613670-59-0Relevant articles and documents
Room-Temperature Benzylic Alkylation of Benzylic Carbonates: Improvement of Palladium Catalyst and Mechanistic Study
Kuwano, Ryoichi,Yokogi, Masashi,Sakai, Ken,Masaoka, Shigeyuki,Miura, Takashi,Won, Sungyong
, p. 1568 - 1579 (2019/09/04)
The palladium catalyst for the nucleophilic substitution of benzyl carbonates was improved by using 1,1′-bis(diisopropylphosphino)ferrocene (DiPrPF) as the ligand. The [Pd(η3-C3H5)(cod)]BF4-DiPrPF catalyst allows the benzylic substitution with soft carbanions to proceed even at 30 °C, affording the desired products in high yields (up to 99% yield). Thermally unstable pyridylmethyl esters are employable as the electrophilic substrates for the benzylic alkylation with the improved catalyst. Furthermore, we investigated the mechanism of the catalytic benzylic alkylation by means of DiPrPF ligand. The palladium(0) complex bearing DiPrPF activates the benzylic C-O bond to form the (benzyl)palladium(II) intermediate at room temperature. The coordination mode of the benzyl ligand would be equilibrium between the η1- and η3-manner. The nucleophile would preferentially react with the η3-benzyl ligand to give the desired product.
Palladium-catalyzed benzylation of active methine compounds without additional base: Remarkable effect of 1,5-cyclooctadiene
Kuwano, Ryoichi,Kondo, Yutaka
, p. 3545 - 3547 (2007/10/03)
(Chemical Equation Presented) The palladium complex prepared from DPPF and Cp(η3-C3H5)Pd is an effective catalyst for the alkylation of active methine compounds with benzylic carbonates under neutral conditions. The additi
