
%0 Journal Article
%A Blair, IA 
%A Bowie, JH 
%T Ion Cyclotron Resonance Studies of Alkylsilyl Ions. II. The Reactions of Ketones, Carboxylic Acids and Esters with the Trimethylsilyl Cation
%J Australian Journal of Chemistry
%D 1979/06/01
%V 32
%N 6
%P 1389-1393
%K 
%R https://doi.org/10.1071/CH9791389
%U https://www.publish.csiro.au/paper/CH9791389 
%X Nucleophilic attack of a ketone, carboxylic acid or ester at the electrophilic centre of the trimethylsilyl cation (Me,Si+) produces a 1:1 adduct. This adduct does not decompose in the case of ketones. Acid adducts decompose primarily by loss of methane, but a minor pathway exists which involves elimination of a ketene. Ester adducts fragment primarily by this latter process through a four-membered transition state. The transfer of hydrogen was shown to arise solely from the acyl group and was shown to proceed with a small deuterium isotope effect. Further decomposition of the resulting ion by loss of methane provides unequivocal proof that esters react predominantly through the alkyl oxygen with the Lewis acid Me3Si+. 
