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 Obstetrics Gynecology   (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)

1. Farina, M. Top. Stereochem. 1987, 17, 1-111.
2. Tomotsu, N.; Ishihara, N.; Newman, T. H.; Malanga, M. T. J. Mol. Catal. A 1998, 128, 167-190.
3. For leading references, see: (a) Hartgerink, J. D.; Clark, T. D.; Ghadiri, M. R. Chem.-Eur. J. 1998, 4, 1367-1372. (b) Diederichsen, U. Angew. Chem., Int. Ed. Engl. 1996, 35, 445-448. (c) Di Blasio, B.; Delduca, V.; Lombardi, A.; Pedone, C.; Lorenzi, G. P.; Benedetti, E. Int. J. Pept. Protein Res. 1995, 45, 100-105.
4. For leading references, see: (a) Hartgerink, J. D.; Clark, T. D.; Ghadiri, M. R. Chem.-Eur. J. 1998, 4, 1367-1372. (b) Diederichsen, U. Angew. Chem., Int. Ed. Engl. 1996, 35, 445-448. (c) Di Blasio, B.; Delduca, V.; Lombardi, A.; Pedone, C.; Lorenzi, G. P.; Benedetti, E. Int. J. Pept. Protein Res. 1995, 45, 100-105.
5. For leading references, see: (a) Hartgerink, J. D.; Clark, T. D.; Ghadiri, M. R. Chem.-Eur. J. 1998, 4, 1367-1372. (b) Diederichsen, U. Angew. Chem., Int. Ed. Engl. 1996, 35, 445-448. (c) Di Blasio, B.; Delduca, V.; Lombardi, A.; Pedone, C.; Lorenzi, G. P.; Benedetti, E. Int. J. Pept. Protein Res. 1995, 45, 100-105.
6. Brintzinger, H. H.; Fischer, D.; Mulhaupt, R.; Rieger, B.; Waymouth, R. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 1143-1170.
7. 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.
8. 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.
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.
15. Swift, G. Acc. Chem. Res. 1993, 26, 105-110.
16. Kricheldorf, H. R.; Kreiser-Saunders: I.; Juergens, C.; Wolter, D. Macromol. Symp. 1996, 103, 85-102.
17. Chiellini, E.; Solaro, R. Adv. Mater. 1996, 8, 305-313.
18. 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.
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.
28. Wisniewski, M.; Le Borgne, A.; Spassky, N. Macromol Chem. Phys. 1997, 198, 1227-1238.
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.
30. Thakur, K. A. M.; Kean, R. T.; Hall, E. S.; Kolstad, J. J.; Munson, E. J. Macromolecules 1998, 31, 1487-1494.
31. Spassky, N.; Wisniewski, M.; Pluta, C.; Le Borgne, A. Macromol. Chem. Phys. 1996, 197, 2627-2637.
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.
33. Thakur, K. A. M.; Kean, R. T.; Zell, M. T.; Padden, B. E.; Munson, E. J. Chem. Commun. 1998, 1913-1914.
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%.