Intramolecular Oxidative Cyclization of Alkenes and Nitriles with Nickel(0)
| Autor: | Masato Ohashi, Masashi Ikawa, Sensuke Ogoshi |
|---|---|
| Rok vydání: | 2011 |
| Předmět: |
Oxidative cyclization
Organic Chemistry chemistry.chemical_element Medicinal chemistry Oxidative addition Inorganic Chemistry Benzonitrile chemistry.chemical_compound Nickel chemistry Yield (chemistry) Intramolecular force Organic chemistry Lewis acids and bases Physical and Theoretical Chemistry After treatment |
| Zdroj: | Organometallics. 30:2765-2774 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/om2001603 |
| Popis: | The use of Me2AlCl as an additive was found to allow the oxidative addition of the Ar–CN bond in 2-(2-methylallyl)benzonitrile on nickel(0) in the presence of PnBu3, giving a trans-arylnickelcyanide complex. In contrast, in the presence of PCy3, the intramolecular oxidative cyclization on nickel(0) took place to afford a nickeladihydropyrrole. Without the addition of Me2AlCl, the quantitative generation of an η2:η2-5-ene-nitrile Ni(0) species, which was definitely converted to the nickeladihydropyrrole after treatment with Me2AlCl, was observed. In addition, TfOH also promoted the oxidative cyclization of the η2:η2-5-ene-nitrile complex to yield the corresponding five-membered aza-nickelacycle. A similar intramolecular oxidative cyclization occurred when 2-allylbenzonitrile was used in the presence of a Lewis acid, such as Me2AlCl, Me2AlOTf, and Me3SiOTf, or of TfOH to give the corresponding nickeladihydropyrroles in quantitative yield. The molecular structures of a series of nickeladihydropyrroles were u... |
| Databáze: | OpenAIRE |
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