A practical and highly active ruthenium-based catalyst that effects the cross metathesis of acrylonitrile

Angewandte Chemie - International Edition

Volumn 41, Issue 21, 2002, Pages 4035-4037

  Love, Jennifer A ^a   Morgan, John P ^a   Trnka, Tina M ^a   Grubbs, Robert H ^a  

^a California Institute of Technology   (United States)

Author keywords

Homogeneous catalysis; Metathesis; N ligands; Ruthenium

Indexed keywords

OLEFINS; RUTHENIUM; SYNTHESIS (CHEMICAL);

CROSS METATHESIS;

CATALYSTS;

ACRYLONITRILE; ALKENE; HETEROCYCLIC COMPOUND; PYRIDINE DERIVATIVE; RUTHENIUM COMPLEX; RUTHENIUM DERIVATIVE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL STRUCTURE; CHEMISTRY; COMPLEX FORMATION; DISSOCIATION; KINETICS; REACTION ANALYSIS; REACTION OPTIMIZATION; RING CLOSING METATHESIS; SYNTHESIS;

ACRYLONITRILE; CATALYSIS; HETEROCYCLIC COMPOUNDS; KINETICS; MOLECULAR STRUCTURE; PYRIDINES; RUTHENIUM COMPOUNDS;

EID: 85034336744     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20021104)41:21<4087::AID-ANIE4087>3.0.CO;2-X     Document Type: Article

References (48)

