We have previously clarified that the strongly electron-withdrawing CF3 group nicely affected the base-mediated proton shift of CF3-containing propargylic or allylic alcohols to afford the corresponding a,b-unsaturated or saturated ketones, respectively, which was applied this time to the Claisen rearrangement after O-allylation of the allylic alcohols with a CF3 group, followed by isomerization to the corresponding allyl vinyl ethers via the proton shift, enabling the desired rearrangement in a tandem fashion, or in a stepwise manner, the latter of which was proved to have attained an excellent diastereoselectivity with the aid of a palladium catalyst.

We have previously clarified that the strongly electron-withdrawing CF3 group nicely affected the base-mediated proton migration reactions of CF3-containinig propargylic or allylic alcohols to afford the corresponding a,b-unsaturated or saturated ketones, respectively, which was applied this time to the Claisen rearrangement after O-allylation of the allylic alcohols, followed by isomerization to the corresponding allyl vinyl ethers, enabling the desired rearrangement in a tandem fashion, or in a stepwise manner where a palladium catalyst attained an excellent diastereoselectivity.