The reaction of N-acetyl perfluoroalkyl substituted 2(1H) pyridones ( 7) with dimethylacetylenedicarboxylate (DMAD) on neutral alumina under solvent free microwave irradiation conditions extended to undergo an inverse electron demand hetero Diels–Alder reaction, however resulted exclusively in E, Z isomers (3:1) of Michael-type N-adducts ( 8). The similar reaction in case of 7a under thermal and photochemical conditions also gave the same products.