To study the intramolecular Diels–Alder cycloadditon of 2H-chromen-2-one as a diene, a series of chiral N-allyl-N-benzylamides that contain a 2H-chromen-2-one moiety were designed for the synthesis of benzo[f]isoindol-1-ones via an intramolecular Diels–Alder and a subsequent retro-Diels–Alder cycloaddition with the expulsion of CO2. Both the yield (80%–89%) and absolute stereocontrol of the tandem reaction were high when an electron-withdrawing group was attached to the dienophile. The double bond in the styrene substructure remained in the products could be further derivatized by dihydroxylation.A series of chiral N-allyl-N-benzylamides that contain a 2H-chromen-2-one moiety were designed for the synthesis of benzo[f]isoindol-1-ones via an intramolecular Diels–Alder and a subsequent retro-Diels–Alder reaction with the expulsion of CO2. Both the yield (80%–89%) and absolute stereocontrol of the tandem reaction were high when an electron-withdrawing group was attached to the dienophile.