We report a detailed synthetic and mechanistic study of an unusual bifunctional, sequential heteroDiels-Alder/ring-opening reaction in which chiral, metal complexed ketene enolates react with oquinones to afford highly enantioenriched, α-hydroxylated carbonyl derivatives in excellent yield. A number of Lewis acids were screened in tandem with cinchona alkaloid derivatives; surprisingly, trans-(Ph 3 P) 2 PdCl 2 was found to afford the most dramatic increase in yield and rate of reaction. A series of Lewis acid binding motifs were explored through molecular modeling, as well as IR, UV and NMR spectroscopy. Our observations document a fundamental mechanistic "switch" -namely the formation of a tandem Lewis base/Lewis acid activated metal enolate in preference to a metalcoordinated quinone species (as observed in other reactions of o-quinone derivatives). This new method was applied to the syntheses of several pharmaceutical targets, each of which was obtained in high yield and enantioselectivity.