Enantioselective lactonization catalyzed by chiral N-heterocyclic carbenes enables access to inherently chiral eight-membered lactones.

Chiral saddle-shaped molecules are an emerging class of compounds with significant potential in both materials science and medicinal chemistry. However, their broader application has been hindered by limited synthetic accessibility. Herein, we report a metal-free, organocatalytic protocol for the oxidative lactonization of readily available aldehydic derivatives, enabling the efficient synthesis of chiral saddle-shaped lactones. The method exhibits excellent enantiocontrol, high yields (nearly quantitative), and broad functional group tolerance, as demonstrated by the synthesis of a small library of structurally diverse products. The scalability of the reaction further underscores its practical utility. Moreover, computational studies provide mechanistic insight into the origin of enantioinduction in N-heterocyclic carbene-catalyzed lactonization.