Ring-opening metathesis polymerization of norbornene in the presence of heteroatom-substituted vinylic compounds: Highly selective synthesis of end-functionalized poly(norbornene)s

Chemistry Letters

Volumn , Issue 5, 1999, Pages 369-370

  Katayama, Hiroyuki ^a   Urushima, Hideto ^a   Ozawa, Fumiyuki ^a  

^a Osaka Prefecture University   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0033241972     PISSN: 03667022     EISSN: None     Source Type: Journal    
DOI: 10.1246/cl.1999.369     Document Type: Article

References (18)

1. T. Morita, B. R. Maughon, and R. H. Grubbs, Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem., 39, 226 (1998); M. A. Hillmyer, S. T. Nguyen, and R. H. Grubbs, Macromolecules, 30, 718 (1997); P. O. Nubel, H. B. Yokelson, C. A. Lutman, W. G. Bouslog, R. T. Behrends, and K. D. Runge, J. Mol. Catal. A, Chem., 115, 43 (1997); M. A. Hillmyer and R. H. Grubbs, Macromolecules, 28, 8662 (1995), and references cited therein.
2. T. Morita, B. R. Maughon, and R. H. Grubbs, Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem., 39, 226 (1998); M. A. Hillmyer, S. T. Nguyen, and R. H. Grubbs, Macromolecules, 30, 718 (1997); P. O. Nubel, H. B. Yokelson, C. A. Lutman, W. G. Bouslog, R. T. Behrends, and K. D. Runge, J. Mol. Catal. A, Chem., 115, 43 (1997); M. A. Hillmyer and R. H. Grubbs, Macromolecules, 28, 8662 (1995), and references cited therein.
3. T. Morita, B. R. Maughon, and R. H. Grubbs, Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem., 39, 226 (1998); M. A. Hillmyer, S. T. Nguyen, and R. H. Grubbs, Macromolecules, 30, 718 (1997); P. O. Nubel, H. B. Yokelson, C. A. Lutman, W. G. Bouslog, R. T. Behrends, and K. D. Runge, J. Mol. Catal. A, Chem., 115, 43 (1997); M. A. Hillmyer and R. H. Grubbs, Macromolecules, 28, 8662 (1995), and references cited therein.
4. T. Morita, B. R. Maughon, and R. H. Grubbs, Polym. Prepr., Am. Chem. Soc., Div. Polym. Chem., 39, 226 (1998); M. A. Hillmyer, S. T. Nguyen, and R. H. Grubbs, Macromolecules, 30, 718 (1997); P. O. Nubel, H. B. Yokelson, C. A. Lutman, W. G. Bouslog, R. T. Behrends, and K. D. Runge, J. Mol. Catal. A, Chem., 115, 43 (1997); M. A. Hillmyer and R. H. Grubbs, Macromolecules, 28, 8662 (1995), and references cited therein.
5. Vinyl ethers are commonly used as a terminator of ROMP: M. A. Hillmyer, W. R. Laredo, and R. H. Grubbs, Macromolecules, 28, 6311 (1995); S. Kanaoka and R. H. Grubbs, Macromolecules, 28, 4707 (1995).
6. Vinyl ethers are commonly used as a terminator of ROMP: M. A. Hillmyer, W. R. Laredo, and R. H. Grubbs, Macromolecules, 28, 6311 (1995); S. Kanaoka and R. H. Grubbs, Macromolecules, 28, 4707 (1995).
7. H. Katayama and F. Ozawa, Chem. Lett., 1998, 67.
8. H. Katayama and F. Ozawa, Organometallics, 17, 5190 (1998).
9. Owing to low efficiency of the vinylidene initiator, the molecular weight observed in the absence of vinylic compounds was significantly higher than that expected from the monomer to catalyst ratio: see Ref. 3.
10. L. R. Gilliom and R. H. Grubbs, J. Am. Chem. Soc., 108 733 (1986).
11. n values are known to be approximately half of the GPC data based on polystyrene standards: Ref. 6; T. J. Katz, S. J. Lee, and N. Acton, Tetrahedron Lett., 1976, 4247; T. J. Katz, and N. Acton, Tetrahedron Lett., 1976, 4251.
12. n values are known to be approximately half of the GPC data based on polystyrene standards: Ref. 6; T. J. Katz, S. J. Lee, and N. Acton, Tetrahedron Lett., 1976, 4247; T. J. Katz, and N. Acton, Tetrahedron Lett., 1976, 4251.
13. P. Schwab, R. H. Grubbs, and J. W. Ziller, J. Am. Chem. Soc., 118, 100 (1996).
14. 3) δ 30.9 (s).
15. This fact indicates that the reaction of 3 with norbornene serves as the rate-determining step of the catalytic cycle in Scheme 1. Therefore, it may be considered that the difference in the polymerization rates dependent upon the CTAs are mainly due to the reactivities of Fischer-type carbene intermediates toward olefin-metathesis. Actually, the isolated thiocarbene complex (3a) exhibited much higher reactivity than the oxycarbene analog toward ROMP of norbornene, which is consistent with the particularly high reactivity of the catalytic system using phenyl vinyl sulfide as a CTA (Table 1, run 5): H. Katayama, H. Urushima, T. Nishioka, and F. Ozawa, unpublished results.
16. 8 may provide the higher reactivity of the present catalytic systems.
17. For olefin-metathesis reactions of Fischer-type carbene complexes, see: M. Mori, in "Alkene Metathesis in Organic Synthesis," ed by A. Fürstner, Springer-Verlag, Berlin (1998), p. 133; M. Hoffmann, M. Buchert, and H.-U. Reissig, Angew. Chem., Int. Ed. Engl., 36, 283 (1997).
18. For olefin-metathesis reactions of Fischer-type carbene complexes, see: M. Mori, in "Alkene Metathesis in Organic Synthesis," ed by A. Fürstner, Springer-Verlag, Berlin (1998), p. 133; M. Hoffmann, M. Buchert, and H.-U. Reissig, Angew. Chem., Int. Ed. Engl., 36, 283 (1997).