Enantioselective de novo construction of 3‑oxindoles via organocatalyzed formal 3 + 2 annulation from simple arylamines

Abstract The de novo construction of enantioenriched 3-hydroxyindolenines and 3-oxindoles from easily available starting materials has been highly desired. Herein, an enantioselectively intermolecular direct 3 + 2 annulation of aryl amine with 2,3-diketoesters to construct 3-hydroxyindolenines with a chiral tertiary alcohol has been disclosed. The results of control experiments and DFT calculation revealed that π − π interaction plays a pivotal role in the enantioselectivity-determining process of 3 + 2 annulation. The following unusual concerted 1,2-ester migration provides a family of chiral 3-oxindoles in good to excellent yields with excellent enantioselectivity.