Abstract
A study on the enyne meta-thesis reaction leading to the formation cyclic compounds using ruthenium-in-denylidene complexes is presented. Several l, 11-dien-6-ynes have been subjected to ruthenium metathesis cyc-lization by using ruthenium-indenyli-dene complexes bearing various phos-phine and N-heterocyclic carbene (NHC) ligands. Interestingly, for some substrates chemodivergent metathesis occurs and is a function of the catalyst employed. This led us to investigate the competing "ene-then-yne" or "yne-then-ene" reaction pathways apparent-ly at play in these systems using both experimental observations and DFT calculations. Experimental and compu-tational studies were found in good agreement and permit to conclude that for phosphine-containing catalysts, the "ene-then-yne" pathway is exclusively adopted. On the other hand, for cata-lysts bearing NHC ligands, both path-ways are possible.
Original language | English (US) |
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Pages (from-to) | 10244-10254 |
Number of pages | 11 |
Journal | Chemistry - A European Journal |
Volume | 15 |
Issue number | 39 |
DOIs | |
State | Published - Oct 5 2009 |
Externally published | Yes |
Keywords
- Density functional calcu-lations
- Enynes
- Homogeneous catalysis
- Metathesis
- N-heterocyclic carbenes
- Ruthenium
ASJC Scopus subject areas
- Catalysis
- Organic Chemistry