Abstract
The Rh(nbd)(l-proline) (nbd = 2,5-norbornadiene) catalyst was synthesised with l-proline as ligand. The achiral monomer phenylacetylene, having two hydroxyl groups and a dodecyl group (DoDHPA), was polymerised for the first time using an isolated chiral Rh(nbd)(l-proline) as catalyst to afford polymers of Mr of 28.5 × 104 and 36.2 × 104. The resulting polymers exhibited the Cotton effect at wavelengths assignable to the main chain, indicating that the polymers adopted one-handed helical conformation. These findings suggest that the rhodium complex with chiral amine may be the true active species for helix-sense-selective polymerisation (HSSP) of DoDHPA.
References
Aoki, T., Kaneko, T., Maruyama, N., Sumi, A., Takahashi, M., Sato, T., & Teraguchi, M. (2003). Helix-sense-selective polymerization of phenylacetylene having two hydroxy groups using a chiral catalytic system. Journal of the American Chemical Society, 125, 6346–6347. DOI: 10.1021/ja021233o.
Bondarev, D., Zedník, J., Plutnarová, I., Vohlídal, J., & Sedláček, J. (2010). Molecular weight and configurational stability of poly[(fluorophenyl)acetylene]s prepared with metathesis and insertion catalysts. Journal of Polymer Science Part A: Polymer Chemistry, 48, 4296–4309. DOI: 10.1002/pola.24218.
Hetterscheid, D. G. H., Hendriksen, C., Dzik, W. I., Smits, J. M. M., van Eck, E. R. H., Rowan, A. E., Busico, V., Vacatello, M., Castell, V. V. A., Segre, A., Jellema, E., Bloemberg, T. G., & de Bruin, B. (2006). Rhodium-mediated stereoselective polymerization of “carbenes”. Journal of the American Chemical Society, 128, 9746–9752. DOI: 10.1021/ja058722j.
Hadano, S., Kishimoto, T., Hattori, T., Tanioka, D., Teraguchi, M., Aoki, T., Kaneko, T., Namikoshi, T., & Marwanta, E. (2009). Helix-sense-selective polymerization of achiral bis(hydroxymethyl)phenylacetylenes bearing alkyl groups of different lengths. Macromolecular Chemistry and Physics, 210, 717–727. DOI: 10.1002/macp.200800594.
Jellema, E., Budzelaar, P. H. M., Reek, J. N. H., & de Bruin, B. (2007). Rh-Mediated polymerization of carbenes: Mechanism and stereoregulation. Journal of the American Chemical Society, 129, 11631–11641. DOI: 10.1021/ja073897+.
Jia, H. G., Teraguchi, M., Aoki, T., Abe, Y., Kaneko, T., Hadano, S., Namikoshi, T., & Marwanta, E. (2009). Two modes of asymmetric polymerization of phenylacetylene having a l-valinol residue and two hydroxy groups. Macromolecules, 42, 17–19. DOI: 10.1021/ma802313z.
Jia, H. G., Teraguchi, M., Aoki, T., Abe, Y., Kaneko, T., Hadano, S., Namikoshi, T., & Ohishi, T. (2010). Three mechanisms of asymmetric polymerization of phenylacetylenes having an l-amino ether residue and two hydroxy groups. Macromolecules, 43, 8353–8362. DOI: 10.1021/ma101424x.
Jia, H. G., Li, J., Zang, Y., Aoki, T., Teraguchi, M., & Kaneko, T. (2012). Two modes of asymmetric polymerization of phenylacetylenes having an l-amino alcohol residue and two hydroxy groups. Journal of Polymer Science Part A: Polymer Chemistry, 50, 5134–5143. DOI: 10.1002/pola.26346.
Kaneko, T., Umeda, Y., Yamamoto, T., Teraguchi, M., & Aoki, T. (2005). Assignment of helical sense for poly(phenylacetylene) bearing achiral galvinoxyl chromophore synthesized by helix-sense-selective polymerization. Macromolecules, 38, 9420–9426. DOI: 10.1021/ma050864a.
Kaneko, T., Umeda, Y., Jia, H. G., Hadano, S., Teraguchi, M., & Aoki, T. (2007). Helix-sense tunability induced by achiral diene ligands in the chiral catalytic system for the helixsense-selective polymerization of achiral and bulky phenylacetylene monomers. Macromolecules, 40, 7098–7102. DOI: 10.1021/ma0713963.
Kim, H. J., Lee, D. H., Lee, S., Suzuki, N., Fujiki, M., Lee, C. L., & Kwak, G. (2013). Optically active conjugated polymer from solvent chirality transfer polymerization in monoterpenes. Macromolecular Rapid Communications, 34, 1471–1479. DOI: 10.1002/marc.201300506.
Kumagai, T., & Itsuno, S. (2002). Asymmetric allylation polymerization of bis(allylsilane) and dialdehyde containing arylsilane structure. Macromolecules, 35, 5323–5325. DOI: 10.1021/ma012023j.
Mawatari, Y., Motoshige, A., Yoshida, Y., Motoshige, R., Sasaki, T., & Tabata, M. (2014). Structural determination of stretched helix and contracted helix having yellow and red colors of poly(2-ethynylnaphthalene) prepared with a [Rh(norbornadiene)Cl]2-triethylamine catalyst. Polymer, 55, 2356–2361. DOI: 10.1016/j.polymer.2014.04.001.
Onishi, N., Shiotsuki, M., Sanda, F., & Masuda, T. (2009). Polymerization of phenylacetylenes with rhodium zwitterionic complexes: Enhanced catalytic activity by π-acidic diene ligands. Macromolecules, 42, 4071–4076. DOI: 10.1021/ma900293t.
Sato, T., Aoki, T., Teraguchi, M., Kaneko, T., & Kim, S. Y. (2004). Role of chiral amine cocatalysts in the helix-sense-selective polymerization of a phenylacetylene using a catalytic system. Polymer, 45, 8109–8114. DOI: 10.1016/j.polymer.2004.09.046.
Teraguchi, M., Tanioka, D., Kaneko, T., & Aoki, T. (2012). Helix-sense-selective polymerization of achiral phenylacetylenes with two N-alkylamide groups to generate the one-handed helical polymers stabilized by intramolecular hydrogen bonds. ACS Macro Letters, 1, 1258–1261. DOI: 10.1021/mz300309c.
Trhlíková, O., Zedník, J., Balcar, H., Brus, J., & Sedláček, J. (2013). [Rh(cycloolefin)(acac)] complexes as catalysts of polymerization of aryl-and alkylacetylenes: Influence of cycloolefin ligand and reaction conditions. Journal of Molecular Catalysis A: Chemical, 378, 57–66. DOI: 10.1016/j.molcata.2013.05.022.
Victoria Jiménez, M., Pérez-Torrente, J. J., Bartolomé, I. M., Vispe, E., Lahoz, F. J., & Oro, L. A. (2009). Cationic rhodium complexes with hemilabile phosphine ligands as polymerization catalyst for high molecular weight stereoregular poly(phenylacetylene). Macromolecules, 42, 8146–8156. DOI: 10.1021/ma901549g.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Rights and permissions
About this article
Cite this article
Jia, HG., Shi, YQ., Ma, LQ. et al. Asymmetric polymerisation of substituted phenylacetylene using chiral Rh(2,5-norbornadiene)(l-proline) catalyst. Chem. Pap. 69, 756–760 (2015). https://doi.org/10.1515/chempap-2015-0075
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1515/chempap-2015-0075