Amine-mediated degradation in olefin metathesis reactions that employ the second-generation Grubbs catalyst

ChemCatChem

Volumn 6, Issue 2, 2014, Pages 459-463

  Lummiss, Justin A M ^a   Ireland, Benjamin J ^a   Sommers, Jacob M ^a   Fogg, Deryn E ^a  

^a UNIVERSITY OF OTTAWA   (Canada)

Author keywords

amines; deactivation; homogeneous catalysis; nucleophile; olefin metathesis

Indexed keywords

1 ,8-DIAZABICYCLO[5.4.0]UNDEC-7-ENE; DEACTIVATION; DEACTIVATION PATHWAYS; HOMOGENEOUS CATALYSIS; OLEFIN METATHESIS; OLEFIN METATHESIS REACTIONS; RING-CLOSING METATHESIS REACTIONS; SECOND GENERATION;

AMINES; NUCLEOPHILES; OLEFINS; REACTION KINETICS;

CATALYSTS;

EID: 84893320355     PISSN: 18673880     EISSN: 18673899     Source Type: Journal    
DOI: 10.1002/cctc.201300861     Document Type: Article

References (37)

1. P. Compain, Adv. Synth. Catal. 2007, 349, 1829-1846. For additional examples cited in review articles, see
2. R. H. Grubbs, Handbook of Metathesis, Wiley-VCH, Weinheim, 2003, Vol. 1, p. 120; Vol. 2, pp. 48-50, Vol. 3, pp. 319-320
3. A. Deiters, S. F. Martin, Chem. Rev. 2004, 104, 2199-2238. For an early report noting the importance of protecting groups in RCM of amine-containing substrates, see
4. G. C. Fu, S. T. Nguyen, R. H. Grubbs, J. Am. Chem. Soc. 1993, 115, 9856-9857.
5. C. P. Woodward, N. D. Spiccia, W. R. Jackson, A. J. Robinson, Chem. Commun. 2011, 47, 779-781.
6. N. K. Yee, V. Farina, I. N. Houpis, N. Haddad, R. P. Frutos, F. Gallou, X.-J. Wang, X. Wei, R. D. Simpson, X. Feng, V. Fuchs, Y. Xu, J. Tan, L. Zhang, J. Xu, L. L. Smith-Keenan, J. Vitous, M. D. Ridges, E. M. Spinelli, M. Johnson, K. Donsbach, T. Nicola, M. Brenner, E. Winter, P. Kreye, W. Samstag, J. Org. Chem. 2006, 71, 7133-7145.
7. H. Wang, S. N. Goodman, Q. Dai, G. W. Stockdale, W. M. Clark, Org. Process Res. Dev. 2008, 12, 226-234.
8. G. O. Wilson, K. A. Porter, H. Weissman, S. R. White, N. R. Sottos, J. S. Moore, Adv. Synth. Catal. 2009, 351, 1817-1825.
9. F. E. Hahn, M. Paas, R. Froehlich, J. Organomet. Chem. 2005, 690, 5816-5821.
10. S. J. P'Pool, H.-J. Schanz, J. Am. Chem. Soc. 2007, 129, 14200-14212.
11. G. Occhipinti, H.-R. Bjorsvik, K. W. Toernroos, V. R. Jensen, Organometallics 2007, 26, 5803-5814.
12. J. S. M. Samec, R. H. Grubbs, Chem. Commun. 2007, 2826-2828.
13. E. Tzur, A. Szadkowska, A. Ben-Asuly, A. Makal, I. Goldberg, K. Wozniak, K. Grela, N. G. Lemcoff, Chem. Eur. J. 2010, 16, 8726-8737.
14. H. Jong, B. O. Patrick, M. D. Fryzuk, Organometallics 2011, 30, 2333-2341.
15. J. A. Love, J. P. Morgan, T. M. Trnka, R. H. Grubbs, Angew. Chem. 2002, 114, 4207-4209
16. Angew. Chem. Int. Ed. 2002, 41, 4035-4037.
17. 3]Cl (not quantified). See Ref. [14].
18. S. H. Hong, A. G. Wenzel, T. T. Salguero, M. W. Day, R. H. Grubbs, J. Am. Chem. Soc. 2007, 129, 7961-7968.
19. D. E. Fogg, H. M. Foucault, in Comprehensive Organometallic Chemistry III, Vol. 11 (Eds.:, R. H. Crabtree, D. M. P. Mingos,), Elsevier, Oxford, 2007, pp. 623-652.
20. a values for the conjugate acids in acetonitrile: n-butylamine a: 18.3; pyrrolidine b: 19.6; morpholine c: 16.6; DBU d, 24.1; cf. 12.6 for pyridine. See:, B. G. Cox, Acids and Bases: Solvent Effects on Acid-Base Strength, Oxford University Press, Croydon, 2013.
21. H. Hoberg, Y. Peres, C. Krüger, Y.-H. Tsay, Angew. Chem. 1987, 99, 799-800
22. Angew. Chem. Int. Ed. Engl. 1987, 26, 771-773.
23. U. Flörke, U. Ortmann, H.-J. Haupt, Acta Crystallogr. Sect. C 1992, 48, 1663-1665.
24. A. M. Joshi, I. S. Thorburn, S. J. Rettig, B. R. James, Inorg. Chim. Acta 1992, 198-200, 283-296.
25. R. Regragui, P. Dixneuf, J. Organomet. Chem. 1988, 344, C 11 -C 14.
26. J. N. Coalter, J. C. Bollinger, O. Eisenstein, K. G. Caulton, New J. Chem. 2000, 24, 925-927
27. J. C. Conrad, D. Amoroso, P. Czechura, G. P. A. Yap, D. E. Fogg, Organometallics 2003, 22, 3634-3636. β-Elimination from alkoxides (either pre-formed or generated in situ from primary alcohols)
28. M. B. Dinger, J. C. Mol, Organometallics 2003, 22, 1089-1095
29. N. J. Beach, J. A. M. Lummiss, J. M. Bates, D. E. Fogg, Organometallics 2012, 31, 2349-2356.
30. These and prior findings highlight the susceptibility of the [Ru]=CHR unit to nucleophilic attack. In related work focusing on decomposition of a phenyl-functionalized NHC, Blechert and co-workers proposed that the benzylidene carbon itself can function as a nucleophile. This pathway was observed only in the presence of atmospheric oxygen. See:, K. Vehlow, S. Gessler, S. Blechert, Angew. Chem. 2007, 119, 8228-8231
31. Angew. Chem. Int. Ed. 2007, 46, 8082-8085.
32. S. M. Hansen, F. Rominger, M. Metz, P. Hofmann, Chem. Eur. J. 1999, 5, 557-566.
33. B. R. Galan, M. Pitak, J. B. Keister, S. T. Diver, Organometallics 2008, 27, 3630-3632.
34. J. A. M. Lummiss, N. J. Beach, J. C. Smith, D. E. Fogg, Catal. Sci. Technol. 2012, 2, 1630-1632.
35. E. F. van der Eide, W. E. Piers, Nat. Chem. 2010, 2, 571-576
36. A. G. Wenzel, G. Blake, D. G. Vander Velde, R. H. Grubbs, J. Am. Chem. Soc. 2011, 133, 6429-6439.
37. T. M. Gregg, J. B. Keister, S. T. Diver, J. Am. Chem. Soc. 2013, 135, in press, DOI:.