Studies on the mechanism of intermolecular enyne metathesis: Kinetic method and alkyne substituent effects

Journal of the American Chemical Society

Volumn 127, Issue 16, 2005, Pages 5762-5763

  Galan, Brandon R ^a   Giessert, Anthony J ^a   Keister, Jerome B ^a   Diver, Steven T ^a  

^a UNIVERSITY AT BUFFALO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

1 HEXENE; ALKYNE DERIVATIVE; BENZOIC ACID; CARBENOID; ETHYLENE;

ARTICLE; CATALYSIS; CHELATION; CHEMICAL STRUCTURE; KINETICS; REACTION ANALYSIS; RING CLOSING METATHESIS; SUBSTITUTION REACTION;

ALKENES; ALKYNES; KINETICS; STRUCTURE-ACTIVITY RELATIONSHIP;

EID: 17744383192     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja050174m     Document Type: Article

References (23)

1. Recent reviews: (a) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317-1382. (b) Poulsen, C. S.; Madsen, R. Synthesis 2003, 1-18. First examples of cross enyne metathesis: (c) Blechert, S.; Stragies, R.; Schuster, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 2518-2520. (d) Kinoshita, A.; Sakakibara, N.; Mori, M. J. Am. Chem. Soc. 1997, 119, 12388-12389.
2. Recent reviews: (a) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317-1382. (b) Poulsen, C. S.; Madsen, R. Synthesis 2003, 1-18. First examples of cross enyne metathesis: (c) Blechert, S.; Stragies, R.; Schuster, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 2518-2520. (d) Kinoshita, A.; Sakakibara, N.; Mori, M. J. Am. Chem. Soc. 1997, 119, 12388-12389.
3. Recent reviews: (a) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317-1382. (b) Poulsen, C. S.; Madsen, R. Synthesis 2003, 1-18. First examples of cross enyne metathesis: (c) Blechert, S.; Stragies, R.; Schuster, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 2518-2520. (d) Kinoshita, A.; Sakakibara, N.; Mori, M. J. Am. Chem. Soc. 1997, 119, 12388-12389.
4. Recent reviews: (a) Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317-1382. (b) Poulsen, C. S.; Madsen, R. Synthesis 2003, 1-18. First examples of cross enyne metathesis: (c) Blechert, S.; Stragies, R.; Schuster, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 2518-2520. (d) Kinoshita, A.; Sakakibara, N.; Mori, M. J. Am. Chem. Soc. 1997, 119, 12388-12389.
5. Ethylene protective effect: Mori, M.; Sakakibara, N.; Kinoshita, A. J. Org. Chem. 1998, 63, 6082-6083.
6. (a) Tonogaki, K.; Mori, M. Tetrahedron Lett. 2002, 43, 2235-2238.
7. (b) Kinoshita, A.; Sakakibara, N.; Mori, M. Tetrahedron 1999, 55, 8155-8167.
8. (c) Smulik, J. A.; Diver, S. T. Org. Lett. 2000, 2, 2271-2274.
9. (a) Giessert, A. J.; Brazis, N. J.; Diver, S. T. Org. Lett. 2003, 5, 3819-3822.
10. (b) Kulkarni, A. A.; Diver, S. T. Org. Lett. 2003, 5, 3463-3466.
11. (c) Kulkarni, A. A,; Diver, S. T. J. Am. Chem. Soc. 2004, 126, 8110-8111.
12. For reported changes in alkyne triple bond stretch on enyne binding to metal, see: Kang, B.; Kim, D.-H.; Do, Y.; Chang, S. Org. Lett. 2003, 5, 3041-3043.
13. See Supporting Information.
14. Both reactions are first order in ruthenium complex 1.
15. A similar trend was observed with 3A and 3B.
16. The kinetic data in this study do not distinguish between these two steps.
17. This is analogous to Grubbs' explanation for the greater reactivity of 1 in alkene metathesis; see ref 11.
18. (a) Sanford, M. S.; Love, J. A.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 6543-6554.
19. (b) Love, J. A.; Sanford, M. S.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 10103-10109.
20. Ethylene metatheses, which must proceed via C (R = H), are slower reactions due to a greater proportion of the ruthenium carbenes existing in resting state B.
21. 3P complex of 1 gave a faster initial reaction rate (3.2 times faster than that of 1), consistent with the partitioning hypothesis. In this case, however, catalysis stalled after ca. 2 catalytic turnovers (ca. 10% conversion).
22. This is the rate of alkyne 2B disappearance. See Supporting Information.
23. 3P 10 times faster than the benzylidene when extrapolated to 25°C. From: Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.