Abstract
The precise placement of functional groups on the chain-ends of macromolecules is a major focus of polymer research. Most common living polymerization techniques offer specific methods of end-functionalization governed by the active propagating species and the kinetics of the polymerization reaction. Ring-opening metathesis polymerization has established itself as one of the most functional-group-tolerant living polymerization techniques known, but this tolerance has limited the number of available functionalization reactions. Metathesis chemists have therefore been required to develop a variety of end-functionalizations, adapting each of them to the reactivity scheme of the particular catalysts used and the complexity of the group to be attached. This review presents an overview of the methods developed for different types and generations of metathesis catalysts that are typically used in such polymerizations. We also present a 'field guide' of functionalization methods highlighting the factors to be considered when choosing the most appropriate approach.
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References
Grubbs, R. H. Handbook of Metathesis (Wiley-VCH, 2003).
Hérisson, J.-L. & Chauvin, Y. Catalyse de transformation des oléfines par les complexes du tungstène. II. Télomérisation des oléfines cycliques en présence d'oléfines acycliques. Makromol. Chem. 141, 161–176 (1971).
Eleuterio, H. C. Polymerization of cyclic olefins. US Patent 3074918 (1963).
Calderon, N., Ofstead, E. A., Ward, J. P., Judy, W. A. & Scott, K. W. Olefin metathesis. I. Acyclic vinylenic hydrocarbons. J. Am. Chem. Soc. 90, 4133–4140 (1968).
Murdzek, J. S. & Schrock, R. R. Low polydispersity homopolymers and block copolymers by ring opening of 5,6-dicarbomethoxynorbornene. Macromolecules 20, 2640–2642 (1987).
Toreki, R. & Schrock, R. R. A well-defined rhenium(VII) olefin metathesis catalyst. J. Am. Chem. Soc. 112, 2448 (1990).
Wallace, K. C., Liu, A. H., Dewan, J. C. & Schrock, R. R. Preparation and reactions of tantalum alkylidene complexes containing bulky phenoxide or thiolate ligands. Controlling ring-opening metathesis polymerization activity and mechanism through choice of anionic ligand. J. Am. Chem. Soc. 110, 4964–4977 (1988).
Schrock, R. R. Multiple metal-carbon bonds for catalytic metathesis reactions (Nobel Lecture). Angew. Chem. Int. Ed. 45, 3748–3759 (2006).
Grubbs, R. H. Olefin-metathesis catalysts for the preparation of molecules and materials (Nobel Lecture). Angew. Chem. Int. Ed. 45, 3760–3765 (2006).
Grubbs, R. H. The development of functional group tolerant ROMP catalysts. J. Macromol. Sci. A 31, 1829–1933 (1994).
Binder, J. B. & Raines, R. T. Olefin metathesis for chemical biology. Curr. Opin. Chem. Biol. 12, 767–773 (2008).
Ulman, M. & Grubbs, R. H. Relative reaction rates of olefin substrates with ruthenium(II) carbene metathesis initiators. Organometallics 17, 2484–2489 (1998).
Maynard, H. D., Okada, S. Y. & Grubbs, R. H. Inhibition of cell adhesion to fibronectin by oligopeptide-substituted polynorbornenes. J. Am. Chem. Soc. 123, 1275–1279 (2001).
Pasut, G. & Veronese, F. M. Polymer–drug conjugation, recent achievements and general strategies. Prog. Polym. Sci. 32, 933–961 (2007).
Nie, Z. & Kumacheva, E. Patterning surfaces with functional polymers. Nature Mater. 7, 277–290 (2008).
Goethals, E. J. Telechelic polymers by cationic ring-opening polymerization. Makromol. Chem. Makromol. Symp. 6, 53–66 (1986).
Goethals, E. J., Van Caeter, P., Du Prez, F. E. & Dubreuil, M. F. Sophisticated macromolecular structures by cationic ring-opening polymerizations. Macromol. Symp. 98, 185–92 (1995).
Gilliom, L. R. & Grubbs, R. H. Titanacyclobutanes derived from strained, cyclic olefins: the living polymerization of norbornene. J. Am. Chem. Soc. 108, 733–742 (1986).
Tebbe, F. N., Parshall, G. W. & Reddy, G. S. Olefin homologation with titanium methylene compounds. J. Am. Chem. Soc. 100, 3611–3613 (1978).
