The First Efficient Catalyzed Acylation of Allylsilanes1

In the presence of catalytic amounts (5 mol %) of BiCl 3 −3 NaI or BiCl 3 −1.5 ZnI 2 acylation of allyltrimethylsilane by a variety of acyl chlorides (RCOCl with R = Me, Et, i- Pr, t- Bu, Ph, 1-adamantyl) proceeded rapidly at room temperature without decarbonylation of the acyl chloride. Allyl ketones were usually obtained in high yield with little or no isomerization to 1-propenyl ketones. Using (3-methylbut-2-enyl)trimethylsilane and Me 2 C CHCOCl, Artemisia ketone was synthesized in nearly quantitative yield after complete allylic transposition.