P−C Bond Activation Chemistry: Evidence for 1,1-Carboboration Reactions Proceeding with Phosphorus−Carbon Bond Cleavage
| Autor: | Gerhard Erker, Olga Ekkert, Roland Fröhlich, Gerald Kehr |
|---|---|
| Rok vydání: | 2011 |
| Předmět: |
Boron Compounds
Models Molecular Molecular Structure Acetylene Aryl Substituent Phosphorus General Chemistry Electrophilic aromatic substitution Crystallography X-Ray Photochemistry Biochemistry Medicinal chemistry Carbon Catalysis chemistry.chemical_compound Organophosphorus Compounds Colloid and Surface Chemistry chemistry Intramolecular force Lewis acids and bases Derivative (chemistry) Bond cleavage |
| Zdroj: | Journal of the American Chemical Society. 133:4610-4616 |
| ISSN: | 1520-5126 0002-7863 |
| Popis: | A series of diarylphosphinyl-substituted acetylenes of the type (aryl)(2)P-C≡C-R (aryl = phenyl or mesityl, R = Ph or n-propyl) react with the strongly Lewis acid reagent B(C(6)F(5))(3) in toluene at elevated temperatures (70-105 °C) to give the 1,1-carboboration products 4. Treatment of bis(diphenylphosphinyl)acetylene with B(C(6)F(5))(3) under analogous conditions proceeded with phosphinyl migration to yield the 1,1-carboboration product 4d, bearing a geminal pair of Ph(2)P substituents at one former acetylene carbon atom and a C(6)F(5) substituent and the remaining -B(C(6)F(5))(2) group at the other. Prolonged thermolysis of 4d resulted in an intramolecular aromatic substitution reaction by means of Ph(2)P attack on the adjacent C(6)F(5) ring to yield the zwitterionic phospha-indene derivative 7. The compounds 4a, 4c, 4d, and 7 were characterized by X-ray diffraction. |
| Databáze: | OpenAIRE |
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