Amass, A. J. & Gregory, D. Anionic to metathesis-transformation polymerization. Br. Polym. J. 19, 263–268 (1987).
Amass, A. J., Bas, S., Gregory, Denis, M. & Mathew C. Block copolymers by metathesis polymerization. Makromol. Chem. 186, 325–330 (1985).
Schwab, P., Grubbs, R. H. & Ziller, J. W. Synthesis and applications of RuCl2(=CHR')(PR3)2: The influence of the alkylidene moiety on metathesis activity. J. Am. Chem. Soc., 118, 100–110 (1996).
Bielawski, C. W., Louie, J. & Grubbs, R. H. Tandem catalysis: Three mechanistically distinct reactions from a single ruthenium complex. J. Am. Chem. Soc., 122, 12872–12873 (2000).
Burtscher, D., Saf, R. & Slugovc, C. Fluorescence-labeled olefin metathesis polymerization initiators. J. Polym. Sci. A 44, 6136–6145 (2006).
Castle, T. C., Hutchings, L. R. & Khosravi, E. Synthesis of block copolymers by changing living anionic polymerization into living ring opening metathesis polymerization. Macromolecules 37, 2035–2040 (2004).
Pine, S. H., Zahler, R., Evans, D. A. & Grubbs, R. H. Titanium-mediated methylene-transfer reactions. Direct conversion of esters into vinyl ethers. J. Am. Chem. Soc. 102, 3270–3272 (1980).
Brown-Wensley, K. A. et al. Cp2TiCH2 complexes in synthetic applications. Pure Appl. Chem. 55, 1733–1744 (1983).
Gilliom, L. R. & Grubbs, R. H. Titanacyclobutanes derived from strained, cyclic olefins: the living polymerization of norbornene. J. Am. Chem. Soc. 108, 733–742 (1986).
Cannizo, L. F. & Grubbs, R. H. End capping of polynorbornene produced by titanacyclobutanes. Macromolecules 20, 1488–1490 (1987).
Risse, W. & Grubbs, R. H. Block and graft copolymers by living ring-opening olefin metathesis polymerization. J. Mol. Catal. 65, 211–217 (1991).
Risse, W. & Grubbs, R. H. Application of Wittig-type reactions of titanacyclobutane end groups for the formation of block and graft copolymers. Macromolecules 22, 4462–4466 (1989).
Schrock, R. R. Living ring-opening metathesis polymerization catalyzed by well-characterized transition-metal alkylidene complexes. Acc. Chem. Res. 23, 158–165 (1990).
Schrock, R. R., Feldman, J., Cannizzo, L. F. & Grubbs, R. H. Ring-opening polymerization of norbornene by a living tungsten alkylidene complex. Macromolecules 20, 1169–1172 (1987).
Murdzek, J. S. & Schrock, R. R. Low polydispersity homopolymers and block copolymers by ring opening of 5,6-dicarbomethoxynorbornene. Macromolecules 20, 2640–2642 (1987).
Schrock, R. R. et al. Synthesis of molybdenum imido alkylidene complexes and some reactions involving acyclic olefins. J. Am. Chem. Soc. 112, 3875–3886 (1990).
Bazan, G. C. et al. Living ring-opening metathesis polymerization of 2,3-difunctionalized norbornadienes by Mo(:CHBu-tert)(:NC6H3Pr-iso2-2,6)(OBu-tert)2. J. Am. Chem. Soc. 112, 8378–8387 (1990).
Albagli, D., Bazan, G. C., Schrock, R. R. & Wrighton, M. S. New functional polymers prepared by ring-opening metathesis polymerization: study of the quenching of luminescence of pyrene end groups by ferrocene or phenothiazine centers in the polymers. J. Phys. Chem. 97, 10211–10216 (1993).
Albagli, D., Bazan, G. C., Schrock, R. R. & Wrighton, M. S. Surface attachment of well-defined redox-active polymers and block polymers via terminal functional groups. J. Am. Chem. Soc. 115, 7328–7334 (1993).
Mitchell, J. O., Gibson, V. C. & Schrock, R. R. Chain-end functionalization of living polymers formed by the ring-opening metathesis polymerization of norbornene. Macromolecules 24, 1220–1221 (1991).
