Mechanism of intermolecular ene-yne metathesis promoted by the Grubbs first-generation catalyst: An alternative entry point to catalysis

Organometallics

Volumn 30, Issue 6, 2011, Pages 1319-1321

  Marshall, Jennifer E ^a   Keister, Jerome B ^a   Diver, Steven T ^a  

^a UNIVERSITY AT BUFFALO   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ENE-YNE; ENTRY POINT; FIRST-ORDER DEPENDENCE; GRUBBS CATALYSTS; RATE DEPENDENCE; TERMINAL ALKYNE;

CATALYSTS; OLEFINS;

ACETYLENE;

EID: 79952910429     PISSN: 02767333     EISSN: 15206041     Source Type: Journal    
DOI: 10.1021/om200133j     Document Type: Article

References (12)

1. Recent reviews: Diver, S. T.; Giessert, A. J. Chem. Rev. 2004, 104, 1317
2. Poulsen, C. S.; Madsen, R. Synthesis 2003, 1 The first examples of ene-yne cross-metathesis employed carbene catalyst 1: Stragies, R.; Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. 1997, 36, 2518
3. Galan, B. R.; Giessert, A. J.; Keister, J. B.; Diver, S. T. J. Am. Chem. Soc. 2005, 127, 5762
4. Dias, E. L.; Nguyen, S. T.; Grubbs, R. H. J. Am. Chem. Soc. 1997, 119, 3887
5. Sanford, M. S.; Love, J. A.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 6543
6. Love, J. A.; Sanford, M. S.; Day, M. W.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 10103
7. For example, a less reactive catalyst might be preferred to achieve a kinetic result, where secondary cross-metathesis is intentionally minimized. For the rules of alkene reactivity for various Grubbs catalysts, see: Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 11360
8. Using a GC assay, we verified the accuracy of the rate determination, showing that (1) the rate of alkyne disappearance was the same as that measured with the IR method and (2) the 1,3-diene product appeared concomitantly with the alkyne disappearance (see Figure S1 in the Supporting Information).
9. 2) exchange with the catalyst 1 to form styrene and carbene complex B, where R = alkyl group, is much faster than ene-yne metathesis.
10. obs = n ln[ 1 ] + ln k. See the Supporting Information.
11. Lippstreu, J. J.; Straub, B. F. J. Am. Chem. Soc. 2005, 127, 7444
12. 3 dissociation to form a 14-electron intermediate, these data may not apply to the catalytic reaction. DFT calculations suggest that alkynes bind more strongly than alkenes with comparable steric properties to 14-electron ruthenium carbene complexes. (9)