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

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‐ion sequence, allowing direct and versatile protocols for stereoselective construction of 1‐indanone scaffolds with high functional group tolerance and wide substrate scope. 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.