A tert-butyl hydroperoxide-promoted multicomponent reaction of isatins, sodium chlorodifluoroacetate, and aliphatic amines has been disclosed. This reaction provides a facile and practical approach for producing functionalized 2-aminobenzoxazinones under transition-metal-free conditions. The preliminary mechanism indicates that the reaction probably proceeds through an intermolecular cyclization process between isatoic anhydride and imine cation intermediates. Notably, the carbon atom at the 2-position of the benzoxazinone ring originated from an unusual quadruple cleavage of sodium chlorodifluoroacetate.