Formation of β-Ruthenium-Substituted Enones from Propargyl Alcohols
| Autor: | Ilia A. Guzei, Xiangdong Jiao, Charles P. Casey |
|---|---|
| Rok vydání: | 2010 |
| Předmět: |
chemistry.chemical_classification
Stereochemistry Dimer Organic Chemistry chemistry.chemical_element Alkyne Propargyl alcohol Medicinal chemistry Ruthenium Inorganic Chemistry chemistry.chemical_compound chemistry Intramolecular force Yield (chemistry) Propargyl Kinetic isotope effect Physical and Theoretical Chemistry |
| Zdroj: | Organometallics. 29:4829-4836 |
| ISSN: | 1520-6041 0276-7333 |
| Popis: | The reaction of the dienone ruthenium dicarbonyl dimer {[2,5-Ph-3,4-Tol(η5-C4CO)]Ru(CO)2}2 (7) with propargyl alcohol at room temperature gave a high yield of β-ruthenium-enal (E)-[2,5-Ph-3,4-Tol(η5-C4COH)]Ru(CO)2(CH═CHCHO) (8E), which was characterized spectroscopically and by X-ray crystallography. Reaction of 7 with pent-2-yn-1-ol led to the kinetic formation of the E-isomer (E)-[2,5-Ph-3,4-Tol(η5-C4COH)]Ru(CO)2[C(CH2CH3)═CHCHO] (10E-Et), which isomerized to an equilibrium mixture of Z- and E-isomers upon heating. The intramolecular nature of the 1,2-hydrogen shifts involved in these reactions was established by the absence of crossover products in the reaction of 7 with a mixture of PhC≡CCH2OH and PhC≡CCD2OH. A primary deuterium isotope effect (kH/kD ≈ 11) was seen on the product-forming step in the reaction of 7 with PhC≡CCHDOH. The reaction of PhC≡CCH3 with 7 produced the alkyne complex [2,5-Ph2-3,4-Tol2(η5-C4COH)]Ru(CO)2(η2-PhC≡CCH3) (14). The key step in the mechanism of the reaction of 7 with pro... |
| Databáze: | OpenAIRE |
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