Titanocene-catalyzed cyclocarbonylation of enynes to cyclopentenones

Journal of the American Chemical Society

Volumn 118, Issue 39, 1996, Pages 9450-9451

  Hicks, Frederick A ^a   Kablaoui, Natasha M ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPENTENONE DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029952824     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9621509     Document Type: Article

References (31)

1. Schore, N. E. In Comprehensive Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon: Kidlington, U.K. 1995; Vol. 12, pp 703.
2. For Co, see: ref 1. For Fe, see: Pearson, A. J.; Dubbert, R. A. Organometallics 1994, 13, 1656. For Mo, see: Mukai, C.; Uchiyama, M.; Hanaoka, M. J. Chem. Soc., Chem. Commun. 1992, 1014. Jeong, N.; Lee, S. J. Tetrahedron Lett. 1993, 34, 4027. For W, see: Hoye, T. R.; Suriano, J. A. J. Am. Chem. Soc. 1993, 115, 1154.
3. For Co, see: ref 1. For Fe, see: Pearson, A. J.; Dubbert, R. A. Organometallics 1994, 13, 1656. For Mo, see: Mukai, C.; Uchiyama, M.; Hanaoka, M. J. Chem. Soc., Chem. Commun. 1992, 1014. Jeong, N.; Lee, S. J. Tetrahedron Lett. 1993, 34, 4027. For W, see: Hoye, T. R.; Suriano, J. A. J. Am. Chem. Soc. 1993, 115, 1154.
4. For Co, see: ref 1. For Fe, see: Pearson, A. J.; Dubbert, R. A. Organometallics 1994, 13, 1656. For Mo, see: Mukai, C.; Uchiyama, M.; Hanaoka, M. J. Chem. Soc., Chem. Commun. 1992, 1014. Jeong, N.; Lee, S. J. Tetrahedron Lett. 1993, 34, 4027. For W, see: Hoye, T. R.; Suriano, J. A. J. Am. Chem. Soc. 1993, 115, 1154.
5. For Co, see: ref 1. For Fe, see: Pearson, A. J.; Dubbert, R. A. Organometallics 1994, 13, 1656. For Mo, see: Mukai, C.; Uchiyama, M.; Hanaoka, M. J. Chem. Soc., Chem. Commun. 1992, 1014. Jeong, N.; Lee, S. J. Tetrahedron Lett. 1993, 34, 4027. For W, see: Hoye, T. R.; Suriano, J. A. J. Am. Chem. Soc. 1993, 115, 1154.
6. (a) Jeong, N.; Hwang, S. H.; Lee, Y.; Chung, Y. K. J. Am. Chem. Soc. 1994, 116, 3159.
7. (b) Lee, B. Y.; Chung, Y. K.; Jeong, N.; Lee, Y.; Hwang, S. H. J. Am. Chem. Soc. 1994, 116, 8793.
8. (c) Lee, N. Y.; Chung, Y. K. Tetrahedron Lett. 1996, 37, 3145.
9. (d) Pagenkopf, B. L.; Livinghouse, T. J. Am. Chem. Soc. 1996, 118, 2285.
10. (a) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1993, 115, 4912.
11. (b) Berk, S. C.; Grossman, R. B.; Buchwald, S. L. J. Am. Chem. Soc. 1994, 116, 8593.
12. Kablaoui, N. M.; Hicks, F. A.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 5818.
13. 2 (Strem Chemicals) was dissolved in hexane and filtered through Celite in a glove box under argon to remove insoluble materials prior to use.
14. 2, Sikora, D. J.; Moriarty, K. J.; Rausch, M. D. In Inorganic Synthesis; Angelici, R. J., Ed.; John Wiley and Sons, Inc.: New York, 1990; Vol. 28, p 248.
15. See supporting information for a representative procedure. Note: Occasionally on very humid days, this procedure gave diminished conversion to product. In these cases, filtration of the substrate through alumina, in a glove box, restored full reactivity.
16. (a) The yields for the two processes compare as follows [old(new)]: entry 1, 80(92); entry 7, 67(90); entry 8, 45(92); entry 9, 54(92).
17. (b) A comparison of the mole percent catalyst used [old(new)]: entry 1, 10(5); entry 7, 10(7.5); entry 8, 10(10); entry 9, 10(5).
18. Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 3182.
19. Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. Unpublished results.
20. (a) Negishi, E.-i.; Holmes, S. J.; Tour, J. M.; Miller, J. A.; Cederbaum, F. E.; Swanson, D. R.; Takahashi, T. J. Am. Chem. Soc. 1989, 111, 3336.
21. (b) See also: Urabe, H.; Hata, T.; Sato, F. Tetrahedron Lett. 1995, 36, 4261.
22. Kent, J. L.; Wan, H.; Brummond, K. M. Tetrahedron Lett. 1995, 36, 2407.
23. (a) Enynes with pendant chelating groups undergo the Pauson-Khand cyclization with accelerated rates and improved yields: Krafft, M. E.; Scott, I. L.; Romero, R. H.; Feihelmann, S.; Van Pelt, C. E. J. Am. Chem. Soc. 1993, 115, 7199.
24. (b) The preponderance of Pauson-Khand reactions employ substrates containing terminal alkynes (see ref 1).
25. Examples of the stoichiometric Pauson-Khand employing an enyne with both an internal alkyne and a 1,2-disubstituted olefin are rare (cf., Camps, F.; Moreto, J. M.; Ricart, S.; Vinas, J. M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1470. Almansa, C.; Carceller, E.; Garcia, E.; Serratosa, F. Synth. Commun. 1988, 18, 1079).
26. Examples of the stoichiometric Pauson-Khand employing an enyne with both an internal alkyne and a 1,2-disubstituted olefin are rare (cf., Camps, F.; Moreto, J. M.; Ricart, S.; Vinas, J. M. Angew. Chem., Int. Ed. Engl. 1991, 30, 1470. Almansa, C.; Carceller, E.; Garcia, E.; Serratosa, F. Synth. Commun. 1988, 18, 1079).
27. (a) Carceller, E.; Centellas, V.; Moyano, A.; Pericas, M. A.; Serratosa, F. Tetrahedron Lett. 1985, 26, 2475.
28. (b) Takano, S.; Inomata, K.; Ogasawara, K. Chem. Lett. 1992, 443.
29. Negishi, E.-i.; Choueiry, D.; Nguyen, T. B.; Swanson, D. R.; Suzuki, N.; Takahashi, T. J. Am. Chem. Soc. 1994, 116, 9751.
30. Hicks, F. A.; Berk, S. C.; Buchwald, S. L. J. Org. Chem. 1996, 61, 2713.
31. A comparison of the diastereoselectivities [old(new)]: entry 7, 12: 1(3.5:1); entry 8, 1.6:1(8:1).