A titanocene-catalyzed intramolecular ene reaction: Cycloisomerization of enynes and dienynes [12]

Journal of the American Chemical Society

Volumn 121, Issue 9, 1999, Pages 1976-1977

  Sturla, Shana J ^a   Kablaoui, Natasha M ^a   Buchwald, Stephen L ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKYNE; TITANOCENE;

CATALYSIS; CHEMICAL REACTION; CYCLIZATION; ISOMERISM; LETTER; STEREOCHEMISTRY;

EID: 0033541036     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9839567     Document Type: Letter

References (37)

1. Hoffmann, H. M. R. Angew. Chem., Int. Ed. Engl. 1969, 8, 556.
2. Taber, D. F. Intramolecular Diels - Alder and Alder Ene Reactions; Springer-Verlag: Berlin, 1984; pp 61-94.
3. (a) Ni: Radetich, B.; RajanBabu, T. V. J. Am. Chem. Soc. 1998, 120, 8007.
4. (b) Ni-Cr: Trost, B. M.; Tour, J. M. J. Am. Chem. Soc. 1987, 109, 5268.
5. (c) For a cobalt-mediated process, see: Llerena, D.; Aubert, C.; Malacria, M. Tetrahedron Lett. 1996, 37, 7027 and Krafft, M.; Wilson, A.; Dasse, O.; Bonega, L.; Cheung, Y.; Fu, Z.; Shao, B.; Scott, I. Tetrahedron Lett. 1998, 39, 5911.
6. (c) For a cobalt-mediated process, see: Llerena, D.; Aubert, C.; Malacria, M. Tetrahedron Lett. 1996, 37, 7027 and Krafft, M.; Wilson, A.; Dasse, O.; Bonega, L.; Cheung, Y.; Fu, Z.; Shao, B.; Scott, I. Tetrahedron Lett. 1998, 39, 5911.
7. For related enyne metathesis reactions, see: (a) Fürstner, A.; Szillat, H.; Gabor, B.; Mynott, R. J. Am. Chem. Soc. 1998, 120, 8305 and references therein. For metallo-ene and related reactions, see: (b) Oppolzer, W. Angew. Chem., Int. Ed. Engl. 1989, 28, 38. (c) Takayama, Y.; Gao, Y.; Sato, F. Angew. Chem., Int. Ed. Engl. 1997, 36, 851.
8. For related enyne metathesis reactions, see: (a) Fürstner, A.; Szillat, H.; Gabor, B.; Mynott, R. J. Am. Chem. Soc. 1998, 120, 8305 and references therein. For metallo-ene and related reactions, see: (b) Oppolzer, W. Angew. Chem., Int. Ed. Engl. 1989, 28, 38. (c) Takayama, Y.; Gao, Y.; Sato, F. Angew. Chem., Int. Ed. Engl. 1997, 36, 851.
9. For related enyne metathesis reactions, see: (a) Fürstner, A.; Szillat, H.; Gabor, B.; Mynott, R. J. Am. Chem. Soc. 1998, 120, 8305 and references therein. For metallo-ene and related reactions, see: (b) Oppolzer, W. Angew. Chem., Int. Ed. Engl. 1989, 28, 38. (c) Takayama, Y.; Gao, Y.; Sato, F. Angew. Chem., Int. Ed. Engl. 1997, 36, 851.
10. See: Trost, B. M.; Krische, M. J. Synlett 1998, 1 and references therein.
11. (a) Trost, B. M.; Lautens, M.; Chan, C.; JeBaratnam, D. J.; Mueller, T. J. Am. Chem. Soc. 1991, 113, 636.
12. (b) Trost, B. M.; Romero, D. L.; Rise, F. J. Am. Chem. Soc. 1994, 116, 4268 and references therein.
13. Trost, B. M. In Studies in Natural Products Chemistry; Atta-ur-Rahman, Ed.; Elsevier: Amsterdam, 1991; Vol. 8; p 277.
14. Goeke, A.; Sawamura, M.; Kuwano, R.; Ito, Y. Angew. Chem., Int. Ed. Engl. 1996, 35, 662.
15. Trost, B. M.; Czeskis, B. A. Tetrahedron Lett. 1994, 35, 211.
16. (a) For a review of zirconium-mediated cyclizations, see: Negishi, E. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, U.K., 1991; Vol. 5, pp 1163-1184.
17. (b) Titanium-mediated cyclization: Urabe H., Hata, T., Sato, F. Tetrahedron Lett. 1995, 36, 4261.
