Nucleophilic Reactivities of Silyl Ketene Acetals and Silyl Enol Ethers Containing (C6F5)3SiO and (C6H5)3SiO Groups Full article
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European Journal of Organic Chemistry
ISSN: 1434-193X , E-ISSN: 1099-0690 |
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Output data | Year: 2005, Volume: 2005, Number: 9, Pages: 1760-1764 Pages count : 5 DOI: 10.1002/ejoc.200400706 | ||||
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Abstract:
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 k2) 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.
Cite:
Dilman A.D.
, Mayr H.
Nucleophilic Reactivities of Silyl Ketene Acetals and Silyl Enol Ethers Containing (C6F5)3SiO and (C6H5)3SiO Groups
European Journal of Organic Chemistry. 2005. V.2005. N9. P.1760-1764. DOI: 10.1002/ejoc.200400706 Scopus OpenAlex
Nucleophilic Reactivities of Silyl Ketene Acetals and Silyl Enol Ethers Containing (C6F5)3SiO and (C6H5)3SiO Groups
European Journal of Organic Chemistry. 2005. V.2005. N9. P.1760-1764. DOI: 10.1002/ejoc.200400706 Scopus OpenAlex
Identifiers:
Scopus: | 2-s2.0-18744376580 |
OpenAlex: | W2098235972 |