Fox, H. H., Lee, J.-K., Park, L. Y. & Schrock, R. R. Synthesis of five- and six-coordinate alkylidene complexes of the type Mo(CHR)(Nar)[OCMe(CF3)2]2Sx and their use as living ROMP initiators or Wittig reagents. Organometallics 12, 759–768 (1993).
Singh, R., Verploegen, E., Hammond, P. T. & Schrock, R. R. Synthesis of ABA triblock copolymers via ring-opening metathesis polymerization using a bimetallic initiator: Influence of a flexible spacer in the side chain liquid crystalline block. Macromolecules 39, 8241–8249 (2006).
Murphy, J. J. & Nomura, K. Precise synthesis of poly(macromonomer)s containing sugars by repetitive ring-opening metathesis polymerization. Chem Commun. 4080–4082 (2005).
Murphy, J. J., Takahashi, S. & Nomura, K. Synthesis of poly(macromonomer)s by repeating ring-opening metathesis polymerization (ROMP) with Mo(CHCMePh)(NAr)(OR) initiators. Macromolecules 34, 4712–4723 (2001).
Murphy, J. J., Kawasaki, T., Fujiki, M. & Nomura, K. Precise synthesis of amphiphilic polymeric architectures by grafting poly(ethylene glycol) to end-functionalized block ROMP copolymers. Macromolecules 38, 1075–1083 (2005).
Murphy, J. J., Furusho, H., Paton, R. M. & Nomura, K. Precise synthesis of poly(macromonomer)s containing sugars by repetitive ROMP and their attachments to poly(ethylene glycol): synthesis, TEM analysis and their properties as amphiphilic block fragments. Chem. Eur. J. 13, 8985–8997 (2007).
Dounis, P. & Feast, W. J. A route to low polydispersity linear and star polyethylenes via ring-opening metathesis polymerization. Polymer 37, 2547 (1996).
Albagli, D., Bazan, G. C., Schrock, R. R. & Wrighton, M. S. Surface attachment of well-defined redox-active polymers and block polymers via terminal functional groups. J. Am. Chem. Soc 115, 7328–7334 (1993).
Coca, S., Paik, H.-J. & Matyjaszewski, K. Block copolymers by transformation of living ring-openeing metathesis polymerization into controlled/“living” atom transfer radical polymerization. Macromolecules 30, 6573–6576 (1997).
Myers, S. B. & Register, R. A. Block copolymers synthesized by ROMP-to-anionic polymerization transformation. Macromolecules 41, 5283 (2008).
Notestein, J. M., Lee, L.-B. W. & Register, R. A. Well-defined diblock copolymers via termination of living ROMP with anionically polymerized macromolecular aldehydes. Macromolecules 35, 1985–1987 (2002).
Slugovc, C., Demel, S. & Stelzer, F. Ring opening metathesis polymerization in donor solvents. Chem. Commun. 2572–2573 (2002).
Feast, W. J., Gibson, V. C., Khosravi, E., Marshall, E. L. & Mitchell, J. P. Bimolecular termination in living ring opening metathesis polymerization. Polymer 33, 872–873 (1992).
Biagini, S. C. G., Davies, R. G., Gibson, V. C., Giles, M. R., Marshall, E. L. & North, M. Ruthenium initiated ring opening metathesis polymerization of amino-acid and –ester functionalised norbornenes and a highly selective chain-end functionalisation reaction using molecular oxygen. Polymer 42, 6669–6671 (2001).
Wu, Z., Nguyen, S. T., Grubbs, R. H. & Zillier, J. W. Reactions of ruthenium carbenes of the type (PPh3)2(X)2Ru:CH-CH:CPh2 (X = Cl and CF3COO) with strained acyclic olefins and functionalized olefins. J. Am. Chem. Soc. 117, 5503–5511 (1995).
Schwab, P., Grubbs, R. H. & Zillier, J. W. Synthesis and applications of RuCl(CHR')(PR): The influence of the alkylidene moiety on metathesis activity. J. Am. Chem. Soc. 118, 100–110 (1996).
Earnshaw, C., Wallis, C. J. & Warren, S. Synthesis of E- and Z- vinyl ethers by the Horner- Wittig reaction. J. Chem. Soc. Perkin Trans. 1, 12, 3099–106 (1979).
Gordon, E. J., Gestwicki, J. E., Strong, L. E. & Kiessling, L. L. Synthesis of end-labeled multivalent ligands for exploring call-surface-receptor-ligand interactions. Chem. Biol. 7, 9–16 (2000).
