Abstract
Tsuji found a reaction that acylsilane can act as a good reagent of acylation for allylester activated by a Pd complex. Detailed experimental studies proved the reaction does not proceed without trifluoroacetic acid instead of a simple acid such as acetic acid. As the reaction is very interesting and important to obtain α,β-unsaturated ketones, the mechanism of the reaction has not understood. In the present study, we investigated the mechanism of the reaction in detail by use of Density Functional Theory (DFT) calculations at the B3LYP/LANL2DZ level of theory. It was confirmed that the reaction proceeds via a TS with a trigonal bipyramid geometry around the trimethylsillyl fragment in the Pd complex. The stability of the binuclear Pd complex, which is a precursor for the catalytic reaction, is the key for importance of trifluoroacetic acid.
