Palladium-catalyzed reaction of γ-silylated allyl acetates proceeding through 1,2-shift of a substituent on silicon

The palladium-catalyzed reaction of γ-silylated allyl acetates with water in the presence of CsF induces a previously unprecedented 1,2-shift of a substituent on silicon to produce allylsilanes in situ. The catalytic activity of the palladium increased when using an electron-poor phosphine ligand possessing fluorinated substituents. Further investigation of the reaction revealed that the approximate order of the migratory aptitude of groups from silicon was PhC≡C, allyl > Bn > Ph, vinyl > alkyl (Me, Et). A density functional theory study was employed to explore the reaction mechanism. Finally, the Hosomi–Sakurai-type allylation of aldehydes with in situ-generated α,γ-disubstituted allylsilanes was also investigated. [Display omitted] •Pd-catalyzed reaction of γ-silylated allyl acetates induced 1,2-shift of a substituent on silicon.•The key to the success of this reaction is the use of a fluorinated phosphine ligand.•A density functional theory study was employed to explore the reaction mechanism.•The utility of this method was demonstrated by Hosomi–Sakurai-type allylation of aldehydes.