Metal‐Free Radical Annulation‐Hydrofunctionalization of 1,6‐Enynes for Stereoselective Synthesis of (E)‐1‐Indanones

Abstract Two metal‐free radical annulation‐hydrofunctionalization cascades of 1,6‐enynes have been established, enabling the complete stereoselectivity to access a wide range of functionalized ( E )‐1‐indanones with moderate to good yields. The reaction pathways involve in situ‐ generated P‐ or S ‐centered radical‐triggered α,β ‐conjugated addition/5‐ exo‐dig cyclization/H‐abstraction sequence, allowing direct and versatile protocols for stereoselective construction of 1‐indanone scaffolds with high functional group tolerance and wide substrate scope.