ROMP-polymers in asymmetric catalysis: The role of the polymer backbone

Advanced Synthesis and Catalysis

Volumn 344, Issue 6-7, 2002, Pages 649-656

  Bolm, Carsten ^a   Tanyeli, Cihangir ^a,b   Grenz, Achim ^a   Dinter, Christian L ^a  

^a RWTH AACHEN UNIVERSITY   (Germany)

^b MIDDLE EAST TECHNICAL UNIVERSITY   (Turkey)

Author keywords

Asymmetric synthesis; Catalysis; Cooperative effects; Polymer support; ROMP

Indexed keywords

EID: 0012934518     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/1615-4169(200208)344:6/7<649::AID-ADSC649>3.0.CO;2-X     Document Type: Article

References (89)

1. a) R. Noyori, Asymmetric Catalysis in Organic Synthesis, Wiley, New York, 1994;
2. b) Comprehensive Asymmetric Catalysis, Vols. I - III, (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, Berlin, 1999;
3. nd edn., (Ed.: I. Ojima), Wiley-VCH, New York, 2000;
4. d) Transition Metals for Organic Synthesis, (Eds.: M. Beller, C. Bolm), Wiley-VCH, Weinheim, 1998.
5. Turnover number (TON) = mol (product)/mol (catalyst); turnover frequency (TOF) = mol (product)/[mol (catalyst) × time].
6. For monographs, see: a) R. A. Sheldon, Chirotechnology, Marcel Dekker, New York, 1993;
7. b) Process Chemistry in the Pharmaceutical Industry, (Ed.: K. G. Gadamasetti), Marcel Dekker, New York, 1999;
8. c) Chirality in Industry, (Eds.: A. N. Collins, G. N. Sheldrake, J. Crosby), Wiley, Chichester, 1992;
9. d) Applied Homogeneous Catalysis with Organometallic Compounds, (Eds.: B. Cornils, W. A. Herrmann), Chap. 3.1, VCH Weinheim, 1996.
10. [1c] pp. 145;
11. b) H.-U. Blaser, F. Spindler, Chimia 1997, 57, 297;
12. [1b] Vol. 3, pp. 1427;
13. d) R. Imwinkelried, Chimia 1997, 51, 300;
14. e) B. Pugin, Chimia 2001, 55, 719.
15. For selected overviews, see: a) Chiral Catalyst Immobilization and Recycling, (Eds.: D. E. DeVos, I. F. J. Vankelecom, P. A. Jacobs), VCH, Weinheim, 2000;
16. b) B. Clapham, T. S. Reger, K. D. Janda, Tetrahedron 2001, 57, 4637;
17. c) D. E. Bergbreiter, J. Polym. Sci. Part A: Polym. Chem. 2001, 39, 2351;
18. d) D. E. Bergbreiter, Catal. Today 1998, 42, 389;
19. e) U. Kragl, T. Dwars, Trends in Biotech. 2001, 19, 442;
20. f) H. P. Wentworth, K. D. Janda, Chem. Commun. 1999, 1917;
21. g) S. J. Shuttleworth, S. M. Allin, P. K. Sharma, Synthesis 1997, 1217;
22. h) C. Bolm, A. Gerlach, Eur. J. Org. Chem. 1998, 21;
23. i) L. Pu, Tetrahedron: Asymmetry 1998, 9, 1457;
24. j) L. Pu, Chem. Eur. J. 1999, 5, 2227;
25. k) L. Pu, Chem. Rev. 1998, 98, 2405;
26. l) S. Bräse, S. Dahmen, Synthesis 2001, 1431.
27. a) E. C. Blossey, W. T. Ford, in Comprehensive Polymer Science. The Synthesis, Characterization, Reactions and Applications of Polymers, Vol. 6, (Eds.: G. Allen, J. C. Bevington), Pergamon Press, New York, 1989, p 81;
28. b) D. C. Sherrington, Chem. Commun. 1998, 2275;
