Radical Carbocyclization Intercepted Reductive C−C Bond Formation Between 1,n‐Enynes or Dienes and Electron‐Poor Olefins/Alkynes

Abstract Metal hydride catalyzed hydrogen atom transfer (MHAT) reaction of 1,6‐enyne and electron‐poor alkene progresses through a radical cascade, involving ene‐yne cyclization and exocyclic C−C bond formation superseding the direct reductive olefin cross‐coupling; which is realized in the current study. The generality of this reaction manifold is demonstrated with a range of functionalized 1,6‐enyne and dienes and involving structurally distinct electron‐poor olefins and alkynes as partners. Current work unveils a merger of MHAT‐based olefin‐hydro functionalization with radical ene‐one cyclization.