Toward the molecular imprinting of titanium Lewis acids: Demonstration of Diels-Alder catalysis

Organometallics

Volumn 17, Issue 15, 1998, Pages 3138-3140

  Santora, Brian P ^a   Larsen, Andrew O ^a   Gagné, Michel R ^a  

^a University of North Carolina at Chapel Hill   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 3843088498     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om980341+     Document Type: Article

References (32)

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4. For reviews see: (a) Wulff, G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1812-1832. (b) Steinke, J.; Sherrington, D. C.; Dunkin, I. R. Adv. Polym. Sci. 1995, 123, 81-125. (c) Shea, K. J. Trends Polym. Sci. 1994, 2, 166-173. (d) Mosbach, K. Trends Biochem. Sci. 1994, 9-14. (e) Wulff, G. In Polymeric Reagents and Catalysis; Ford, W. T., Ed.; ACS Symposium Series 308; American Chemical Society: Washington, DC, 1986; pp 186-230.
5. For reviews see: (a) Wulff, G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1812-1832. (b) Steinke, J.; Sherrington, D. C.; Dunkin, I. R. Adv. Polym. Sci. 1995, 123, 81-125. (c) Shea, K. J. Trends Polym. Sci. 1994, 2, 166-173. (d) Mosbach, K. Trends Biochem. Sci. 1994, 9-14. (e) Wulff, G. In Polymeric Reagents and Catalysis; Ford, W. T., Ed.; ACS Symposium Series 308; American Chemical Society: Washington, DC, 1986; pp 186-230.
6. For reviews see: (a) Wulff, G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1812-1832. (b) Steinke, J.; Sherrington, D. C.; Dunkin, I. R. Adv. Polym. Sci. 1995, 123, 81-125. (c) Shea, K. J. Trends Polym. Sci. 1994, 2, 166-173. (d) Mosbach, K. Trends Biochem. Sci. 1994, 9-14. (e) Wulff, G. In Polymeric Reagents and Catalysis; Ford, W. T., Ed.; ACS Symposium Series 308; American Chemical Society: Washington, DC, 1986; pp 186-230.
7. For reviews see: (a) Wulff, G. Angew. Chem., Int. Ed. Engl. 1995, 34, 1812-1832. (b) Steinke, J.; Sherrington, D. C.; Dunkin, I. R. Adv. Polym. Sci. 1995, 123, 81-125. (c) Shea, K. J. Trends Polym. Sci. 1994, 2, 166-173. (d) Mosbach, K. Trends Biochem. Sci. 1994, 9-14. (e) Wulff, G. In Polymeric Reagents and Catalysis; Ford, W. T., Ed.; ACS Symposium Series 308; American Chemical Society: Washington, DC, 1986; pp 186-230.
8. (a) Mutsui, J.; Nicholls, I. A.; Karube, I.; Mosbach, K. J. Org. Chem. 1996, 61, 5414-5417.
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11. For examples of molecularly imprinted metal complexes see: (a) Krebs, J. F.; Borovik, A. S. Chem. Commun. 1998, 553-554. (b) Krebs, J. F.; Borovik, A. S. J. Am. Chem. Soc. 1995, 117, 10593-10594. (c) Mallik, S.; Plunkett, S. D.; Dhal, P.; Johnson, R. D.; Pack, D.; Shnek, D.; Arnold, F. H. New J. Chem. 1994, 18, 299-304 and references therein. (d) Fujii, Y.; Matsutani, K.; Kikuchi, K. J. Chem. Soc., Chem. Commun. 1985, 415-417. (e) Minutolo, F.; Pini, D.; Salvadori, P. Tetrahedron. Lett. 1996, 37, 3375-3378.
12. For examples of molecularly imprinted metal complexes see: (a) Krebs, J. F.; Borovik, A. S. Chem. Commun. 1998, 553-554. (b) Krebs, J. F.; Borovik, A. S. J. Am. Chem. Soc. 1995, 117, 10593-10594. (c) Mallik, S.; Plunkett, S. D.; Dhal, P.; Johnson, R. D.; Pack, D.; Shnek, D.; Arnold, F. H. New J. Chem. 1994, 18, 299-304 and references therein. (d) Fujii, Y.; Matsutani, K.; Kikuchi, K. J. Chem. Soc., Chem. Commun. 1985, 415-417. (e) Minutolo, F.; Pini, D.; Salvadori, P. Tetrahedron. Lett. 1996, 37, 3375-3378.
13. For examples of molecularly imprinted metal complexes see: (a) Krebs, J. F.; Borovik, A. S. Chem. Commun. 1998, 553-554. (b) Krebs, J. F.; Borovik, A. S. J. Am. Chem. Soc. 1995, 117, 10593-10594. (c) Mallik, S.; Plunkett, S. D.; Dhal, P.; Johnson, R. D.; Pack, D.; Shnek, D.; Arnold, F. H. New J. Chem. 1994, 18, 299-304 and references therein. (d) Fujii, Y.; Matsutani, K.; Kikuchi, K. J. Chem. Soc., Chem. Commun. 1985, 415-417. (e) Minutolo, F.; Pini, D.; Salvadori, P. Tetrahedron. Lett. 1996, 37, 3375-3378.
