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The palladium-on-charcoal-catalyzed chemo-, regio-, and stereoselective 1,4-hydrosilylation and transfer hydrogenation reactions of α,β-unsaturated aldehydes and ketones with triethylsilane have been investigated with a combination of experimental and theoretical methods. The reaction mechanism has been studied experimentally by monitoring the reactions by 1H NMR from aliquots withdrawn from the stirred reaction mixtures, labeling experiments, and control experiments. Our density functional theory results indicate that both aforementioned reactions are initiated with a dissociative adsorption of the triethylsilane on the palladium catalyst. In the hydrosilylation reaction, the α,β-unsaturated aldehyde or cyclic ketone is adsorbed on the silyl-covered palladium catalyst, where it is first irreversibly O-silylated and then reduced by a hydride addition to the 4-position. The O-silylation step has a low barrier, and it essentially freezes the solution-phase s-trans:s-cis conformer ratio in the form of enol s...

Pd/C-Catalyzed Hydrosilylation of Enals and Enones with Triethylsilane: Conformer Populations Control the Stereoselectivity