Abstract
The first helical double-stranded polymer by ring-opening metathesis polymerization (ROMP) of a bisnorbornene derivative and the replication of a single-stranded polynorbornene leading to its complementary polynorbornene derivative are described. Base-promoted hydrolysis of this polymer affords the corresponding single-stranded polymer and the linker, ferrocene-1,1'-dicarboxylic acid, in excellent yield. Three forms (helical, supercoil, and ladder) of the polymer have been observed by scanning tunneling microscopy (STM) and simulated by molecular mechanical and dynamical calculations. The polymer thus obtained has a structural resemblance to DNA by having similar width, number of monomeric units per pitch, five-membered rings in the polymeric frame, perpendicular linkers to the backbones, and similar spacing between neighboring monomeric units. In the replication study, the single-stranded polynorbornene acts as a template for norbornene monomer adhesion via ester linkage. This polymer is treated with Grubbs-I catalyst to proceed the ROMP to afford the corresponding unsymmetric double-stranded polymer. After hydrolysis, a complementary polynorbornenecarboxylic acid is produced. This approach may provide a versatile entry for the design, synthesis, and physicochemical investigations of new types of polymers for simulation of biological systems as well as materials applications.
Conference
International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS-14), International Symposium on Organometallic Chemistry Directed Toward Organic Synthesis, OMCOS, Organometallic Chemistry Directed Toward Organic Synthesis, 14th, Nara, Japan, 2007-08-02–2007-08-06
References
1. G. W. Coates, R. M. Waymouth. In Comprehensive Organometallic Chemistry II, E. W. Abel, F. G. A. Stone, G. Wilkinson (Eds.), Vol. 12, Chap. 12.11, Elsevier, Oxford (1995).Search in Google Scholar
2. R. H. Grubbs (Ed.). Handbook of Metathesis, Wiley-VCH, Weinheim (2003).10.1002/9783527619481Search in Google Scholar
3. A. Mori, M. S. Mohamed Ahmed. In Comprehensive Organometallic Chemistry III, R. H. Crabtree, D. M. P. Mingos (Eds.), Vol. 11, Chap. 11.19, Elsevier, Oxford (2007).Search in Google Scholar
4. doi:10.1039/b609412k, T.-Y. Luh, Y.-J. Cheng. Chem. Commun. 4669 (2006).Search in Google Scholar
5. doi:10.1002/asia.200600026, C.-M. Chou, W.-Q. Chen, J.-H. Chen, C.-L. Lin, J.-C. Tseng, C.-F. Lee, T.-Y. Luh. Chem. Asian J. 1, 46 (2006).Search in Google Scholar
6. doi:10.1002/anie.200503406, H.-C. Yang, S.-Y. Lin, H.-c. Yang, C.-L. Lin, L. Tsai, S.-L. Huang, I.-W. P. Chen, C.-h. Chen, B.Y. Jin, T.-Y. Luh. Angew. Chem., Int. Ed. 45, 726 (2006).Search in Google Scholar
7. doi:10.1002/anie.200700472, N.-T. Lin, S.-Y. Lin, S.-L Lee, C.-h. Chen, C.-H. Hsu, L.-P. Hwang, Z.-Y. Xie, C.-H. Chen, S.-L. Huang, T.-Y. Luh. Angew. Chem., Int. Ed. 46, 4481 (2007).Search in Google Scholar
8. doi:10.1073/pnas.84.9.2565, J.-M. Lehn, A. Rigault, J. Siegel, J. Harrowfield, B. Chevrier, D. Moras. Proc. Natl. Acad. Sci. USA 84, 2565 (1987).Search in Google Scholar
9. doi:10.1021/cr960053s, C. Piguet, G. Bernardinelli, G. Hopfgartner. Chem. Rev. 97, 2005 (1997).Search in Google Scholar
10. doi:10.1021/cr0103672, M. Albrecht. Chem. Rev. 101, 3457 (2001).Search in Google Scholar
11. D. J. Hill, M. J. Mio, R. B. Prince, T. S. Hughes, J. S. Moore. Chem. Rev. 101, 3893 (2001) and refs. therein.10.1021/cr990120tSearch in Google Scholar PubMed
12. Y. Furusho, E. Yashima. Chem. Rec. 7, 1 (2007) and refs. therein.10.1002/tcr.20097Search in Google Scholar PubMed
13. doi:10.1021/ja0275358, G. J. Gabriel, B. L. Iverson. J. Am. Chem. Soc. 124, 15174 (2002).Search in Google Scholar
