Ca(NTf2)2/HFIP‐Mediated Direct and Mild Rearrangement of Cyclopropyl Carbinols to E‐Homoallylic Triflimides

Abstract Unsaturated triflimides, especially homoallylic triflimide species, are rarely assessable. Herein, we disclose a Ca(NTf 2 ) 2 /HFIP‐mediated direct chemo‐, regio‐, and stereoselective rearrangement of diverse cyclopropyl carbinols to exclusive E ‐homoallylic triflimides in moderate to excellent yields at room temperature, in which Ca(NTf 2 ) 2 was used as both the OH activator and the triflimide anion source. This protocol shows excellent substrate/functional group tolerance with an emphasis on those substrates bearing strong electron‐withdrawing functional groups.