Total Synthesis of the Diterpenes (+)-Randainin D and (+)-Barekoxide via Photoredox-Catalyzed Deoxygenative Allylation

Abstract

We report the first enantioselective total synthesis of diterpenoid randainin D, which possesses a hydroazulenone core with a β-substituted butenolide moiety on the cycloheptane ring. The trans-5/7 ring system was formed via a highly challenging ringclosing metathesis delivering the tetrasubstituted cycloheptenone. The butenolide moiety was installed via a novel deoxygenative allylation under Ir-photoredox catalysis, employing methyl oxalate as a red/ox tag. Moreover, the developed allylation was successfully utilized in the 7-step total synthesis of (+)-barekoxide. This study suggests that this deoxygenative allylation method is a promising strategy for the formation of Cq−C(sp 3 ) bonds (Cq = quaternary center) in the context of natural product synthesis.