Abstract

   1,7-Enynes usually undergo cyclizative double functionalization. Herein, we report a conceptual radical-based non-cyclizative linear remote double functionalization of enynes. Different from classic facile cyclizations involving two unsaturated carbon-carbon bonds, the alkyl radical generated in situ undergoes the hydrogen atom transfer with the propargylic C-H bond to generate a propargylic radical via a highly chemo- & regio-selective radical addition with the C=C bond over the C≡C bond, which would be in equilibrium with an allenyl radical. Subsequent exclusive trapping with TMSCN afforded a variety of CF₃-contained allenenitriles tolerating many functional groups with great synthetic potentials in the presence of copper catalyst. In addition to 1,5-hydrogen atom transfer, 1,6-hydrogen atom transfer and even 1,7-hydrogen atom transfer have also been observed. This protocol opens a new dimension for the reactions of compounds with multiple unsaturated units.