Copper-Photocatalyzed Contra-Thermodynamic Isomerization of Polarized Alkenes

The contra-thermodynamic isomerization of alpha- and beta-substituted cinnamate derivatives catalyzed by the Cu(OAc)(2)/rac-BINAP complex under blue light irradiation is reported. The use of an oxazolidinone template, which favored the complexation of the copper catalyst to the substrate, allowed the E -> Z isomerization of the catalytically formed chromophore under simple and robust reaction conditions in good to excellent ratios. The mechanism of this process based on the transient formation of a chromophore was also studied.