14. doi:10.1038/370126a0, A. Harada, J. Li, M. Kamachi. Nature 370, 126 (1990).Search in Google Scholar
15. doi:10.1021/ja011575e, S. Nagahama, A. Matsumoto. J. Am. Chem. Soc. 123, 12176 (2001).Search in Google Scholar
16. doi:10.1021/ja026205k, T. E. O. Screen, J. R. G. Thorne, R. G. Denning, D. G. Bucknall, H. L. Anderson. J. Am. Chem. Soc. 124, 9712 (2002).Search in Google Scholar
17. doi:10.1021/ja025650c, H. Tang, J. Sun, J. Jiang, X. Zhou, T. Hu, P. Xie, R. Zhang. J. Am. Chem. Soc. 124, 10482 (2002).Search in Google Scholar
18. doi:10.1021/ja067613h, T. Sugimoto, T. Suzuki, S. Shinkai, K. Sada. J. Am. Chem. Soc. 129, 270 (2007).Search in Google Scholar
19. doi:10.1002/9783527619481.ch34, J. G. Hamilton. In Handbook of Metathesis, Vol. 3, R. H. Grubbs (Ed.), pp. 143-179, Wiley-VCH, Weinheim (2003).Search in Google Scholar
20. doi:10.1021/ja952676d, P. Schwab, R. H. Grubbs, J. W. Ziller. J. Am. Chem. Soc. 118, 100 (1996).Search in Google Scholar
21. doi:10.1002/chem.200500770, W.-Y. Lin, M. G. Murugesh, S. Sudhakar, H.-C. Yang, H.-C. Tai, C.-S. Chang, Y.-H. Liu, Y. Wang, Y. I.-W. P. Chen, C.-h. Chen, T.-Y. Luh. Chem.Eur. J. 12, 324 (2006).Search in Google Scholar
22. doi:10.1021/cr990248a, M. R. Buchmeiser. Chem. Rev. 100, 1565 (2000).Search in Google Scholar
23. doi:10.1016/S1381-1169(00)00227-2, E. Khosravi, W. J. Feast, A. A. Al-Hajaji, T. Leejarkpai. J. Mol. Catal. 160, 1 (2000).Search in Google Scholar
24. doi:10.1002/marc.200500578, D. Wang, L. Yang, U. Decker, M. Findeisen, M. R. Buchmeiser. Macromol. Rapid Commun. 26, 1757 (2005).Search in Google Scholar
25. doi:10.1021/ma9812783, L. Delaude, A. Demonceau, A. F. Noels. Macromolecules 32, 2091 (1999).Search in Google Scholar
26. doi:10.1002/asia.200700011, W.-Y. Lin, H.-W. Wang, Z.-C. Liu, J. Xu, C.-W. Chen, Y.-C. Yang, S.-L. Huang, H.-C. Yang, T.Y. Luh. Chem. Asian J. 2, 764 (2007).Search in Google Scholar
27. The numberings of the monomeric unit in polynorbornene backbone are based on the numberings of norbornenes.Search in Google Scholar
28. W.-Y. Lin, Z. Zhang, Z.-C. Liu, J. Xu, J. Cai. Unpublished results.Search in Google Scholar
29. C. P. Brock, Y. Fu. Acta Crystallogr., Sect. B: Struct. Sci. 53, 928 (1977).Search in Google Scholar
30. doi:10.1016/j.tet.2007.02.094, Y.-Y. Lai, N.-T. Lin, Y.-H. Liu, Y. Wang, T.-Y. Luh. Tetrahedron 63, 6051 (2007).Search in Google Scholar
31. doi:10.1016/0022-0728(91)85056-U, G. Denuault, M. V. Mirkin, A. J. Bard. J. Electroanal. Chem. 308, 27 (1992).Search in Google Scholar
32. C.-L. Lin. Unpublished results.Search in Google Scholar
33. doi:10.1002/anie.200400656, X. Liu, D. R. Liu. Angew. Chem., Int. Ed. 43, 4848 (2004).Search in Google Scholar
34. doi:10.1002/1521-3773(20010702)40:13<2382::AID-ANIE2382>3.0.CO;2-G, L. J. Prins, D. N. Reinhoudt, P. Timmerman. Angew. Chem., Int. Ed. 40, 2382 (2001).Search in Google Scholar
35. doi:10.1039/a803602k, A. Robertson, A. J. Sinclair, D. Philp. Chem. Soc. Rev. 29, 141 (2000).Search in Google Scholar
36. doi:10.1126/science.256.5060.1179, Q. Feng, T. K. Park, J. Rebek Jr. Science 256, 1179 (1992).Search in Google Scholar
37. doi:10.1021/ar00051a004, L. E. Orgel. Acc. Chem. Res. 28, 109 (1995).Search in Google Scholar
38. doi:10.2174/1385272013375085, Z.-Y. J. Zhan, J. Ye, X. Li, D. G. Lynn. Curr. Org. Chem. 5, 885 (2001).Search in Google Scholar
39. doi:10.1021/jo00425a040, P. G. Gassman, W. N. Schenk. J. Org. Chem. 42, 918 (1977).Search in Google Scholar
40. doi:10.1021/jo00033a048, T. Sato, J. Otera, H. Nozaki. J. Org. Chem. 57, 2166 (1992).Search in Google Scholar
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