TBHP/I2 Synergistically Promoted Three-Component Reaction of Isatins, Amines and Methylhetarenes: Transition-Metal-Free Access to 2-Hetarylquinazolin-4(3H)-ones

A TBHP/I₂ synergistically promoted three-component reaction of readily available isatins, amines, and methylhetarenes has been established. This transition-metal-free approach provides a concise and practical pathway for the assembly of structurally novel 2-hetarylquinazolin-4(3H)-ones, featuring a wide substrate scope and excellent functional group tolerance. Mechanistic investigations revealed that the TBHP-mediated Baeyer-Villiger-type rearrangement of isatins and the I₂-promoted sp³ C-H functionalization of methylhetarenes constituted crucial steps within the reaction sequences. Furthermore, gram-scale synthesis and late-stage modification of the resulting products were successfully implemented.