Mechanistically inspired catalysts for enantioselective desymmetrizations by olefin metathesis

Chemistry - A European Journal

Volumn 14, Issue 28, 2008, Pages 8690-8695

  Fournier, Pierre André ^a   Savoie, Jolaine ^a   Stenne, Brice ^a   Bédard, Marion ^a   Grandbois, Alain ^a   Collins, Shawn K ^a  

^a UNIVERSITÉ DE MONTRÉAL   (Canada)

Author keywords

Asymmetric catalysis; Desymmetrization; N heterocyclic carbenes; Olefin metathesis; Ruthenium

Indexed keywords

CATALYSTS; DOPING (ADDITIVES); ENANTIOSELECTIVITY; OLEFINS;

ASYMMETRIC CATALYSIS; DESYMMETRIZATION; N-HETEROCYCLIC CARBENES; OLEFIN METATHESIS; RUTHENIUM;

CATALYSIS;

ALKENE;

ARTICLE; CATALYSIS; CHEMISTRY; STEREOISOMERISM;

ALKENES; CATALYSIS; STEREOISOMERISM;

EID: 53849097052     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200800642     Document Type: Article

References (45)

1. For recent reviews on asymmetric olefin metathesis, see: a) A. H. Hoveyda. in Handbook of Metathesis; R. H.Grubbs, Ed.; Wiley-VCH: Weinheim, Germany, 2003, Vol.2, Chapter 2,3;
2. b) R. R. Schrock, A. H. Hoveyda, Angew. Chem. 2003, 115, 4740-4782;
3. Angew. Chem. Int. Ed. 2003, 42, 4592-4633;
4. c) A. H. Hoveyda, R. R. Schrock. Chem. Eur. J. 2001, 7, 945-950.
5. see also d) A. H. Hoveyda, A. R. Zhugralin, Nature 2007, 450, 243-251.
6. T. J. Seiders, D. W. Ward, R. H. Grubbs, Org. Lett. 2001, 3, 3225-3228.
7. a) T. W. Funk, J. M. Berlin, R. H. Grubbs, J. Am. Chem. Soc. 2006, 128, 1840-1846;
8. b) J. M. Berlin, S. D. Goldberg, R. H. Grubbs, Angew. Chem. 2006, 118, 7753-7757;
9. Angew. Chem. Int. Ed. 2006, 45, 7591-7595.
10. A. H. Hoveyda, D. G. Gillingham, J. J. Van Veldhuizen, O. Kataoka, S. B. Garber, J. S. Kingsbury, J. P. Harrity, A. Org. Biomol. Chem. 2004, 2, 8-23.
11. a) J. J. Van Veldhuizen, S. B. Garber, J. S. Kingsbury, A. H. Hoveyda, J. Am. Chem. Soc. 2002, 124, 4954-4955;
12. b) J. J. Van Veldhuizen, D. G. Gillingham, S. B. Garber. O. Kataoka, A. H. Hoveyda, J. Am. Chem. Soc 2003, 125, 12502-12508;
13. c) J. J. Van Veldhuizen, J. E. Campbell, R. E. Giudici, A. H. Hoveyda, J. Am. Chem. Soc. 2005, 127, 6877-6882.
14. M. Bornand, P. Chen. Angew. Chem. 2005, 117, 8123-8125;
15. Angew. Chem. Int. Ed. 2005, 44, 7909-7911.
16. a) C. Coslabile, L. Cavallo, J. Am. Chem. Soc. 2004, 726, 9592-9600;
17. b) A. Correa, L. Cavallo, J. Am. Chem. Soc. 2006, 128, 13352-13353.
18. P.-A. Fournier, S. K. Collins, Organometallics 2007, 26, 2945-2949.
19. M. Bornand, S. Torker, P. Chen, Organometallics 2007, 26, 3585-3596.
20. R. E. Giudici, A. H. Hoveyda, J. Am. Chem. Soc. 2007, 129, 3824-3825.
21. For other examples of olefin metathesis catalysts that contain monodentate Ci-symmetric NHCs see : a) K. Vehlow, S. Maechling, S. Blechert, Organometallics 2006, 25, 25-28;
22. b) M. B. Dinger, P. Nieczypor, J. C. Mol. Organometallics 2003, 22, 5291-5296;
23. c) N. Ledoux, B. Allaert, S. Pattyn, H. Vander Mierde, C. Vercaemst, F. Verpoort, Chem. Eur. J. 2006, 12, 4654-4661.
24. See the Supporting Information for full details.
