Stereoselective ring-opening polymerization of meso-lactide: Synthesis of syndiotactic poly(lactic acid)

Journal of the American Chemical Society

Volumn 121, Issue 16, 1999, Pages 4072-4073

  Ovitt, Tina M ^a   Coates, Geoffrey W ^a  

^a Department of Population Medicine and Diagnostic Sciences   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

POLYLACTIC ACID; POLYMER;

ARTICLE; CHEMICAL REACTION; CHEMICAL STRUCTURE; EVAPORATION; MOLECULAR WEIGHT; POLYMERIZATION; REACTION ANALYSIS; STRUCTURE ANALYSIS; SYNTHESIS;

EID: 0033611946     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990088k     Document Type: Article

References (35)

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9. For some exceptions and recent examples, see: (a) Yasuda, H.; Ihara, E. Adv. Polym. Sci. 1997, 133, 53-101. (b) Brookhart, M.; Wagner, M. I. J. Am. Chem. Soc. 1996, 118, 7219-7220. (c) Kemnitzer, J. E.; McCarthy, S. P.; Gross, R. A. Macromolecules 1993, 26, 1221-1229. (d) Resconi, L.; Abis, L.; Francisconi, G. Macromolecules 1992, 25, 6814-6817. (e) Reference 2.
10. For some exceptions and recent examples, see: (a) Yasuda, H.; Ihara, E. Adv. Polym. Sci. 1997, 133, 53-101. (b) Brookhart, M.; Wagner, M. I. J. Am. Chem. Soc. 1996, 118, 7219-7220. (c) Kemnitzer, J. E.; McCarthy, S. P.; Gross, R. A. Macromolecules 1993, 26, 1221-1229. (d) Resconi, L.; Abis, L.; Francisconi, G. Macromolecules 1992, 25, 6814-6817. (e) Reference 2.
11. For examples of syndiospecific catalysts that exhibit site control, see: (a) Alt, H. G.; Samuel, E. Chem. Soc. Rev. 1998, 27, 323-329 and references therein. (b) Herzog, T. A.; Zubris, D. L.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 11988-11989. (c) O'Dell, R.; McConville, D. H.; Hofmeister, G. E.; Schrock, R. R. J. Am. Chem. Soc. 1994, 116, 3414-3423.
12. For examples of syndiospecific catalysts that exhibit site control, see: (a) Alt, H. G.; Samuel, E. Chem. Soc. Rev. 1998, 27, 323-329 and references therein. (b) Herzog, T. A.; Zubris, D. L.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 11988-11989. (c) O'Dell, R.; McConville, D. H.; Hofmeister, G. E.; Schrock, R. R. J. Am. Chem. Soc. 1994, 116, 3414-3423.
13. For examples of syndiospecific catalysts that exhibit site control, see: (a) Alt, H. G.; Samuel, E. Chem. Soc. Rev. 1998, 27, 323-329 and references therein. (b) Herzog, T. A.; Zubris, D. L.; Bercaw, J. E. J. Am. Chem. Soc. 1996, 118, 11988-11989. (c) O'Dell, R.; McConville, D. H.; Hofmeister, G. E.; Schrock, R. R. J. Am. Chem. Soc. 1994, 116, 3414-3423.
14. Two possible scenarios are (1) the cyclic monomer has two stereocenters of the same configuration (enantiopure), and the polymerization process inverts one of the centers during the ring-opening process and (2) the cyclic monomer has two stereocenters of opposite configuration (meso), and the initiator stereoselectively opens it with retention of stereochemistry. Both form syndiotactic polymer.
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19. For examples of Al-, Mg-, Sn-, and Y-based alkoxide initiators, see: (a) Dubois, P.; Jacobs, C.; Jérôme, R.; Tessié, P. Macromolecules 1991, 24, 2266-2270. (b) Chisholm, M. H.; Eilerts, N. W. Chem. Commun. 1996, 853-854. (c) Kricheldorf, H. R.; Lee, S. R.; Bush, S. Macromolecules 1996, 29, 1375-1381. (d) Stevels, W. M.; Ankoné, M. J. K.; Dijkstra, P. J.; Feijen, J. Macromolecules 1996, 29, 3332-3333.
20. For examples of Al-, Mg-, Sn-, and Y-based alkoxide initiators, see: (a) Dubois, P.; Jacobs, C.; Jérôme, R.; Tessié, P. Macromolecules 1991, 24, 2266-2270. (b) Chisholm, M. H.; Eilerts, N. W. Chem. Commun. 1996, 853-854. (c) Kricheldorf, H. R.; Lee, S. R.; Bush, S. Macromolecules 1996, 29, 1375-1381. (d) Stevels, W. M.; Ankoné, M. J. K.; Dijkstra, P. J.; Feijen, J. Macromolecules 1996, 29, 3332-3333.
21. For examples of Al-, Mg-, Sn-, and Y-based alkoxide initiators, see: (a) Dubois, P.; Jacobs, C.; Jérôme, R.; Tessié, P. Macromolecules 1991, 24, 2266-2270. (b) Chisholm, M. H.; Eilerts, N. W. Chem. Commun. 1996, 853-854. (c) Kricheldorf, H. R.; Lee, S. R.; Bush, S. Macromolecules 1996, 29, 1375-1381. (d) Stevels, W. M.; Ankoné, M. J. K.; Dijkstra, P. J.; Feijen, J. Macromolecules 1996, 29, 3332-3333.
