222531-32-0Relevant articles and documents
Nucleophilic reactivities of silyl ketene acetals and silyl enol ethers containing (C6F5)3SiO and (C6H 5)3SiO groups
Dilman, Alexander D.,Mayr, Herbert
, p. 1760 - 1764 (2005)
The kinetics of the reactions of tris(pentafluorophenyl)silyl and triphenylsilyl ketene acetals and enol ethers with benzhydrylium cations have been measured photometrically. The second-order rate constants (log k 2) have been used to determine the nucleophilicity parameters of these π systems, which provide a quantitative comparison of their reactivities with those of other types of nucleophiles. A change from, trimethylsilyloxy to triphenylsilyloxy reduces reactivity by only a factor of ten, while replacement of triphenylsilyloxy with tris(pentafluorophenyl)silyloxy decreases the nucleophilicity of the enolate C=C double bond by three to four orders of magnitude. The cation-stabilizing ability of the tris(pentafluorophenyl)silyloxy group is thus similar to that of a methyl group. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005.