ORGN 599 |
Modular assembly and applications of electron-rich phosphine ligands from fluorinated aromatic building blocks
| Shahla Yekta and Andrei K. Yudin. Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, ON M5S 3H6, Canada |
We have shown that diphenyl and dialkyl phosphines can selectively replace fluorine atoms at the 7-position of polyfluorinated naphthol and binaphthol building blocks (82% and 64% yield for 1a and 1b respectively). Surprisingly, the phosphorus center remains sufficiently electron-rich despite the presence of the remaining fluorine atoms. For instance, the 31P-77Se coupling constant for 1b (729 Hz) is very close to the well-known 2-(dicylcohexylphosphino) biphenyl (2, 732 Hz). Further nucleophilic modification with nitrogen-, oxygen-, phosphorus-, and sulphur- containing fragments has enabled us to generate diverse heterocyclic catalyst precursors. The resulting electron-rich phosphines have been used in late transition metal-catalyzed transformations and nucleophilic catalysis such as the Baylis-Hillman reaction. These and related results will be discussed. |
| |
|
Bioorganic, Molecular Recognition, Asymmetric Reactions and Syntheses
11:00 AM-1:00 PM, Wednesday, September 10, 2003 Javits Convention Center -- Hall 1B/1C, Poster
Division of Organic Chemistry
The 226th ACS National Meeting, New York, NY, September 7-11, 2003
|