A series of ruthenium(II) ester-carbene complexes as olefin metathesis initiators: Metathesis of acrylates

Tetrahedron Letters

Volumn 41, Issue 24, 2000, Pages 4689-4693

  Ulman, Michael ^a   Belderrain, Tomás R ^a   Grubbs, Robert H ^a  

^a California Institute of Technology ^*  (United States)

Author keywords

Acrylate; Carbene; Catalyst; Olefin metathesis; Ring opening; Ruthenium

Indexed keywords

ACRYLIC ACID; CARBENE; CYCLOHEXENE DERIVATIVE; RUTHENIUM;

ARTICLE; CHEMICAL BINDING; METAL BINDING; ORGANIC CHEMISTRY; POLYMERIZATION; STRAIN DIFFERENCE; THERMODYNAMICS;

EID: 0034660543     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(00)00696-1     Document Type: Article

References (18)

1. For recent reviews, see: (a) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413;
2. (b) Armstrong, S. K. J. Chem. Soc., Perkin Trans. 1 1998, 371.
3. (a) Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887;
4. (b) Weskamp, T.; Schattenmann, W. C.; Spiegler, M.; Herrmann, W. A. Angew. Chem., Int. Ed. Engl. 1998, 37, 2490; also see corrigendum: Weskamp, T.; Schattenmann, W. C.; Spiegler, M.; Herrmann, W. A. Angew. Chem., Int. Ed. Engl. 1999, 38, 262;
5. (b) Weskamp, T.; Schattenmann, W. C.; Spiegler, M.; Herrmann, W. A. Angew. Chem., Int. Ed. Engl. 1998, 37, 2490; also see corrigendum: Weskamp, T.; Schattenmann, W. C.; Spiegler, M.; Herrmann, W. A. Angew. Chem., Int. Ed. Engl. 1999, 38, 262;
6. © Scholl, M.; Trnka, T. M.; Morgan, J. P.; Grubbs, R. H. Tetrahedron Lett. 1999, 40, 2247;
7. (d) Huang, J.; Stevens, E. D.; Nolan, S. P.; Petersen, J. L. J. Am. Chem. Soc. 1999, 121, 2674;
8. (e) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Organic Letters 1999, 1, 953.
9. (a) Chang, S.; Jones, L.; Wang, C. M.; Henling, L. M.; Grubbs, R. H. Organometallics 1998, 17, 3460;
10. (b) Sanford, M. S.; Henling, L. M.; Grubbs, R. H. Organometallics 1998, 17, 5384.
11. Ulman, M.; Grubbs, R. H. Organometallics 1998, 17, 2484.
12. (a) Belderrain, T. R.; Grubbs, R. H. Organometallics 1997, 16, 4001;
13. (b) similar chemistry was independently reported: Olivan, M.; Caulton, K. G. Chem. Commun. 1997, 1733.
14. The use of ethyl diazoacetate to initiate metathesis was also studied by: Demonceau, A.; Noels, A. F.; Saive, E.; Hubert, A. J. J. Mol. Cat. 1992, 76, 123.
15. France, M. B. PhD Thesis. California Institute of Technology, 1995.
16. Ulman, M.; Grubbs, R. H. J. Org. Chem. 1999, 64, 7202.
17. The decomposition data obtained for the first 20 min of decomposition did not fit second order kinetics. For a more detailed discussion of the decomposition pathways for the ruthenium catalysts, see Ref. 8.
18. The catalysts based on N-heterocyclic carbene ligands reported in Ref. 2b-e are very active for propagating olefin metathesis but the rates of catalyst initiation are rather slow and significantly lower than for the ester-carbenes. In metathesis initiated by the ester-carbenes, the ester-carbene functionality is lost in the first catalyst turnover so the rates of propagation are equivalent to those achieved with the other bis-phosphine initiators. In claiming that the ester-carbenes are the most active catalysts, the implication is only for the first turnover after which the ester functionality is lost.