γ,d-Epoxy-α,β-enoates contain three different electrophilic functional groups including the epoxide, olefin and ester functionalities, which provide opportunities for S_N2-epoxide opening, allylic substitution, and 1,4- conjugated addition. The chemo-, regio and stereoselective reactions of γ,d-epoxy-α,β-enoates could provide a versatile template for acyclic stereoselection and for stereocontrolled heterocyclic synthesis.

Oxirane cleavage with MgBr₂ according to an established procedure afforded an allylic bromide suitable for sequential allylic substitution reactions. The epoxide could also be cleaved with AcBr or AcCl to afford the γ-acetoxyl-allylic halides, which underwent a copper-mediated allylic S_N2' substitution to afford α-substituted allylic acetates. Primary and secondary amines undergo conjugate additions to the epoxy enoates in the presence of Lewis acids. Dialkylzinc reagents, in the presence of catalytical amounts of CuCN, effect allylic substitution on the vinyl oxirane (i.e. S_N2' substitution). The development of these chemoselective reactions will be described in detail and the degree of regio- and stereoselectivity for each reaction will be discussed.