Gestwicki, J. E., Cairo, C. W., Mann, D. A., Owen, R. M. & Kiessling, L. L. Selective immobilization of multivalent ligands for surface plasmon resonance and fluorescence microscopy. Anal. Biochem. 305, 149–155 (2002).
Pontrello, J. K., Allen, M. J., Underbakke, E. S. & Kiessling, L. L. Solid-phase synthesis of polymers using the ring-opening metathesis polymerization. J. Am. Chem. Soc. 127, 14536–14537 (2005).
Chen, B., Metera, K. & Sleiman, H. F. Biotin-terminated ruthenium bipyridine ring-opening metathesis polymerization copolymers: Synthesis and self-assembly with streptavidin. Macromolecules 38, 1084–1090 (2005).
Owen, R. M., Gestwicki, J. E., Young, T. & Kiessling, L. L. Synthesis and applications of end-labeled neoglycopolymers. Org. Lett. 4, 2293–2296 (2002).
Mangold, S. L., Carpenter, R. T. & Kiessling, L. L. Synthesis of fluorogenic polymers for visualizing cellular internalization. Org. Lett. 10, 2997–3000 (2008).
Katayama, H., Yonezawa, F., Nagao, M. & Ozawa, F. Ring-opening metathesis polymerization of norbornene using vinylic ethers as chain-transfer agents: Highly selective synthesis of monofunctional macroinitiators for atom transfer radical polymerization. Macromolecules 35, 1133–1136 (2002).
Katayama, H., Urushima, H. & Ozawa, F. Olefin metathesis reactions using vinylideneruthenium(II) complexes as catalyst precursors. J. Organomet. Chem. 606, 16–25 (2000).
Katayama, H., Urushima, H., Nishioka, T., Wada, C., Nagao, M. & Ozawa, F. Highly selective ring-opening/cross-metathesis reactions of norbornene derivatives using selenocarbene complexes as catalysts. Angew. Chem. Int. Ed. 39, 4513–4515 (2000).
Caskey, S. R., Stewart, M. H., Kivela, J. E., Sootsman, J. R., Johnson, M. J. A. & Kampf, J. W. Two generalizable routes to terminal carbide complexes. J. Am. Chem. Soc. 127, 16750–16751 (2005).
Caskey, S. R., Stewart, M. H., Johnson, M. J. A. & Kampf, J. W. Carbon-carbon bond formation at a neutral terminal carbide ligand: Generation of cyclopropenylidene and vinylidene complexes. Angew. Chem. Int. Ed. 45, 7422–7424 (2006).
Macnaughtan, M. L., Johnson, M. J. A. & Kampf, J. W. Olefin metathesis reactions with vinyl halides: Formation, observation, and fate of the ruthenium-monohalomethylidene moiety. J. Am. Chem. Soc. 129, 7708–7709 (2007).
Hilf, S., Grubbs, R. H. & Kilbinger, A. F. M. End capping ring-opening olefin metathesis polymerization polymers with vinyl lactones. J. Am. Chem. Soc. 130, 11040–11048 (2008).
Lexer, C., Saf, R. & Slugovc, C. Acrylates as termination reagent for the preparation of semi-telechelic polymers made by ring opening metathesis polymerization. J. Polym. Sci. A 47, 299–305 (2009).
Li, M. -H., Keller, P. & Albouy, P.-A. Novel liquid crystalline block copolymers by ATRP and ROMP. Macromolecules 36, 2284–2292 (2003).
Matson, J. B. & Grubbs, R. H. ROMP–ATRP block copolymers prepared from monotelechelic poly(oxa)norbornenes using a difunctional terminating agent. Macromolecules 41, 5626–5631 (2008).
Gozgen, A., Dag, A., Durmaz, H., Sirkecioglu, O., Hizal, G. & Tunca, U. ROMP-NMP-ATRP combination for the preaparation of 3-miktoarm star terpolymer via click chemistry. J. Polym. Sci. A1 47, 497–504 (2009).
Schrock, R. R. et al. Evaluation of cyclopentene-based chain-transfer agents for living ring-opening metathesis polymerization. Macromolecules 22, 3191–3200 (1989).
Crowe, W. E., Mitchell, J. P., Gibson, V. C. & Schrock, R. R. Chain-transfer agents for living ROMP [ring opening metathesis polymerization] reactions of norbornene. Macromolecules 23, 3534–3536 (1990).