14. For examples of molecularly imprinted metal complexes see: (a) Krebs, J. F.; Borovik, A. S. Chem. Commun. 1998, 553-554. (b) Krebs, J. F.; Borovik, A. S. J. Am. Chem. Soc. 1995, 117, 10593-10594. (c) Mallik, S.; Plunkett, S. D.; Dhal, P.; Johnson, R. D.; Pack, D.; Shnek, D.; Arnold, F. H. New J. Chem. 1994, 18, 299-304 and references therein. (d) Fujii, Y.; Matsutani, K.; Kikuchi, K. J. Chem. Soc., Chem. Commun. 1985, 415-417. (e) Minutolo, F.; Pini, D.; Salvadori, P. Tetrahedron. Lett. 1996, 37, 3375-3378.
15. For examples of molecularly imprinted metal complexes see: (a) Krebs, J. F.; Borovik, A. S. Chem. Commun. 1998, 553-554. (b) Krebs, J. F.; Borovik, A. S. J. Am. Chem. Soc. 1995, 117, 10593-10594. (c) Mallik, S.; Plunkett, S. D.; Dhal, P.; Johnson, R. D.; Pack, D.; Shnek, D.; Arnold, F. H. New J. Chem. 1994, 18, 299-304 and references therein. (d) Fujii, Y.; Matsutani, K.; Kikuchi, K. J. Chem. Soc., Chem. Commun. 1985, 415-417. (e) Minutolo, F.; Pini, D.; Salvadori, P. Tetrahedron. Lett. 1996, 37, 3375-3378.
16. (a) Wulff, G.; Gross, T.; Schönfeld, R. Angew. Chem., Int. Ed. Engl. 1997, 36, 1962-1964.
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19. Duff, A. W.; Kamarudin, R. A.; Lappert, M. F.; Norton, R. J. J. Chem. Soc., Dation Trans. 1986, 489-498.
20. Composition: 75% divinylbenzene, 18.5% styrene, 6.25% 1b, AIBN, 1:1 volume ratio of porogen (toluene) to monomers.
21. Vapor phase osmometry experiments have confirmed the monomeric nature of 1a, ensuring that no aggregate structures get imprinted.
22. Repeating these experiments using the non-cross-linkable 1a allows the template molecule to be recovered intact, in good yield, by washing the polymer with toluene.
23. Hexadiene gives a negligible background rate and is considered an unreactive diene; see: Evans, D. A.; Murry, J. A.; von Matt, P.; Norcross, R. D.; Miler, S. J. Angew. Chem., Int. Ed. Engl. 1995, 34, 798-800.
24. For a molecular imprinted polymer that catalyzes the Diels-Alder reaction, see: Liu, X.; Mosbach, K. Macromol. Rapid Commun. 1997, 18, 609-615.
25. Hillhouse, G. L.; Bulls, A. R.; Santarsiero, B. D.; Bercaw, J. E. Organometallics 1988, 7, 1309-1312.
26. For recent references on asymmetric Ti-catalyzed Diels-Alder reactions, see: (a) Gothelf, K. V.; Jorgensen, K. A. J. Chem. Soc., Perkin Trans. 2 1997, 111-115 and references therein. (b) Haase, C.; Sarko, C. R.; DiMare, M. J. Org. Chem. 1995, 60, 1777-1787 and references therein. (c) Seebach, D.; Dahinden, R.; Marti, R. E.; Beck, A. K.; Plattner, D. A.; Kühnle, F. N. M. J. Org. Chem. 1995, 60, 1788-1799.
27. For recent references on asymmetric Ti-catalyzed Diels-Alder reactions, see: (a) Gothelf, K. V.; Jorgensen, K. A. J. Chem. Soc., Perkin Trans. 2 1997, 111-115 and references therein. (b) Haase, C.; Sarko, C. R.; DiMare, M. J. Org. Chem. 1995, 60, 1777-1787 and references therein. (c) Seebach, D.; Dahinden, R.; Marti, R. E.; Beck, A. K.; Plattner, D. A.; Kühnle, F. N. M. J. Org. Chem. 1995, 60, 1788-1799.
28. For recent references on asymmetric Ti-catalyzed Diels-Alder reactions, see: (a) Gothelf, K. V.; Jorgensen, K. A. J. Chem. Soc., Perkin Trans. 2 1997, 111-115 and references therein. (b) Haase, C.; Sarko, C. R.; DiMare, M. J. Org. Chem. 1995, 60, 1777-1787 and references therein. (c) Seebach, D.; Dahinden, R.; Marti, R. E.; Beck, A. K.; Plattner, D. A.; Kühnle, F. N. M. J. Org. Chem. 1995, 60, 1788-1799.
29. We assume, on the basis of the stoichiometry of materials, a catalyst loading of 140 μmol/g of polymer in P1 and further assume a 100% conversion to the dichloride for P2. Inaccessible sites will reduce the effective concentration of catalyst (∼5-10% based on literature precedence; see ref 2).
30. The small decrease in dienophile observed in Figure 2 is a result of a slow substrate decomposition process not observed with the dichloride.
31. Under the pseudo-first-order conditions employed, neither 2 nor P2 behaves ideally, as some curvature in the plots is observed, suggestive of competitive inhibition byproduct. The precipitation of 2 upon diene addition complicates the direct comparison of these systems.
32. 4 does not catalyze the Diels-Alder reaction.