1. a) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18;
2. b) A. F̈rstner, Angew. Chem. 2000, 112, 3012; Angew. Chem. Int. Ed. 2000, 39, 3140.
3. b) A. F̈rstner, Angew. Chem. 2000, 112, 3012; Angew. Chem. Int. Ed. 2000, 39, 3140.
4. a) M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953;
5. b) A. K. Chatterjee, R. H. Grubbs, Org. Lett. 1999, 1, 1751;
6. c) J. P. Morgan, C. Morrill, R. H. Grubbs, Org. Lett. 2002, 4, 67;
7. d) A. K. Chatterjee, D. P. Sanders, R. H. Grubbs, Org. Lett. 2002, 4, 1939.
8. a) A. K. Chatterjee, J. P. Morgan, M. Scholl, R. H. Grubbs, J. Am. Chem. Soc. 2000, 122, 3783;
9. b) T. L. Choi, C. W. Lee, A. K. Chatterjee, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 10417;
10. c) A. K. Chatterjee, T. L. Choi, R. H. Grubbs, Synlett 2001, 1034;
11. d) T. L. Choi, A. K. Chatterjee, R. H. Grubbs, Angew. Chem. 2001, 113, 1317; Angew. Chem. Int. Ed. 2001, 40, 1277;
12. d) T. L. Choi, A. K. Chatterjee, R. H. Grubbs, Angew. Chem. 2001, 113, 1317; Angew. Chem. Int. Ed. 2001, 40, 1277;
13. e) K. Grela, M. Bieniek, Tetrahedron Lett. 2001, 42, 6425;
14. f) M. Lera, C. J. Hayes, Org. Lett. 2001, 3, 2765.
15. T. M. Trnka, M. W. Day, R. H. Grubbs, Angew. Chem. 2001, 113, 3549; Angew. Chem. Int. Ed. 2001, 40, 3441.
16. T. M. Trnka, M. W. Day, R. H. Grubbs, Angew. Chem. 2001, 113, 3549; Angew. Chem. Int. Ed. 2001, 40, 3441.
17. a) W. E. Crowe, D. R. Goldberg, J. Am. Chem. Soc. 1995, 117, 5162;
18. b) W. E. Crowe, D. R. Goldberg, Z. J. Zhang, Tetrahedron Lett. 1996, 37, 2117;
19. c) O. Br̈mmer, A. R̈ckert, S. Blechert, Chem. Eur. J. 1997, 3, 441.
20. a) S. Randl, S. Gessler, H. Wakamatsu, S. Blechert, Synlett 2001, 430;
21. b) S. Randl, N. Buschmann, S. J. Cannon, S. Blechert, Synlett 2001, 1547;
22. c) S. Gessler, S. Randl, S. Blechert, Tetrahedron Lett. 2000, 41, 9973.
23. For the first synthesis of complex 4, see: S. B. Garber, J. S. Kingsbury, B. L. Gray, A. H. Hoveyda, J. Am. Chem. Soc. 2000, 122, 8168.
24. a) J. Cossy, S. BouzBouz, A. H. Hoveyda, J. Organomet. Chem. 2001, 634, 215;
25. b) D. L. Wright, L. C. Usher, M. Estrella-Jimenez, Org. Lett. 2001, 3, 4275.
26. 2Ru=CHPh], see: O. M. Blanco, L. Castedo, Synlett 1999, 557.
27. T. M. Cameron, A. S. Gamble, K. A. Abboud, J. M. Boncella, Chem. Commun. 2002, 1148.
28. For a comparison of precatalysts that provide different active species, see: A. F̈rstner, L. Ackermann, B. Gabor, R. Goddard, C. W. Lehmann, R. Mynott, F. Stelzer, O. R. Thiel, Chem. Eur. J. 2001, 7, 3236.
29. a) M. S. Sanford, M. Ulman, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 749;
30. b) M. S. Sanford, J. A. Love, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 6543.
31. Homodimerization has been omitted for simplicity.
32. J. A. Love, M. S. Sanford, M. W. Day, R. H. Grubbs, J. Am. Chem. Soc. 2002, submitted.
33. 31P NMR magnetizationtransfer experiments is ineffective. Instead, the initiation rate constant can be determined from the rate of the stoichiometric reaction of the catalyst with ethyl vinyl ether. See ref. [14] for an additional discussion.
34. a) H. Wakamatsu, S. Blechert, Angew. Chem, 2002, 114, 2509; Angew. Chem. Int. Ed. 2002, 41, 2403;
35. a) H. Wakamatsu, S. Blechert, Angew. Chem, 2002, 114, 2509; Angew. Chem. Int. Ed. 2002, 41, 2403;
36. b) H. Wakamatsu, S. Blechert, Angew. Chem. 2002, 114, 832; Angew. Chem. Int. Ed. 2002, 41, 794.
37. b) H. Wakamatsu, S. Blechert, Angew. Chem. 2002, 114, 832; Angew. Chem. Int. Ed. 2002, 41, 794.
38. The E/Z ratios obtained with all the catalysts are similar, with the Z isomer formed preferentially. This has been observed with the molybdenum-based catalyst as well as with ruthenium-based catalysts; see refs. [5] and [6].
39. M. S. Sanford, J. A. Love, R. H. Grubbs, Organometallics 2001, 20, 5314.
40. Bispyridine complexes are formed preferentially to monopyridine complexes. In comparison, monophosphane complexes are preferred over bisphosphane complexes. These preferences are likely to arise from steric factors.
41. This procedure has been performed with comparable efficiency on a 50-g scale at Materia, Inc. (Pasadena, CA); S. Hajela, 2002, personal communication.
42. These results do not distinguish between a dissociative or associative mechanism.
43. init estimates were determined is given in the Supporting Information.
44. a) C. W. Bielawski, R. H. Grubbs, Angew. Chem. 2000, 112, 3025; Angew. Chem. Int. Ed. 2000, 39, 2903;
45. a) C. W. Bielawski, R. H. Grubbs, Angew. Chem. 2000, 112, 3025; Angew. Chem. Int. Ed. 2000, 39, 2903;
46. b) T. Weskamp, F. J. Kohl, W. Hieringer, D. Gliech, W. A. Herrmann, Angew. Chem. 1999, 111, 2573; Angew. Chem. Int. Ed. 1999, 38, 2416;
47. b) T. Weskamp, F. J. Kohl, W. Hieringer, D. Gliech, W. A. Herrmann, Angew. Chem. 1999, 111, 2573; Angew. Chem. Int. Ed. 1999, 38, 2416;
48. E. L. Dias, R. H. Grubbs, Organometallics 1998, 17, 2758.