Reported herein is an inverse-electron-demand oxa-Diels-Alder reaction that is remotely β,γ-regioselective with β,γ-unsaturated amides and β,γ-unsaturated-α-ketoesters using a bifunctional catalyst. It can provide different kinds of dihydropyrans bearing three subsequent chiral carbon centers in good to high yield (61-99%) and with complete enantioselectivity (99 to >99% ee). Furthermore, a larger-scale experiment confirmed the reliability of the current reaction, and further effective transformation of the product has been realized.