
TY  - JOUR
A1  - Blair, IA 
A1  - Bowie, JH 
T1  - Ion Cyclotron Resonance Studies of Alkylsilyl Ions. II. The Reactions of Ketones, Carboxylic Acids and Esters with the Trimethylsilyl Cation
JF  - Australian Journal of Chemistry
JO  - Aust. J. Chem.
Y1  - 1979
VL  - 32
IS  - 6
SP  - 1389
EP  - 1393
KW  - 
UR  - https://doi.org/10.1071/CH9791389 
N2  - 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+. 
ER  -