18. (c) Titanium-catalyzed cyclization: Berk, S. C.; Grossman, R. B.; Buchwald, S. J. Am. Chem. Soc. 1994, 116, 8593.
19. Hicks, F. A.; Kablaoui, N. M.; Buchwald, S. L. J. Am. Chem. Soc. 1996, 118, 9450.
20. Gell, K. I.; Schwartz, J. J. Am. Chem. Soc. 1981, 103, 2687.
21. Energy minimization was performed using MacSpartan Plus PM3 method.
22. 1 symmetry and is oriented perpendicular to the plane in which the metallacycles in Figure 2 are drawn. For a discussion of the structure of bis(cyclopentadienyl)-metal complexes, see: Lauher, J. W.; Hoffmann, R. J. Am. Chem. Soc. 1976, 98, 1729.
23. A complex mixture results when ether 8 is used as a substrate in the cycloisomerization reaction. Although titanium reagents have been shown to induce the cyclization of allylic ethers, these substrates are known to be problematic in reactions using zirconium reagents. Grossman, R. B.; Buchwald, S. L. J. Org. Chem. 1992, 57, 5803.
24. 1H NMR and GC as well as an elemental analysis for one experiment with each substrate.
25. RajanBabu, T. V.; Nugent, W. A., Taber, D. F.; Fagan, P. J. J. Am. Chem. Soc. 1988, 110, 7128. Lund, E. C.; Livinghouse, T. J. Org. Chem. 1989, 54, 4487. Pagenkopf, B. L.; Lund, E. C.; Livinghouse, T. Tetrahedron 1995, 51, 4421.
26. RajanBabu, T. V.; Nugent, W. A., Taber, D. F.; Fagan, P. J. J. Am. Chem. Soc. 1988, 110, 7128. Lund, E. C.; Livinghouse, T. J. Org. Chem. 1989, 54, 4487. Pagenkopf, B. L.; Lund, E. C.; Livinghouse, T. Tetrahedron 1995, 51, 4421.
27. RajanBabu, T. V.; Nugent, W. A., Taber, D. F.; Fagan, P. J. J. Am. Chem. Soc. 1988, 110, 7128. Lund, E. C.; Livinghouse, T. J. Org. Chem. 1989, 54, 4487. Pagenkopf, B. L.; Lund, E. C.; Livinghouse, T. Tetrahedron 1995, 51, 4421.
28. For reactions of allenes, see: Schuster, H. F.; Coppola, G. M. Allenes In Organic Synthesis; John Wiley & Sons: New York, 1984.
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31. (c) The formation of allenes via β-hydride elimination of vinyl complexes has been proposed as an intermediate step in several palladium-catalyzed reactions, see: Kudota, I.; Shibuya, A.; Gyoung, Y. S.; Yamamolo, Y. J. Am. Chem. Soc. 1998, 120, 1062 and references therein.
32. (a) Rh: Jolly, R. S.; Leudtke, G.; Sheehan, D.; Livinghouse, T. J. Am. Chem. Soc. 1990, 112, 4965. McKinstry, L.; Livinghouse, T. Tetrahedron 1994, 50, 6145. Gilbertson, S. R.; Hoge, G. S. Tetrahedron Lett. 1998, 39, 2075.
33. (a) Rh: Jolly, R. S.; Leudtke, G.; Sheehan, D.; Livinghouse, T. J. Am. Chem. Soc. 1990, 112, 4965. McKinstry, L.; Livinghouse, T. Tetrahedron 1994, 50, 6145. Gilbertson, S. R.; Hoge, G. S. Tetrahedron Lett. 1998, 39, 2075.
34. (a) Rh: Jolly, R. S.; Leudtke, G.; Sheehan, D.; Livinghouse, T. J. Am. Chem. Soc. 1990, 112, 4965. McKinstry, L.; Livinghouse, T. Tetrahedron 1994, 50, 6145. Gilbertson, S. R.; Hoge, G. S. Tetrahedron Lett. 1998, 39, 2075.
35. (b) Ni: Wender, P. A.; Jenkins, T. E. J. Am. Chem. Soc. 1989, 111, 6432. Wender, P. A.; Smith, T. E. J. Org. Chem. 1996, 61, 824.
36. (b) Ni: Wender, P. A.; Jenkins, T. E. J. Am. Chem. Soc. 1989, 111, 6432. Wender, P. A.; Smith, T. E. J. Org. Chem. 1996, 61, 824.
37. (c) Pd: Kumar, K.; Jolly, R. S. Tetrahedron Lett. 1998, 39, 3047.