Base-Mediated Claisen Rearrangement of CF3-Containing Bisallyl Ethers |
| |
Authors: | Yoko Hamada Rio Matsunaga Tomoko Kawasaki-Takasuka Takashi Yamazaki |
| |
Institution: | Division of Applied Chemistry, Institute of Engineering, Tokyo University of Agriculture and Technology, 2-24-16 Nakamachi, Koganei 184-8588, Japan; (Y.H.); (R.M.); (T.K.-T.) |
| |
Abstract: | 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 α,β-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. |
| |
Keywords: | Claisen rearrangement isomerization trifluoromethyl Cieplak rule |
|
|