22. meso-Lactide can be synthesized with purity greater than 99%, see: Entenmann, G.; Bendix, D. (Boehringer Ingelheim), German Patent DE 3,820,299, 1988; Chem. Abstr. 1989, 110, 213592w.
23. There are several reports of the polymerization of 1; however, none demonstrate efficient stereochemical control to produce syndiotactic PLA: (a) Thakur, K. A. M.; Kean, R. T.; Hall, E. S.; Kolstad, J. J.; Lindgren, T. A.; Doscotch, M. A.; Siepmann, J. I.; Munson, E. J. Macromolecules 1997, 30, 2422-2428. (b) Kricheldorf, H. R.; Lee, S. R. Polymer 1995, 36, 2995-3003. (c) Kricheldorf, H. R.; Boetteher, C. Makromol Chem. 1993, 194, 1653-1664. (d) Kricheldorf, H. R.; Boettcher, C. J. Macromol Sci., Pure Appl. Chem. 1993, A30, 441-448. (e) Chabot, F.; Vert, M.; Chapelle, S.; Granger, P. Polymer 1983, 24, 53-59.
24. There are several reports of the polymerization of 1; however, none demonstrate efficient stereochemical control to produce syndiotactic PLA: (a) Thakur, K. A. M.; Kean, R. T.; Hall, E. S.; Kolstad, J. J.; Lindgren, T. A.; Doscotch, M. A.; Siepmann, J. I.; Munson, E. J. Macromolecules 1997, 30, 2422-2428. (b) Kricheldorf, H. R.; Lee, S. R. Polymer 1995, 36, 2995-3003. (c) Kricheldorf, H. R.; Boetteher, C. Makromol Chem. 1993, 194, 1653-1664. (d) Kricheldorf, H. R.; Boettcher, C. J. Macromol Sci., Pure Appl. Chem. 1993, A30, 441-448. (e) Chabot, F.; Vert, M.; Chapelle, S.; Granger, P. Polymer 1983, 24, 53-59.
25. There are several reports of the polymerization of 1; however, none demonstrate efficient stereochemical control to produce syndiotactic PLA: (a) Thakur, K. A. M.; Kean, R. T.; Hall, E. S.; Kolstad, J. J.; Lindgren, T. A.; Doscotch, M. A.; Siepmann, J. I.; Munson, E. J. Macromolecules 1997, 30, 2422-2428. (b) Kricheldorf, H. R.; Lee, S. R. Polymer 1995, 36, 2995-3003. (c) Kricheldorf, H. R.; Boetteher, C. Makromol Chem. 1993, 194, 1653-1664. (d) Kricheldorf, H. R.; Boettcher, C. J. Macromol Sci., Pure Appl. Chem. 1993, A30, 441-448. (e) Chabot, F.; Vert, M.; Chapelle, S.; Granger, P. Polymer 1983, 24, 53-59.
26. There are several reports of the polymerization of 1; however, none demonstrate efficient stereochemical control to produce syndiotactic PLA: (a) Thakur, K. A. M.; Kean, R. T.; Hall, E. S.; Kolstad, J. J.; Lindgren, T. A.; Doscotch, M. A.; Siepmann, J. I.; Munson, E. J. Macromolecules 1997, 30, 2422-2428. (b) Kricheldorf, H. R.; Lee, S. R. Polymer 1995, 36, 2995-3003. (c) Kricheldorf, H. R.; Boetteher, C. Makromol Chem. 1993, 194, 1653-1664. (d) Kricheldorf, H. R.; Boettcher, C. J. Macromol Sci., Pure Appl. Chem. 1993, A30, 441-448. (e) Chabot, F.; Vert, M.; Chapelle, S.; Granger, P. Polymer 1983, 24, 53-59.
27. There are several reports of the polymerization of 1; however, none demonstrate efficient stereochemical control to produce syndiotactic PLA: (a) Thakur, K. A. M.; Kean, R. T.; Hall, E. S.; Kolstad, J. J.; Lindgren, T. A.; Doscotch, M. A.; Siepmann, J. I.; Munson, E. J. Macromolecules 1997, 30, 2422-2428. (b) Kricheldorf, H. R.; Lee, S. R. Polymer 1995, 36, 2995-3003. (c) Kricheldorf, H. R.; Boetteher, C. Makromol Chem. 1993, 194, 1653-1664. (d) Kricheldorf, H. R.; Boettcher, C. J. Macromol Sci., Pure Appl. Chem. 1993, A30, 441-448. (e) Chabot, F.; Vert, M.; Chapelle, S.; Granger, P. Polymer 1983, 24, 53-59.
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29. Thakur, K. A. M.; Kean, R. T.; Hall, E. S.; Kolstad, J. J.; Lindgren, T. A.; Doscotch, M. A.; Siepmann, J. I.; Munson, E. J. Macromolecules 1997, 30, 2422-2428.
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32. 3, followed by reaction with methanol. We discovered that a catalytically inactive bimetallic byproduct is formed in approximately 30% yield using this preparation, prompting our modified route. The structure of this unusual compound will be reported separately.
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34. 14 Therefore we attribute the high degree of syndiospecificity in this reaction to an enantiomorphic site-control mechanism.
35. 2). For Figure 1, [rmr] = 3.9%, [rrr] + [mrm] + [rrm] + [mrr] = 96.1%.