Despite tremendous advances in enantioselective catalysis of the Diels-Alder reaction, the use of simple alpha,beta-unsaturated esters, one of the most abundant and useful class of dienophiles, is still severely limited in scope due to their low reactivity. We report here a catalytic asymmetric Diels-Alder methodology for a large variety of alpha,beta-unsaturated methyl esters and different dienes based on extremely reactive silylium imidodiphos-phorimidate (IDPi) Lewis acids. Mechanistic insights from accurate domain-based local pair natural orbital coupled-cluster (DLPNO-CCSD (T)) calculations rationalize the catalyst control and stereochemical outcome.