Poly(1,4:2,2-butanetetrayl). A novel polyspirane via metallocenium-catalyzed ring-opening - Zipping-up polymerization of methylenecyclopropane

Journal of the American Chemical Society

Volumn 118, Issue 6, 1996, Pages 1547-1548

  Jia, Li ^a   Yang, Xinmin ^a   Yang, Shengtian ^a   Marks, Tobin J ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; ORGANOMETALLICS; PARAFFINS; POLYMERIZATION; ZIRCONIUM COMPOUNDS;

METALLOCENIUM; METHYLENECYCLOPROPANE; POLYBUTANETETRAYL; POLYSPIRANES;

POLYMERS;

CYCLOALKANE; CYCLOPROPANE DERIVATIVE; POLYCYCLIC HYDROCARBON;

ARTICLE; DRUG SYNTHESIS; NUCLEAR MAGNETIC RESONANCE; POLYMERIZATION; REACTION ANALYSIS;

EID: 0030087681     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja953195x     Document Type: Article

References (33)

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6. 0 catalysis; see: (a) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128-6129. (b) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5874. (c) Lancaster, S. J.; Robinson, O. B.; Bochmann, M.; Coles, S. J.; Hursthouse, M. B. Organometallics 1995, 14, 2456-2462. (d) Erker, G.; Ahlers, W.; Frohlich, R. J. Am. Chem. Soc. 1995, 117, 5853-5854. (e) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-219. (f) Flores, J. C.; Chien, J. C. W.; Rausch, M. D. Organometallics 1995, 14, 1827-1833. (g) Pellecchia, C.; Pappalardo, D.; Oliva, L.; Zambelli, A. J. Am. Chem. Soc. 1995, 117, 6593-6594. (h) Yang, X.; Stern, C., Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
7. 0 catalysis; see: (a) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128-6129. (b) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5874. (c) Lancaster, S. J.; Robinson, O. B.; Bochmann, M.; Coles, S. J.; Hursthouse, M. B. Organometallics 1995, 14, 2456-2462. (d) Erker, G.; Ahlers, W.; Frohlich, R. J. Am. Chem. Soc. 1995, 117, 5853-5854. (e) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-219. (f) Flores, J. C.; Chien, J. C. W.; Rausch, M. D. Organometallics 1995, 14, 1827-1833. (g) Pellecchia, C.; Pappalardo, D.; Oliva, L.; Zambelli, A. J. Am. Chem. Soc. 1995, 117, 6593-6594. (h) Yang, X.; Stern, C., Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
8. 0 catalysis; see: (a) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128-6129. (b) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5874. (c) Lancaster, S. J.; Robinson, O. B.; Bochmann, M.; Coles, S. J.; Hursthouse, M. B. Organometallics 1995, 14, 2456-2462. (d) Erker, G.; Ahlers, W.; Frohlich, R. J. Am. Chem. Soc. 1995, 117, 5853-5854. (e) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-219. (f) Flores, J. C.; Chien, J. C. W.; Rausch, M. D. Organometallics 1995, 14, 1827-1833. (g) Pellecchia, C.; Pappalardo, D.; Oliva, L.; Zambelli, A. J. Am. Chem. Soc. 1995, 117, 6593-6594. (h) Yang, X.; Stern, C., Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
9. 0 catalysis; see: (a) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128-6129. (b) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5874. (c) Lancaster, S. J.; Robinson, O. B.; Bochmann, M.; Coles, S. J.; Hursthouse, M. B. Organometallics 1995, 14, 2456-2462. (d) Erker, G.; Ahlers, W.; Frohlich, R. J. Am. Chem. Soc. 1995, 117, 5853-5854. (e) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-219. (f) Flores, J. C.; Chien, J. C. W.; Rausch, M. D. Organometallics 1995, 14, 1827-1833. (g) Pellecchia, C.; Pappalardo, D.; Oliva, L.; Zambelli, A. J. Am. Chem. Soc. 1995, 117, 6593-6594. (h) Yang, X.; Stern, C., Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
10. 0 catalysis; see: (a) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128-6129. (b) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5874. (c) Lancaster, S. J.; Robinson, O. B.; Bochmann, M.; Coles, S. J.; Hursthouse, M. B. Organometallics 1995, 14, 2456-2462. (d) Erker, G.; Ahlers, W.; Frohlich, R. J. Am. Chem. Soc. 1995, 117, 5853-5854. (e) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-219. (f) Flores, J. C.; Chien, J. C. W.; Rausch, M. D. Organometallics 1995, 14, 1827-1833. (g) Pellecchia, C.; Pappalardo, D.; Oliva, L.; Zambelli, A. J. Am. Chem. Soc. 1995, 117, 6593-6594. (h) Yang, X.; Stern, C., Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
