Chalcogen‐Bonding‐Catalyzed Three‐Component Synthesis of Spirocyclic Enones from Sesamol, Aldehydes, and Dienes

Spirocyclic enones are vital motifs in natural products and medicinal chemistry, yet their synthesis often requires multistep procedures or prefunctionalized reactants. A metal‐ and oxidant‐free approach to the synthesis of spirocyclic enones that uses simple reactants without prefunctionalization remains underdeveloped. Here we report a chalcogen‐bonding‐catalyzed three‐component assembly of sesamol, aldehydes, and dienes, enabling efficient access to diverse spirocyclic enones. This method employs cooperative chalcogen‐bonding and anion‐binding interactions to activate the aldehyde and sesamol reactants, affording the spirocyclic products in reasonable yields with high diastereoselectivity. Chalcogen bonding has emerged as a new concept in catalysis, but its application in multicomponent reactions remains largely unexplored. This work demonstrates its implementation in a three‐component transformation, offering a promising strategy for constructing complex molecular scaffolds.