Total synthesis of (+)-bourgeanic acid utilizing o-DPPB-directed allylic substitution.

The lichen metabolite (+)-bourgeanic acid has been synthesized utilizing a new strategy for the construction of propionate motifs relying on the o-DPPB-directed copper-mediated allylic substitution. This synthesis features the o-DPPB-directed allylic substitution employing a chiral Grignard reagent, Sharpless asymmetric epoxidation, and reductive epoxide ring opening with a higher order dimethylcuprate to set the four stereogenic centers of the aliphatic depside.