Chiral Isothiourea‐Catalyzed Acylative Dynamic Kinetic Resolution of 3‐Hydroxyphthalides for Enantioselective Synthesis of Phthalidyl Esters

Comprehensive Summary Phthalides serve as core structures pervasive in a wide array of natural products and drug molecules, which display a diverse array of biological activities. We report herein a highly efficient dynamic kinetic resolution of 3‐hydroxyphthalides by chiral isothioureas (ITUs) catalyzed asymmetric acylation, facilitating the effective synthesis of a variety of chiral phthalidyl esters with good yields and enantioselectivities. Notably, this reaction features mild reaction conditions, expansive substrate scope as well as good functional group compatibility. In addition, the practicality of this method is underscored by the large‐scale synthesis, reduced catalyst loading experiment and the synthesis of the chiral phthalidyl ester prodrug.