11. 0 catalysis; see: (a) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128-6129. (b) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5874. (c) Lancaster, S. J.; Robinson, O. B.; Bochmann, M.; Coles, S. J.; Hursthouse, M. B. Organometallics 1995, 14, 2456-2462. (d) Erker, G.; Ahlers, W.; Frohlich, R. J. Am. Chem. Soc. 1995, 117, 5853-5854. (e) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-219. (f) Flores, J. C.; Chien, J. C. W.; Rausch, M. D. Organometallics 1995, 14, 1827-1833. (g) Pellecchia, C.; Pappalardo, D.; Oliva, L.; Zambelli, A. J. Am. Chem. Soc. 1995, 117, 6593-6594. (h) Yang, X.; Stern, C., Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
12. 0 catalysis; see: (a) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128-6129. (b) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5874. (c) Lancaster, S. J.; Robinson, O. B.; Bochmann, M.; Coles, S. J.; Hursthouse, M. B. Organometallics 1995, 14, 2456-2462. (d) Erker, G.; Ahlers, W.; Frohlich, R. J. Am. Chem. Soc. 1995, 117, 5853-5854. (e) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-219. (f) Flores, J. C.; Chien, J. C. W.; Rausch, M. D. Organometallics 1995, 14, 1827-1833. (g) Pellecchia, C.; Pappalardo, D.; Oliva, L.; Zambelli, A. J. Am. Chem. Soc. 1995, 117, 6593-6594. (h) Yang, X.; Stern, C., Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
13. 0 catalysis; see: (a) Deck, P. A.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 6128-6129. (b) Wu, Z.; Jordan, R. F.; Petersen, J. L. J. Am. Chem. Soc. 1995, 117, 5867-5874. (c) Lancaster, S. J.; Robinson, O. B.; Bochmann, M.; Coles, S. J.; Hursthouse, M. B. Organometallics 1995, 14, 2456-2462. (d) Erker, G.; Ahlers, W.; Frohlich, R. J. Am. Chem. Soc. 1995, 117, 5853-5854. (e) Coates, G. W.; Waymouth, R. M. Science 1995, 267, 217-219. (f) Flores, J. C.; Chien, J. C. W.; Rausch, M. D. Organometallics 1995, 14, 1827-1833. (g) Pellecchia, C.; Pappalardo, D.; Oliva, L.; Zambelli, A. J. Am. Chem. Soc. 1995, 117, 6593-6594. (h) Yang, X.; Stern, C., Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10015-10031.
14. n catalysis see: (a) Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283-362. (b) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (c) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623-4640. (d) Molander, G. A.; Hoberg, J. O. J. Org. Chem. 1992, 57, 3266-3268. (e) Heeres, H. J.; Renkema, J.; Booji, M.; Meetsma, A.; Teuben, J. H. Organometallics 1988, 7, 2495-2502. (f) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51-55. (g) Jeske, G.; Lauke, H.; Mauermann, H.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8111-8118.
15. n catalysis see: (a) Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283-362. (b) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (c) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623-4640. (d) Molander, G. A.; Hoberg, J. O. J. Org. Chem. 1992, 57, 3266-3268. (e) Heeres, H. J.; Renkema, J.; Booji, M.; Meetsma, A.; Teuben, J. H. Organometallics 1988, 7, 2495-2502. (f) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51-55. (g) Jeske, G.; Lauke, H.; Mauermann, H.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8111-8118.
16. n catalysis see: (a) Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283-362. (b) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (c) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623-4640. (d) Molander, G. A.; Hoberg, J. O. J. Org. Chem. 1992, 57, 3266-3268. (e) Heeres, H. J.; Renkema, J.; Booji, M.; Meetsma, A.; Teuben, J. H. Organometallics 1988, 7, 2495-2502. (f) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51-55. (g) Jeske, G.; Lauke, H.; Mauermann, H.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8111-8118.
