric Pauson-Khand reactions, see: (a) Bladon, P.; Pauson, P. L.; Brunner, H.; Eder, R. J. Organomet. Chem. 1988, 355, 449. (b) Castro, J.; Sorensen, H.; Riera, A.; Morin, C.; Moyano, A.; Pericas, M. A.; Greene, A. E. J. Am. Chem. Soc. 1990, 112, 9388. (c) Verdaguer, X.; Moyano, A.; Pericas, M. A.; Riera, A.; Bernardes, V.; Greene, A. E.; Alvarez-Larena, A.; Piniella, J. F. J. Am. Chem. Soc. 1994, 116, 2153. (d) Hay, A. M.; Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Organometallics 1995, 14, 4986. (e) Park, H.-L.; Lee, B. Y., Kang, Y. K.; Chung, Y. K. Organometallics 1995, 14, 3104. (f) Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Synlett 1995, 1085.
11. For examples of stoichiometric asymmetric Pauson-Khand reactions, see: (a) Bladon, P.; Pauson, P. L.; Brunner, H.; Eder, R. J. Organomet. Chem. 1988, 355, 449. (b) Castro, J.; Sorensen, H.; Riera, A.; Morin, C.; Moyano, A.; Pericas, M. A.; Greene, A. E. J. Am. Chem. Soc. 1990, 112, 9388. (c) Verdaguer, X.; Moyano, A.; Pericas, M. A.; Riera, A.; Bernardes, V.; Greene, A. E.; Alvarez-Larena, A.; Piniella, J. F. J. Am. Chem. Soc. 1994, 116, 2153. (d) Hay, A. M.; Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Organometallics 1995, 14, 4986. (e) Park, H.-L.; Lee, B. Y., Kang, Y. K.; Chung, Y. K. Organometallics 1995, 14, 3104. (f) Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Synlett 1995, 1085.
12. For examples of stoichiometric asymmetric Pauson-Khand reactions, see: (a) Bladon, P.; Pauson, P. L.; Brunner, H.; Eder, R. J. Organomet. Chem. 1988, 355, 449. (b) Castro, J.; Sorensen, H.; Riera, A.; Morin, C.; Moyano, A.; Pericas, M. A.; Greene, A. E. J. Am. Chem. Soc. 1990, 112, 9388. (c) Verdaguer, X.; Moyano, A.; Pericas, M. A.; Riera, A.; Bernardes, V.; Greene, A. E.; Alvarez-Larena, A.; Piniella, J. F. J. Am. Chem. Soc. 1994, 116, 2153. (d) Hay, A. M.; Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Organometallics 1995, 14, 4986. (e) Park, H.-L.; Lee, B. Y., Kang, Y. K.; Chung, Y. K. Organometallics 1995, 14, 3104. (f) Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Synlett 1995, 1085.
13. For examples of stoichiometric asymmetric Pauson-Khand reactions, see: (a) Bladon, P.; Pauson, P. L.; Brunner, H.; Eder, R. J. Organomet. Chem. 1988, 355, 449. (b) Castro, J.; Sorensen, H.; Riera, A.; Morin, C.; Moyano, A.; Pericas, M. A.; Greene, A. E. J. Am. Chem. Soc. 1990, 112, 9388. (c) Verdaguer, X.; Moyano, A.; Pericas, M. A.; Riera, A.; Bernardes, V.; Greene, A. E.; Alvarez-Larena, A.; Piniella, J. F. J. Am. Chem. Soc. 1994, 116, 2153. (d) Hay, A. M.; Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Organometallics 1995, 14, 4986. (e) Park, H.-L.; Lee, B. Y., Kang, Y. K.; Chung, Y. K. Organometallics 1995, 14, 3104. (f) Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Synlett 1995, 1085.
14. For examples of stoichiometric asymmetric Pauson-Khand reactions, see: (a) Bladon, P.; Pauson, P. L.; Brunner, H.; Eder, R. J. Organomet. Chem. 1988, 355, 449. (b) Castro, J.; Sorensen, H.; Riera, A.; Morin, C.; Moyano, A.; Pericas, M. A.; Greene, A. E. J. Am. Chem. Soc. 1990, 112, 9388. (c) Verdaguer, X.; Moyano, A.; Pericas, M. A.; Riera, A.; Bernardes, V.; Greene, A. E.; Alvarez-Larena, A.; Piniella, J. F. J. Am. Chem. Soc. 1994, 116, 2153. (d) Hay, A. M.; Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Organometallics 1995, 14, 4986. (e) Park, H.-L.; Lee, B. Y., Kang, Y. K.; Chung, Y. K. Organometallics 1995, 14, 3104. (f) Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Synlett 1995, 1085.
15. For examples of stoichiometric asymmetric Pauson-Khand reactions, see: (a) Bladon, P.; Pauson, P. L.; Brunner, H.; Eder, R. J. Organomet. Chem. 1988, 355, 449. (b) Castro, J.; Sorensen, H.; Riera, A.; Morin, C.; Moyano, A.; Pericas, M. A.; Greene, A. E. J. Am. Chem. Soc. 1990, 112, 9388. (c) Verdaguer, X.; Moyano, A.; Pericas, M. A.; Riera, A.; Bernardes, V.; Greene, A. E.; Alvarez-Larena, A.; Piniella, J. F. J. Am. Chem. Soc. 1994, 116, 2153. (d) Hay, A. M.; Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Organometallics 1995, 14, 4986. (e) Park, H.-L.; Lee, B. Y., Kang, Y. K.; Chung, Y. K. Organometallics 1995, 14, 3104. (f) Kerr, W. J.; Kirk, G. G.; Middlemiss, D. Synlett 1995, 1085.
16. 1H NMR indicates the presence of acetone, a coproduct also found in the Brintzinger synthesis.
17. 2 (0.025 mmol, 8 mg), toluene (2 mL), and the substrate (0.50 mmol). The Schlenk is removed from the glovebox, attached to a Schlenk line, evacuated, and backfilled with 14 psig CO. Caution: Appropriate precautions should be taken when performing reactions under elevated CO pressure. The reaction mixture is heated to 90 °C for 12-16 h. After cooling the reaction mixture to room temperature, the CO is cautiously released in the hood. The crude reaction mixture is filtered through a plug of silica gel with the aid of diethyl ether and purified by flash chromatography. Note: All substrates were passed through a plug of alumina (except for entry 1) in the glovebox to remove adventitious moisture. The substrate for entry 1 was distilled under vacuum and stored in the glovebox.
18. The absolute configuration for these products was assigned based upon an X-ray crystal structure of the cyclopentenone from entry 5. Details will be published in the full paper.
19. We note that a 1,6-enyne containing a terminal alkyne and a 1,7-enyne could be cyclized with this catalyst system (20 mol%) but with lower levels of enantioselectivity (51 and 47% ee, respectively).
20. The Thorpe-Ingold effect has often been demonstrated to promote the Pauson-Khand cyclization. For examples, see ref 1.
21. Hicks, F. A.; Buchwald, S. L. Unpublished results.
22. 2d However, any related mechanism must involve metallacycle formation as the enantioselectivity determining step. All related modes of metallacycle formation still involve the same steric issues presented here.