Quantitative ring-closing metathesis of polyolefins

Journal of the American Chemical Society

Volumn 118, Issue 1, 1996, Pages 229-230

  Coates, Geoffrey W ^a   Grubbs, Robert H ^a  

^a California Institute of Technology   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001623127     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9532603     Document Type: Article

References (22)

1. For reviews covering the functionalization of unsaturated polymers, see: (a) McGrath, M. P.; Sail, E D.; Tremont, S. J. Chem. Rev. 1995, 95, 381-398. (b) Schulz, D. N.; Turner, S. R.; Golub, M. A. Rubber Chem. Technol. 1982, 55, 809-859 and references therein.
2. For reviews covering the functionalization of unsaturated polymers, see: (a) McGrath, M. P.; Sail, E D.; Tremont, S. J. Chem. Rev. 1995, 95, 381-398. (b) Schulz, D. N.; Turner, S. R.; Golub, M. A. Rubber Chem. Technol. 1982, 55, 809-859 and references therein.
3. For a review, see: Bartlett, P. A. In Asymmetric Synthesis.; Morrison, J. D., Ed.: Academic Press: Orlando, 1983, Vol 3, pp 341-409.
4. For transition-metal-catalyzed polyolefin cyclizations, see: (a) Tietze, L. F.; Beifuss, U. Angew. Chem., Int. Ed. Engl. 1993, 32, 131-163. (b) Trost, B. M.; Shi, Y J. Am. Chem. Soc. 1993, 115, 9421-9438.
5. For transition-metal-catalyzed polyolefin cyclizations, see: (a) Tietze, L. F.; Beifuss, U. Angew. Chem., Int. Ed. Engl. 1993, 32, 131-163. (b) Trost, B. M.; Shi, Y J. Am. Chem. Soc. 1993, 115, 9421-9438.
6. Grubbs, R. H.; Miller, S. J.; Fu, G. C. Acc. Chem. Res. 1995, 28, 446-452 and references therein.
7. Schwab, P , France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041.
8. These polymers contain 97% 1.2-units. Halasa, A. F.; Lohr, D. F.; Hall, J. E. J. Polym. Sci., Polym. Chem. Ed. 1981, 19, 1357-1360.
9. The resonances in Figure 1 at 5.0 and 5.4 ppm are likely due to end groups (vide infra).
10. (a) Cheng, H. N.; Khasat, N. P. J. Appl. Polvm. Sci. 1988, 35, 825-829.
11. (b) Resconi, L.; Waymouth, R. M. J. Am. Chem. Soc. 1990, 112, 4953-4954.
12. Coates, G. W.; Waymouth, R M. J. Am. Chem. Soc. 1993. 115, 91-98
13. The polymer samples were prepared according to ref 6 (25 °C, 1,2-dipiperidinoethane:butyllithium ratio of 5.0).
14. (a) Hummel, K. Pure Appl. Chem. 1982, 54, 351-364.
15. (b) Hummel, K. In Olefin Metathesis and Polymerization Catalysts; Imamoglu, Y., Zümreoglu-Karan, B., Amass, A. J., Eds.; Kluwer Academic Publishers: Dordrecht, 1990; pp 209-232.
16. (c) Thorn-Csányi, E. Rubber Chem. Technol. 1994, 67, 786-796 and references therein.
17. The maximum degree of polymerization of the cyclized polymer should be inversely proportional to the fraction of 1,4-units.
18. Oskam, J. H.; Fox, H. H.; Yap, K. B.; McConville, D. H.; O'Dell, R.; Lichtenstein, B. J.; Schrock, R. R. J. Organomet. Chem. 1993, 459, 185-198 and references therein.
19. 1,2-PZP was chosen over 1.2-PBD due to its greater solubility in benzene, and catalyst 4 was employed due to its high reactivity with disubstituted olefins.
20. Ricci, G.; Italia, S.; Porri, L. Macromolecules 1994, 27, 868-869.
21. (a) Flory, P. J. J. Am. Chem. Soc. 1939, 61, 1518-1521.
22. (b) Platé, N. A.; Noah, O. V. Adv. Polym. Sci. 1979, 31, 133-173.