25975-32-0Relevant academic research and scientific papers
α-Umpolung of Ketones via Enol Cation Radicals. Mechanistic and Synthetic Aspects
Schmittel, Michael,Levis, Michael
, p. 1935 - 1938 (2007/10/02)
The novel α-Umpolung of ketones via intermediate enol cation radicals has been explored mechanistically and tested for different nucleophiles that are compatible to the oxidative conditions.The rate of the reaction was determined indicating that enolizati
Mechanistic Change in Acid-Catalyzed Hydrolysis of Silyl Vinyl Ethers
Novice, Marilyn H.,Seikaly, Hani R.,Seiz, Annette D.,Tidwell, Thomas T.
, p. 5835 - 5838 (2007/10/02)
tert-Butyldimethylsilyl vinyl ethers t-BuMe2SiOCR=CH2 hydrolyze in 50percent CH3CN - H2O with general and specific acid catalysis and a linear dependence of log kH+ on ?p+(R), indicating that the reaction occurs with rate-determing proton transfer to carbon (the ADE2 mechanism).By contrast the rates of trimethylsilyl vinyl ethers Me3SiOCR=CH2 are not correlated by ?p+(R) but still depend on proton and general acid concentrations.Nucleophilic attack on silicon is implicated in the rate-determing step of the latter compounds, and the possibilities for the details of this process are considered.
