Asymmetric Bisvinylogous Aldolation of Aldehydes via 2-Oxonia-Cope Rearrangement Enabling Total Stereochemical Control

Highly stereoselective 2-oxonia-Cope rearrangement reactions between newly designed bisvinylogous aldolation synthons and aldehydes, which can provide epsilon-hydroxy-alpha,beta,gamma,delta-unsaturated esters with excellent enantioselectivities, as well as with unprecedented E- and Z-selectivities without regioselectivity issues, are described.