Asymmetric Construction of the Core of C₆, C₇-Epoxy Daphnane Diterpenoid Orthoesters

Abstract

Asymmetric construction of the core of C6, C7-epoxy daphnane diterpenoid orthoesters is developed through a convergent synthetic strategy. The salient features include a diastereoselective nucleophilic assembly of two bulky cyclic fragments, an oxidative cleavage/transesterification/aldol cascade to fashion the seven-membered ring, and a base-mediated transesterification/retro-aldol/aldol/epoxidation cascade to install the epoxy moiety with proper stereochemistry.