17. n catalysis see: (a) Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283-362. (b) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (c) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623-4640. (d) Molander, G. A.; Hoberg, J. O. J. Org. Chem. 1992, 57, 3266-3268. (e) Heeres, H. J.; Renkema, J.; Booji, M.; Meetsma, A.; Teuben, J. H. Organometallics 1988, 7, 2495-2502. (f) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51-55. (g) Jeske, G.; Lauke, H.; Mauermann, H.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8111-8118.
18. n catalysis see: (a) Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283-362. (b) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (c) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623-4640. (d) Molander, G. A.; Hoberg, J. O. J. Org. Chem. 1992, 57, 3266-3268. (e) Heeres, H. J.; Renkema, J.; Booji, M.; Meetsma, A.; Teuben, J. H. Organometallics 1988, 7, 2495-2502. (f) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51-55. (g) Jeske, G.; Lauke, H.; Mauermann, H.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8111-8118.
19. n catalysis see: (a) Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283-362. (b) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (c) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623-4640. (d) Molander, G. A.; Hoberg, J. O. J. Org. Chem. 1992, 57, 3266-3268. (e) Heeres, H. J.; Renkema, J.; Booji, M.; Meetsma, A.; Teuben, J. H. Organometallics 1988, 7, 2495-2502. (f) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51-55. (g) Jeske, G.; Lauke, H.; Mauermann, H.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8111-8118.
20. n catalysis see: (a) Schaverien, C. J. Adv. Organomet. Chem. 1994, 36, 283-362. (b) Fu, P.-F.; Brard, L.; Li, Y.; Marks, T. J. J. Am. Chem. Soc. 1995, 117, 7157-7168. (c) Shapiro, P. J.; Cotter, W. D.; Schaefer, W. P.; Labinger, J. A.; Bercaw, J. E. J. Am. Chem. Soc. 1994, 116, 4623-4640. (d) Molander, G. A.; Hoberg, J. O. J. Org. Chem. 1992, 57, 3266-3268. (e) Heeres, H. J.; Renkema, J.; Booji, M.; Meetsma, A.; Teuben, J. H. Organometallics 1988, 7, 2495-2502. (f) Watson, P. L.; Parshall, G. W. Acc. Chem. Res. 1985, 18, 51-55. (g) Jeske, G.; Lauke, H.; Mauermann, H.; Schumann, H.; Marks, T. J. J. Am. Chem. Soc. 1985, 107, 8111-8118.
21. (a) Yang, X.; Jia, L.; Marks, T. J. J. Am. Chem. Soc. 1993, 115, 3392-3393.
22. (b) Yang, X.; Seyam, A. M.; Fu, P.-F.; Marks, T. J. Macromolecules 1994, 27, 4625-4626.
23. We thank Dr. W. V. Metanomski of Chemical Abstracts Service for assistance with the nomenclature.
24. Methylenecyclopropane was synthesized according to a literature procedure and purified by trap-to-trap distillation: Köster, R.; Arora, S.; Binger, P. Angew. Chem., Int. Ed. Engl. 1969, 8, 205-206.
25. 3-allyl species.
26. n: C, 88.82. H, 11.18. Found: C. 87.50; H. 11.28. (b) Fisons VG Tofspec and 70-VSE spectrometers were used for UV laser desorption and field desorption mass spectrometry, respectively. A FDMS spectrum is included in the supporting information.
27. The gated inverse decoupling mode was chosen to suppress NOE effects and to thus obtain accurate integrals: Levy, G. C.; Lichter, R. L.; Nelson, G. L. Carbon-13 Nuclear Magnetic Spectroscopy; Wiley: New York, 1982; pp 38-44.
28. See supporting information.
29. (a) Trost, B. M.; Shi, Y. J. Am. Chem. Soc. 1993, 115, 9421-9438.
30. (b) Dispirane and trispirane structures have also been produced by organoscandium catalysts: Bunel, E. E., Ph.D. Thesis, California Institute of Technology. 1989. We thank Prof. J. E. Bercaw for making us aware of this result.
31. This behavior is reminiscent of that of CO-olefin copolymers: Jiang. Z.; Sen. A. J. Am. Chem. Soc. 1995, 117, 4455-4467 and references therein.
32. GPC in 1,2,4-trichlorobenzene is polystyrene. We consider the molecular weights to be "apparent" pending suitable calibration.
33. In principle, ring-unopened cyclopropyl groups could be located either in the middle of the backbone or at the chain end. If in the middle, the zipping-up reaction affording five-membered rings would presumably be halted at cyclopropyl group "kinks", and as a result, large quantities of structure A would remain unzipped. This is not observed, and the cyclopropyl group location is most reasonably assigned to the polymer chain end.