25. Throughout this manuscript, syn refers to the case in which the N-alkyl group of the NHC ligand is on the same side as the Ru carbene.
26. Reactivity studies were performed as outlined in: T. Ritter, A. Hejl, A. G. Wenzel, T. W. Funk, R. H. Grubbs, Organometallics 2006, 25, 5740-5745.
27. 1H NMR experiments to determine the rotation barriers of the NHC ligands in catalysts 4, 5, and 6. However, due to the instability of 5 and 6 at higher temperatures, (catalysts 5 and 6 decompose in solution over a period of twenty minutes making variable temperature NMR experiments difficult to perform), we have not been able to collect any meaningful data at this time.
28. 2.
29. The product yields from the desymmetrizations can be highly variable since many of the products are highly volatile. There is no indication that the crude reaction mixtures contain any homocoupling or decomposition products.
30. Halide additives have also been used with Ru-based catalysts containing C,-symmelric bidentate ligands. See reference [5c].
31. For recent efforts in improving catalyst reactivity through benzylidine modification see: a) M. Bieniek, R. Bujok, M. Cabaj, N. Lugan, G. Lavigne, D. Aril, Grela, J. Am. Chem. Soc. 2006, 128, 13652-13653;
32. b) R. Bujok, M. Bieniek, M. Masnyk, A. Michrowska, A. Sarosiek, H. Stepowska, D. ArIt, K. Grela, J. Org. Chem. 2004, 69, 6894-6896;
33. c) A. Michrowska, R. Bujok, S. Harutyunyan, V. Sashuk, G. Dolgonos, K. Grela, J. Am. Chem. Soc. 2004, 126, 9318-9325;
34. d) M. Barbasiewicz, A. Szadkowska, R. Bujok, K. Grela. Organometallics 2006, 25, 3599-3604.
35. For a review of efforts to improve catalyst efficiency through NHC modification, see: a) E. Colacino, J. Martinez, F. Lamaty, Coord. Chem. Rev. 2007, 251, 726-764; for examples of electronic and steric modification in asymmetric olefin metathesis, see reference [5b]; for examples of C,-symmetric NHCs see reference [11];
36. for metathesis catalysts containing thiazol-2-ylidene ligands, see: b) G. C. Vougioukalakis, R. H. Grubbs, J. Am. Chem. Soc. 2008, 130, 2234-2245;
37. for examples of six-membered NHC ligands or cyclohexane-annelated ligands, see: c) K. Weigl, K. Koehler, S. Dechert, F. Meyer, Organometallics 2005, 24, 4049-4056;
38. d) L. Yang, M. Mayr, K. Wurst, M. R. Buchmeiser, Chem. Eur. J. 2004, 10, 5761-5770;
39. for four-membered ring NHC ligands see: e) E. Despagnet-Ayoub, R. H. Grubbs, J. Am. Chem. Soc. 2004, 126, 10198-10199;
40. f) E. Despagnet-Ayoub, R. H. Grubbs, Organometallics 2005, 24, 338-340;
41. for some recent modifications of N-aryl substituents on the NHC ligand see: g) I. C. Stewart, C. J. Douglas, R. H. Grubbs, Org. Lett. 2008, 10, 441 -444;
42. h) I. C. Stewart, T. Ung, A. A. Pletnev, J. M. Berlin, R. H. Grubbs, Y. Schrodi, Org. Lett. 2007, 9, 1589-1592;
43. i) J. M. Berlin, K. Campbell, T. Ritter, T. W. Funk. A. Chlenov, R. H. Grubbs, Org. Lett. 2007, 9, 1339-1342;
44. j) L. Jafarpour, E. D. Stevens, S. P. Nolan, J. Organomet. Chem. 2000, 606, 49-54;
45. k) A. Furstner, L. Ackermann, B. Gabor, R. Goddard, C. W. Lehmann, R. Mynott, F. Stelzer, O. R. Thiel, Chem. Eur. J. 2001, 7, 3236-3253.