Stereoselective carbon?carbon bond formation is one of the most important types
of bond construction in organic chemistry. A mild and acid free catalyst system for the
hydrovinylation reaction utilizing a cationic, ruthenium center is described. A catalytic
amount of RuHCl(CO)(PCy3)2 (2) activated with AgOTF or AgSbF6 at room
temperature was found to be an effective catalyst system for the hydrovinylation of
vinylarenes and the intramolecular hydrovinylation (IHV) of 1,6-dienes.
Vinylarenes with both electron-donating and electron-withdrawing substituents
reacted with ethylene at room temperature to provide the desired 3-arylbutenes in
moderate to excellent yield (60-99%) under mild reaction conditions, while the IHV
reaction of 1, 6 dienes provided greater than 90% of product conversion. We also
developed the first hydrovinylation catalyst containing a chelating, bidentate phosphine
ligand that provides the desired product.
Our ruthenium-based catalytic system has also proven to give an appealing
reactivity profile in favor of the desired arylbutenes without promoting undesirable
oligomerization and isomerization.
| Identifer | oai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-2009-08-2929 |
| Date | 14 January 2010 |
| Creators | Sanchez, Richard P., Jr |
| Contributors | Connell, Brian T. |
| Source Sets | Texas A and M University |
| Language | en_US |
| Detected Language | English |
| Type | Book, Thesis, Electronic Thesis |
| Format | application/pdf |
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