Rationally Designed Chiral Synthons Enabling Asymmetric Z- and E‑Selective Vinylogous Aldol Reactions of Aldehydes

In a conceptually different approach, highly stereoselective 2-oxonia-Cope rearrangement reactions between rationally designed nonracemic vinylogous aldolation synthons and aldehydes are described to provide δ-hydroxy-α,β-unsaturated esters with excellent enantioselectivities and, for the first time, unprecedented Z- and E-selectivities without the regioselectivity issue.