29. [3c] pp. 575;
30. d) D. A. Annis, E. N. Jacobsen, J. Am. Chem. Soc. 1999, 121, 4147, and cited references therein.
31. For selected examples and related efforts, see: a) H. Han, K. D. Janda, J. Am. Chem. Soc. 1996, 118, 7632;
32. b) C. Bolm, A. Gerlach, Angew. Chem. Int. Ed. 1997, 36, 741;
33. c) A. Mandoli, D. Pini, S. Orlandi, F. Mazzini, P. Salvadori, Tetrahedron: Asymmetry 1998, 9, 1479;
34. d) M. Felder, G. Giffels, C. Wandrey, Tetrahedron: Asymmetry 1997, 8, 1975;
35. e) S. Rissom, J. Beliczey, G. Giffels, U. Kragl, C. Wandrey, Tetrahedron: Asymmetry 1999, 10, 923.
36. For monographs on metathesis, see: a) K. J. Ivin, J. C. Mol, Olefin Metathesis and Metathesis Polymerization, Academic Press, San Diego, 1997;
37. b) Ring-Opening Polymerization, (Ed.: D. J. Brunelle), Hanser, Munich, 1992;
38. c) Metal Carbenes in Organic Synthesis, (Ed.: F. Zaragosa Dorwald), Wiley-VCH, Weinheim, 1999.
39. For recent reviews on metathesis reactions, see: a) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18;
40. b) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413;
41. c) M. Schuster, S. Blechert, Angew. Chem. Int. Ed. Engl. 1997, 36, 2036;
42. d) C. Pariya, K. N. Jayaprakash, A. Sarkar, Coord. Chem. Rev. 1998, 168, 1;
43. e) S. K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998, 371;
44. f) A. Fürstner, Angew. Chem. Int. Ed. 2000, 39, 3012.
45. C. Bolm, C. L. Dinter, A. Seger, H. Höcker, J. Brozio, J. Org. Chem. 1999, 64, 5730.
46. For examples of other ROMP polymers bearing achiral ligands for catalysts and reagents for synthesis, see: a) A. Grenz, S. Ceccarelli, C. Bolm, Chem. Commun. 2001, 1726;
47. b) M. R. Buchmeiser, K. Wurst, J. Am. Chem. Soc. 1999, 121, 11101;
48. c) A. G. M. Barrett, S. M. Cramp, A. J. Hennessy, P. A. Procopiou, R. S. Roberts, Org. Lett. 2001, 3, 271, and references cited therein.
49. For reviews, see: a) L. Pu, H. B. Yu, Chem. Rev. 2001, 101, 757;
50. b) R. Noyori, M. Kitamura, Angew. Chem. Int. Ed. Engl. 1991, 30, 49;
51. c) K. Soai, S. Niwa, Chem. Rev. 1992, 92, 833.
52. For examples of other polymer-supported ligands for this reaction, see: a) S. Itsuno, J. M. J. Fréchet, J. Org. Chem. 1987, 52, 4140;
53. b) S. Itsuno, Y. Sukuria, K. Ito, T. Maruyama, S. Nakahama, J. M. J. Fréchet, J. Org. Chem. 1990, 55, 304;
54. c) K. Soai, S. Niwa, M. Watanabe, J. Org. Chem. 1988, 53, 927;
55. d) K. Soai, S. Niwa, M. Watanabe, J. Chem. Soc. Perkin Trans. 1 1989, 109;
56. e) K. Soai, M. Watanabe, Tetrahedron: Asymmetry 1991, 2, 97;
57. f) M. Watanabe, K. Soai, J. Chem. Soc. Perkin Trans. 1 1994, 837;
58. g) K. Soai, M. Watanabe, A. Yamamoto, J. Org. Chem. 1990, 55, 4832;
59. h) M. Watanabe, S. Araki, Y. Butsugan, M. Uemura, Chem. Express 1990, 5, 761;
60. i) C. Dreisbach, G. Wischnewski, U. Kragl, C. Wandrey, J. Chem. Soc. Perkin Trans. 1 1995, 875;