Benedicto, A. D., Claverie, J. P. & Grubbs, R. H. Molecular weight distribution of living polymerization involving chain-transfer agents: Computational results, analytical solutions, and experimental investigations using ring-opening metathesis polymerization. Macromolecules 28, 500–511 (1995).
Bielawski, C. W., Benitez, D., Morita, T. & Grubbs, R. H. Synthesis of end-functionalized poly(norbornene)s via ring-opening metathesis polymerization. Macromolecules 34, 8610–8618 (2001).
Hillmyer, M. A., Nguyen, S. & Grubbs, R. H. Utility of a ruthenium metathesis catalyst for the preparation of end-functionalized polybutadiene. Macromolecules 30, 718–721 (1997).
Morita, T., Maughon, B. R., Bielawski, C. W. & Grubbs, R. H. A ring-opening metathesis polymerization (ROMP) approach to carboxyl- and amino-terminated telechelic poly(butadiene)s. Macromolecules 33, 6621–6623 (2000).
Ji, S., Hoye, T. T. & Macosko, C. W. Controlled synthesis of high molecular weight telechelic polybutadienes by ring-opening metathesis polymerization Macromolecules 37, 5458–5489 (2004).
Maughon, B. R., Morita, T., Bielawski, C. W. & Grubbs, R. H. Synthesis of cross-linkable telechelic poly(butenylene)s derived from ring-opening metathesis polymerization. Macromolecules 33, 1929–1935 (2000).
Scherman, O. A., Rutenberg, I. M. & Grubbs, R. H. Direct synthesis of soluble, end-functionalized polyenes and polyacetylene block copolymers. J. Am. Chem. Soc. 125, 8515–8522 (2003).
Xia, Y., Verduzco, R., Grubbs, R. H. & Kornfield, J. A. Well-defined liquid crystal gels from telechelic polymers. J. Am. Chem. Soc. 130, 1735–1740 (2008).
Matson, J. B., Virgil, S. C. & Grubbs, R. H. Pulsed-addition ring-opening metathesis polymerization: catalyst-economical syntheses of homopolymers and block copolymers. J. Am. Chem. Soc. 131, 3355–3362 (2009).
Fraser, C., Hillmyer, M. A., Gutierrez, E. & Grubbs, R. H. Degradable cyclooctadiene/acetal copolymers: Versatile precursors to 1,4-hydroxytelechelic polybutadiene and hydroxytelechelic polyethylene. Macromolecules 28, 7256–7261 (1995).
Hilf, S., Berger- Nicoletti, E., Grubbs, R. H. & Kilbinger, A. F. M. Mono-functional metathesis polymers via sacrificial diblock copolymers. Angew. Chem. Int. Ed. 45, 8045–8048 (2006).
Perrier, S. & Wang, X. Sacrificial synthesis. Nature 445, 271 (2007).
Hilf, S. & Kilbinger, A. F. M. An all-ROMP route to graft copolymers. Macromol. Rapid Commun. 28, 1225–1230 (2007).
Hilf, S., Hanik, N. & Kilbinger, A. F. M. A “click” approach to ROMP block copolymers. J. Polym. Sci. A 46, 2913–2921 (2008).
Hilf, S., Grubbs, R. H. & Kilbinger, A. F.M Sacrificial synthesis of hydroxy-functionalized ROMP polymers: An efficiency study. Macromolecules 41, 6006–6011 (2008).
Hilf, S. & Kilbinger, A. F. M. Thiol functionalized ROMP polymers via sacrificial synthesis. Macromolecules 42, 4127–4133 (2009).
Hilf, S. & Kilbinger, A. F. M. Sacrificial synthesis of hydroxy-telechelic metathesis polymers via multiblock copolymers. Macromolecules 42, 1099–1106 (2009).
Acknowledgements
S.H. thanks the POLYMAT Graduate School of Excellence and the IRTG International Research Training Group (University of Mainz) for funding. A.F.M.K. thanks the Deutsche Forschungsgemeinschaft (DFG) for financial support.
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Hilf, S., Kilbinger, A. Functional end groups for polymers prepared using ring-opening metathesis polymerization. Nature Chem 1, 537–546 (2009). https://doi.org/10.1038/nchem.347
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DOI: https://doi.org/10.1038/nchem.347
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