61. j) D. Seebach, A. K. Beck, Chimica 1997, 51, 293;
62. k) D. Seebach, R. E. Marti, T. Hintermann, Helv. Chim. Acta 1996, 79, 1710;
63. l) P. J. Comina, A. K. Beck, D. Seebach, Org. Proc. Res. Develop. 1998, 2, 18;
64. m) C. Halm, M. J. Kurth, Angew. Chem. Int. Ed. Engl. 1998, 37, 510;
65. n) A. Vidal-Ferran, N. Bampos, A. Moyano, M. A. Pericàs, A. Riera, J. K. M. Sanders, J. Org. Chem. 1998, 63, 6309;
66. o) D. W. L. Sung, P. Hodge, P. W. Stratford, J. Chem. Soc. Perkin Trans. 1 1999, 1463;
67. p) G. Liu, J. A. Ellman, J. Org. Chem. 1995, 60, 7712;
68. q) S. J. Bae, S.-W. Kim, T. Hyeon, B. M. Kim, Chem. Commun. 2000, 31;
69. r) S.-W. Kim, S. J. Bae, T. Hyeon, B. M. Kim, Microporous Mesoporous Mater. 2001, 44-45, 523.
70. a) K. Saigo, M. Usui, K. Jikuchi, E. Shimada, T. Mukaiyama, Bull. Chem. Soc. Jpn. 1977, 50, 1863;
71. b) T. Mukaiyama, Angew. Chem. Int. Ed. Engl. 1979, 18, 707.
72. a) C. Bolm, A. Gerlach, C. L. Dinter, Synlett 1999, 195;
73. b) C. Bolm, I. Schiffers, C. L. Dinter, A. Gerlach, J. Org. Chem. 2000, 65, 6984;
74. c) C. Bolm, I. Schiffers, C.L. Dinter, L. Defrère, A. Gerlach, G. Raabe, Synthesis 2001, 1719.
75. P. Schwab, M. B. France, J. W. Ziller, R. H. Grubbs, Angew. Chem. Int. Ed. Engl. 1995, 34, 2039.
76. The polymerizations were run to complete monomer conversion. After treatment of the reaction mixture with ethyl vinyl ether followed by removal of all volatiles the polymers were used in the catalysis as such without further purification.
77. PDI = polydispersity index.
78. a) U. Kragl, C. Dreisbach, C. Wandrey, in Applied Homogeneous Catalysis with Organometallic Compounds, (Eds.: B. Cornils, W. A. Herrmann), VCH Weinheim, 1996, pp. 832;
79. b) U. Kragl, C. Dreisbach, Angew. Chem. Int. Ed. Engl. 1996, 35, 642;
80. c) J. Wöltinger, K. Drauz, A. S. Bommarius, Appl. Catal. A: General 2001, 227, 171.
81. An enantioselectivity of 94% ee was achieved previously (ref.[13p]; for 10 mol % of 1). Use of 2 gave (S)-10 with 81% ee.
82. Generally, the activities of the polymeric catalysts were slightly lower than those of their monomeric counterparts. Thus, with the latter full conversion was achieved in reactions performed overnight, whereas with the former the conversions remained in the range of 80 to 85% after the standard reaction time of 48 h.
83. T. Nakano, Y. Okamoto, Chem. Rev. 2001, 101, 4013.
84. If the regioselectivity in the ROMP were perfect, a homochiral polymer backbone would result.
85. a) C. Bolm, K. Muñiz, J. P. Hildebrand, Org. Lett. 1999, 1, 491;
86. b) K. Muñiz, C. Bolm, Chem. Eur. J. 2000, 6, 2309;
87. c) See also: S. Y. Zhang, C. Girard, H. B. Kagan, Tetrahedron: Asymmetry 1995, 6, 2637.
88. A. Cohen, E. D. Bergmann, Tetrahedron 1966, 22, 3545.
89. K. Soai, A. Ookawa, T. Kaba, K. Ogawa, J. Am. Chem. Soc. 1987, 109, 7111.